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Sample records for lanthanide doped ceria

  1. Incubational domain characterization in lightly doped ceria

    SciTech Connect

    Li Zhipeng; Mori, Toshiyuki; John Auchterlonie, Graeme; Zou Jin; Drennan, John

    2012-08-15

    Microstructures of both Gd- and Y-doped ceria with different doping level (i.e., 10 at% and 25 at%) have been comprehensively characterized by means of high resolution transmission electron microscopy and selected area electron diffraction. Coherent nano-sized domains can be widely observed in heavily doped ceria. Nevertheless, it was found that a large amount of dislocations actually exist in lightly doped ceria instead of heavily doped ones. Furthermore, incubational domains can be detected in lightly doped ceria, with dislocations located at the interfaces. The interactions between such linear dislocations and dopant defects have been simulated accordingly. As a consequence, the formation mechanism of incubational domains is rationalized in terms of the interaction between intrinsic dislocations of doped ceria and dopant defects. This study offers the insights into the initial state and related mechanism of the formation of nano-sized domains, which have been widely observed in heavily rare-earth-doped ceria in recent years. - Graphical abstract: Interactions between dislocations and dopants lead to incubational domain formation in lightly doped ceria. Highlights: Black-Right-Pointing-Pointer Microstructures were characterized in both heavily and light Gd-/Y-doped ceria. Black-Right-Pointing-Pointer Dislocations are existed in lightly doped ceria rather than heavily doped one. Black-Right-Pointing-Pointer Interactions between dislocations and dopant defects were simulated. Black-Right-Pointing-Pointer Formation of dislocation associated incubational domain is rationalized.

  2. Optimization of ionic conductivity in doped ceria

    PubMed Central

    Andersson, David A.; Simak, Sergei I.; Skorodumova, Natalia V.; Abrikosov, Igor A.; Johansson, Börje

    2006-01-01

    Oxides with the cubic fluorite structure, e.g., ceria (CeO2), are known to be good solid electrolytes when they are doped with cations of lower valence than the host cations. The high ionic conductivity of doped ceria makes it an attractive electrolyte for solid oxide fuel cells, whose prospects as an environmentally friendly power source are very promising. In these electrolytes, the current is carried by oxygen ions that are transported by oxygen vacancies, present to compensate for the lower charge of the dopant cations. Ionic conductivity in ceria is closely related to oxygen-vacancy formation and migration properties. A clear physical picture of the connection between the choice of a dopant and the improvement of ionic conductivity in ceria is still lacking. Here we present a quantum-mechanical first-principles study of the influence of different trivalent impurities on these properties. Our results reveal a remarkable correspondence between vacancy properties at the atomic level and the macroscopic ionic conductivity. The key parameters comprise migration barriers for bulk diffusion and vacancy–dopant interactions, represented by association (binding) energies of vacancy–dopant clusters. The interactions can be divided into repulsive elastic and attractive electronic parts. In the optimal electrolyte, these parts should balance. This finding offers a simple and clear way to narrow the search for superior dopants and combinations of dopants. The ideal dopant should have an effective atomic number between 61 (Pm) and 62 (Sm), and we elaborate that combinations of Nd/Sm and Pr/Gd show enhanced ionic conductivity, as compared with that for each element separately. PMID:16478802

  3. Ceria co-doping: synergistic or average effect?

    PubMed

    Burbano, Mario; Nadin, Sian; Marrocchelli, Dario; Salanne, Mathieu; Watson, Graeme W

    2014-05-14

    Ceria (CeO2) co-doping has been suggested as a means to achieve ionic conductivities that are significantly higher than those in singly doped systems. Rekindled interest in this topic over the last decade has given rise to claims of much improved performance. The present study makes use of computer simulations to investigate the bulk ionic conductivity of rare earth (RE) doped ceria, where RE = Sc, Gd, Sm, Nd and La. The results from the singly doped systems are compared to those from ceria co-doped with Nd/Sm and Sc/La. The pattern that emerges from the conductivity data is consistent with the dominance of local lattice strains from individual defects, rather than the synergistic co-doping effect reported recently, and as a result, no enhancement in the conductivity of co-doped samples is observed. PMID:24658460

  4. Nanodomain formation and distribution in Gd-doped ceria

    SciTech Connect

    Li, Zhi-Peng; Mori, Toshiyuki; Auchterlonie, Graeme John; Zou, Jin; Drennan, John

    2012-03-15

    Highlights: Black-Right-Pointing-Pointer Comprehensive investigation of nanodomain formation and distribution in Gd-doped ceria. Black-Right-Pointing-Pointer Direct experimental evidence of nanodomain formation at grain boundaries. Black-Right-Pointing-Pointer Nanodomain at grain boundaries would be another possible reason for grain boundary resistivity. -- Abstract: A comprehensive study, with a combination of diverse analytical techniques, was performed to investigate nanodomain formation and distribution in gadolinium-doped ceria. It is illustrated that the nanodomain formation, originating from the aggregation and segregation of dopant cations together with associated charge-compensating oxygen vacancies, is ubiquitous throughout doped ceria. The formation of nanodomains is not limited to bulk areas as previously reported but exists at grain boundaries as well. With enhanced ordering level, such nanodomains formed at grain boundaries will decrease the ionic conductivity as a result of hindered the mobility of oxygen vacancies in doped ceria. Particularly, the nanodomains formed at grain boundaries, with strong defect interactions due to enrichment of dopants and ordered oxygen vacancies, are suggested to be another possible reason for the grain-boundary resistance, other than the widely accepted space-charge layers.

  5. Defects clustering and ordering in di- and trivalently doped ceria

    SciTech Connect

    Li, Zhi-Peng; Mori, Toshiyuki; Zou, Jin; Drennan, John

    2013-02-15

    Graphical abstract: Display Omitted Highlights: ► Defect structures in trivalently and divalently doped ceria has been elucidated. ► Dumbbell structure is a universal basic vacancy structure in fluorite oxides. ► Electrostatic attraction dominates elastic interaction in doped ceria. ► Provide a physical picture of conductivity behavior in aliovalently doped ceria. -- Abstract: The formation and growth of defect clusters in CeO{sub 2}-M{sub 2}O{sub 3} (M = La{sup 3+}, Pr{sup 3+}, Sm{sup 3+}, Gd{sup 3+}, Dy{sup 3+}, Y{sup 3+}, Yb{sup 3+}) and CeO{sub 2}-DO (N = Cd{sup 2+}, Ca{sup 2+}, Sr{sup 2+}, Ba{sup 2+}) binary solid solutions have been comparatively studied by atomistic simulations based on energy minimization of atomic interactions. The calculation ensemble, including both divalent and trivalent dopants, shows a similar energetic tendency for defect species (dopants and associated oxygen vacancies) to aggregate and grow. The dumbbell structure has been verified as a universal vacancy structure in oxygen deficient fluorite lattice. Nevertheless, it also demonstrates different tendencies of dopant–vacancy associations that depend on dopant valence and radius. The dopant is site-selective in trivalent defect clusters correlated with dopant size. While in divalent solid solutions, clusters adopt similar dopant–vacancy locations. Furthermore, all clusters in divalently doped ceria have stronger dopant–vacancy associations/interactions compared to those in trivalent ones. As a consequence, the correlation of the dopant size as well as valence effects on oxygen-ion conductivity has been illustrated based on an ordered defect cluster model. This study thereby offers insight into the physical picture of ionic conductivity behavior experimentally obtained in aliovalently doped ceria.

  6. Lanthanide doped strontium-barium cesium halide scintillators

    SciTech Connect

    Bizarri, Gregory; Bourret-Courchesne, Edith; Derenzo, Stephen E.; Borade, Ramesh B.; Gundiah, Gautam; Yan, Zewu; Hanrahan, Stephen M.; Chaudhry, Anurag; Canning, Andrew

    2015-06-09

    The present invention provides for a composition comprising an inorganic scintillator comprising an optionally lanthanide-doped strontium-barium, optionally cesium, halide, useful for detecting nuclear material.

  7. Lanthanide-doped upconverting phosphors for bioassay and therapy

    NASA Astrophysics Data System (ADS)

    Guo, Huichen; Sun, Shiqi

    2012-10-01

    Lanthanide-doped fluorescent materials have gained increasing attention in recent years due to their unique luminescence properties which have led to their use in wide-ranging fields including those of biological applications. Aside from being used as agents for in vivo imaging, lanthanide-doped fluorescent materials also present many advantages for use in bioassays and therapy. In this review, we summarize the applications of lanthanide-doped up-converting phosphors (UCPs) in protein and gene detection, as well as in photodynamic and gene therapy in recent years, and outline their future potential in biological applications. The current report could serve as a reference for researchers in relevant fields.

  8. Disinfection effects of undoped and silver-doped ceria powders of nanometer crystallite size

    PubMed Central

    Tsai, Dah-Shyang; Yang, Tzu-Sen; Huang, Yu-Sheng; Peng, Pei-Wen; Ou, Keng-Liang

    2016-01-01

    Being endowed with an ability of capturing and releasing oxygen, the ceria surface conventionally assumes the role of catalyzing redox reactions in chemistry. This catalytic effect also makes possible its cytotoxicity toward microorganisms at room temperature. To study this cytotoxicity, we synthesized the doped and undoped ceria particles of 8–9 nm in size using an inexpensive precipitation method and evaluated their disinfecting aptitudes with the turbidimetric and plate count methods. Among the samples being analyzed, the silver-doped ceria exhibits the highest sterilization ability, yet the undoped ceria is the most intriguing. The disinfection effect of undoped ceria is moderate in magnitude, demanding a physical contact between the ceria surface and bacteria cell wall, or the redox catalysis that can damage the cell wall and result in the cell killing. Evidently, this effect is short-range and depends strongly on dispersion of the nanoparticles. In contrast, the disinfection effects of silver-doped ceria reach out several millimeters since it releases silver ions to poison the surrounding microorganisms. Additionally, the aliovalent silver substitution creates more ceria defects. The synergetic combination, silver poisoning and heterogeneous redox catalysis, lifts and extends the disinfecting capability of silver-doped ceria to a superior level. PMID:27330294

  9. Disinfection effects of undoped and silver-doped ceria powders of nanometer crystallite size.

    PubMed

    Tsai, Dah-Shyang; Yang, Tzu-Sen; Huang, Yu-Sheng; Peng, Pei-Wen; Ou, Keng-Liang

    2016-01-01

    Being endowed with an ability of capturing and releasing oxygen, the ceria surface conventionally assumes the role of catalyzing redox reactions in chemistry. This catalytic effect also makes possible its cytotoxicity toward microorganisms at room temperature. To study this cytotoxicity, we synthesized the doped and undoped ceria particles of 8-9 nm in size using an inexpensive precipitation method and evaluated their disinfecting aptitudes with the turbidimetric and plate count methods. Among the samples being analyzed, the silver-doped ceria exhibits the highest sterilization ability, yet the undoped ceria is the most intriguing. The disinfection effect of undoped ceria is moderate in magnitude, demanding a physical contact between the ceria surface and bacteria cell wall, or the redox catalysis that can damage the cell wall and result in the cell killing. Evidently, this effect is short-range and depends strongly on dispersion of the nanoparticles. In contrast, the disinfection effects of silver-doped ceria reach out several millimeters since it releases silver ions to poison the surrounding microorganisms. Additionally, the aliovalent silver substitution creates more ceria defects. The synergetic combination, silver poisoning and heterogeneous redox catalysis, lifts and extends the disinfecting capability of silver-doped ceria to a superior level.

  10. Variable temperature electrochemical strain microscopy of Sm-doped ceria

    SciTech Connect

    Jesse, Stephen; Morozovska, A. N.; Kalinin, Sergei V; Eliseev, E. A.; Yang, Nan; Doria, Sandra; Tebano, Antonello

    2013-01-01

    Variable temperature electrochemical strain microscopy has been used to study the electrochemical activity of Sm-doped ceria as a function of temperature and bias. The electrochemical strain microscopy hysteresis loops have been collected across the surface at different temperatures and the relative activity at different temperatures has been compared. The relaxation behavior of the signal at different temperatures has been also evaluated to relate kinetic process during bias induced electrochemical reactions with temperature and two different kinetic regimes have been identified. The strongly non-monotonic dependence of relaxation behavior on temperature is interpreted as evidence for water-mediated mechanisms.

  11. Synthesis and silica coating of calcia-doped ceria/mica nanocomposite by seeded polymerization technique

    NASA Astrophysics Data System (ADS)

    El-Toni, Ahmed Mohamed; Yin, Shu; Sato, Tsugio

    2006-05-01

    Calcia-doped ceria is of potential interest as an ultraviolet (UV) radiation blocking material in personal care products because of the excellent UV light absorption property and low catalytic ability for the oxidation of organic materials superior to undoped ceria. In order to reduce the oxidation catalytic activity further, calcia-doped ceria was coated with amorphous silica by means of seeded polymerization technique. Generally, nanoparticles of inorganic materials do not provide a good coverage for human skin because of the agglomeration of the particles. The platy particles are required to enhance the covering ability of inorganic materials. This can be accomplished by synthesis of calcia-doped ceria/mica nanocomposite with subsequent silica coating to control catalytic activity of calcia-doped ceria. Calcia-doped ceria/mica nanocomposite was prepared by soft solution chemical method followed by silica coating via seeded polymerization technique. Silica coated calcia-doped ceria/mica nanocomposite was characterized by X-ray diffraction, SEM, TEM, XPS and FT-IR.

  12. Coating of calcia-doped ceria with amorphous silica shell by seeded polymerization technique

    SciTech Connect

    El-Toni, Ahmed Mohamed . E-mail: el-toni@mail.tagen.tohoku.ac.jp; Yin, Shu; Yabe, Shinryo; Sato, Tsugio

    2005-07-12

    Calcia-doped ceria is of potential interest as an ultraviolet (UV) radiation blocking material in personal care products. However, its high catalytic ability for oxidation of organic materials makes it difficult to use as a sunscreen material. Therefore, calcia-doped ceria was coated with amorphous silica by means of seeded polymerization technique in order to depress its oxidation catalytic ability. The catalytic ability as well as UV-shielding ability was investigated for coated particles.

  13. Lanthanide-doped hollow nanomaterials as theranostic agents.

    PubMed

    Kang, Xiaojiao; Li, Chunxia; Cheng, Ziyong; Ma, Ping'an; Hou, Zhiyao; Lin, Jun

    2014-01-01

    The field of theranostics has sprung up to achieve personalized medicine. The theranostics fuses diagnostic and therapeutic functions, empowering early diagnosis, targeted drug delivery, and real-time monitoring of treatment effect into one step. One particularly attractive class of nanomaterials for theranostic application is lanthanide-doped hollow nanomaterials (LDHNs). Because of the existence of lanthanide ions, LDHNs show outstanding fluorescent and paramagnetic properties, enabling them to be used as multimodal bioimaging agents. Synchronously, the huge interior cavities of LDHNs are able to be applied as efficacious tools for storage and delivery of therapeutic agents. The LDHNs can be divided into two types based on difference of component: single-phase lanthanide-doped hollow nanomaterials and lanthanide-doped hollow nanocomposites. We describe the synthesis of first kind of nanomaterials by use of hard template, soft template, template-free, and self-sacrificing template method. For lanthanide-doped hollow nanocomposites, we divide the preparation strategies into three kinds (one-step, two-step, and multistep method) according to the synthetic procedures. Furthermore, we also illustrate the potential bioapplications of these LDHNs, including biodetection, imaging (fluorescent imaging and magnetic resonance imaging), drug/gene delivery, and other therapeutic applications.

  14. Gadolinia-Doped Ceria Cathodes for Electrolysis of CO2

    NASA Technical Reports Server (NTRS)

    Adler, Stuart B.

    2009-01-01

    Gadolinia-doped ceria, or GDC, (Gd(0.4)Ce(0.6)O(2-delta), where the value of delta in this material varies, depending on the temperature and oxygen concentration in the atmosphere in which it is being used) has shown promise as a cathode material for high-temperature electrolysis of carbon dioxide in solid oxide electrolysis cells. The polarization resistance of a GDC electrode is significantly less than that of an otherwise equivalent electrode made of any of several other materials that are now in use or under consideration for use as cathodes for reduction of carbon dioxide. In addition, GDC shows no sign of deterioration under typical temperature and gas-mixture operating conditions of a high-temperature electrolyzer. Electrolysis of CO2 is of interest to NASA as a way of generating O2 from the CO2 in the Martian atmosphere. On Earth, a combination of electrolysis of CO2 and electrolysis of H2O might prove useful as a means of generating synthesis gas (syngas) from the exhaust gas of a coal- or natural-gas-fired power plant, thereby reducing the emission of CO2 into the atmosphere. The syngas a mixture of CO and H2 could be used as a raw material in the manufacture, via the Fisher-Tropsch process, of synthetic fuels, lubrication oils, and other hydrocarbon prod

  15. Imaging space charge regions in Sm-doped ceria using electrochemical strain microscopy

    SciTech Connect

    Chen, Qian Nataly; Li, Jiangyu; Adler, Stuart B.

    2014-11-17

    Nanocrystalline ceria exhibits a total conductivity several orders of magnitude higher than microcrystalline ceria in air at high temperature. The most widely accepted theory for this enhancement (based on fitting of conductivity data to various transport and kinetic models) is that relatively immobile positively charged defects and/or impurities accumulate at the grain boundary core, leading to a counterbalancing increase in the number of mobile electrons (small polarons) within a diffuse space charge region adjacent to each grain boundary. In an effort to validate this model, we have applied electrochemical strain microscopy to image the location and relative population of mobile electrons near grain boundaries in polycrystalline Sm-doped ceria in air at 20–200 °C. Our results show the first direct (spatially resolved) evidence that such a diffuse space charge region does exist in ceria, and is localized to both grain boundaries and the gas-exposed surface.

  16. Synthesis and Characterization of Pure and Doped Ceria Films by Sol-Gel and Sputtering

    SciTech Connect

    Koch, K.T.; Saraf, L.

    2004-01-01

    Pure and doped Ceria are known for their ability to gain or lose Oxygen, which is of interest to the Solid Oxide Fuel Cell (SOFC) and catalyst community. Current efforts are focused in SOFCs to reduce the operating temperature of the cell while maintaining ionic conduction. Ceria is known for its high ionic conductivity in the intermediate temperature region. (600-800° C) We have prepared pure and doped Ceria films by Sol-gel and magnetron sputtering methods. Enhanced grain-boundary contribution in the conductivity can be studied in the Sol-gel process due to excellent control over the synthesis conditions, which enabled us to control the average grain size. Sputtered films were grown and investigated as a prelude to possible multi-layered CeO2 structures in the near future. These films were characterized by X-ray diffraction (XRD), nuclear reaction analysis (NRA), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and Oxygen conduction measurements. We have observed greater volume diffusion in nanocrystalline Ceria compared to bulk polycrystalline films as a result of low density. Near surface diffusion properties with increasing temperature indicate a decrease in the volume diffusion as a result of grain growth. However, a linear increase in O2 content at ~600nm depth was observed and can be correlated to the redistribution of O2 in the samples. Surface roughness of <111> and <200> oriented Ceria films on Al2O3 and YSZ was observed to be 0.13nm and 0.397nm, respectively. In the case of Ceria grown on YSZ, structural properties from XRD results showed a highly oriented structure with cube on cube growth. XRD results from Ceria grown on Al2O3 showed an oriented structure whose degree of orientation appeared to be partially dependent on substrate temperature. Preliminary XPS results indicate reduction in Ceria from the Ce4+ to Ce3+ state near the surface.

  17. Transition-Metal Doped Ceria Microspheres with Nanoporous Structures for CO Oxidation

    PubMed Central

    Zhou, Lin; Li, Xiaoxiao; Yao, Ze; Chen, Zhuwen; Hong, Mei; Zhu, Rongshu; Liang, Yongye; Zhao, Jing

    2016-01-01

    Catalytic oxidation of carbon monoxide (CO) is of great importance in many different fields of industry. Until now it still remains challenging to use non-noble metal based catalysts to oxidize CO at low temperature. Herein, we report a new class of nanoporous, uniform, and transition metal-doped cerium (IV) oxide (ceria, CeO2) microsphere for CO oxidation catalysis. The porous and uniform microsphere is generated by sacrificed polymer template. Transition-metals, like Cu, Co, Ni, Mn and Fe, were doped into CeO2 microspheres. The combination of hierarchical structure and metal doping afford superior catalytic activities of the doped ceria microspheres, which could pave a new way to advanced non-precious metal based catalysts for CO oxidation. PMID:27030159

  18. Two-dimensional, high valence-doped ceria: Ce6WO12(100)/W(110)

    NASA Astrophysics Data System (ADS)

    Stetsovych, Vitalii; Skála, Tomáš; Beran, Jan; Dvořák, Filip; Mazur, Daniel; Tsud, Nataliya; Mašek, Karel; Mysliveček, Josef; Matolín, Vladimír

    2016-05-01

    Doping of oxides for catalytic applications represents one of the most used strategies for improving their catalytic performance. Model catalyst systems for doped oxides that would contain the dopant atoms in a well-defined geometry allowing for investigation of relationships between structure and reactivity are however rare. Here we report on preparation and structural properties of two-dimensional W-doped ceria on W(110) substrate. This model system adopts geometry of two-dimensional Ce6WO12 (100)-oriented thin film, including isolated W6+ ions that donate the charge to Ce3+ ions and act as high-valence dopants. The system represents a model catalyst for prospective use in investigating the role of W6+ active sites in CeOx-WOx catalysts and high valence dopants in ceria in general.

  19. Thickness Dependency of Thin Film Samaria Doped Ceria for Oxygen Sensing

    SciTech Connect

    Sanghavi, Rahul P.; Nandasiri, Manjula I.; Kuchibhatla, Satyanarayana V N T; Jiang, Weilin; Varga, Tamas; Nachimuthu, Ponnusamy; Engelhard, Mark H.; Shutthanandan, V.; Thevuthasan, Suntharampillai; Kayani, Asghar N.; Prasad, Shalini

    2011-01-01

    High temperature oxygen sensors are widely used for exhaust gas monitoring in automobiles. This particular study explores the use of thin film single crystalline samaria doped ceria as the oxygen sensing material. Desired signal to noise ratio can be achieved in a material system with high conductivity. From previous studies it is established that 6 atomic percent samarium doping is the optimum concentration for thin film samaria doped ceria to achieve high ionic conductivity. In this study, the conductivity of the 6 atomic percent samaria doped ceria thin film is measured as a function of the sensing film thickness. Hysteresis and dynamic response of this sensing platform is tested for a range of oxygen pressures from 0.001 Torr to 100 Torr for temperatures above 673 K. An attempt has been made to understand the physics behind the thickness dependent conductivity behavior of this sensing platform by developing a hypothetical operating model and through COMSOL simulations. This study can be used to identify the parameters required to construct a fast, reliable and compact high temperature oxygen sensor.

  20. Performance Evaluation of an Oxygen Sensor as a Function of the Samaria Doped Ceria Film Thickness

    SciTech Connect

    Sanghavi, Rahul P.; Nandasiri, Manjula I.; Kuchibhatla, Satyanarayana V N T; Nachimuthu, Ponnusamy; Engelhard, Mark H.; Shutthanandan, V.; Jiang, Weilin; Thevuthasan, Suntharampillai; Kayani, Asghar N.; Prasad, Shalini

    2010-12-01

    The current demand in the automobile industry is in the control of air-fuel mixture in the combustion engine of automobiles. Oxygen partial pressure can be used as an input parameter for regulating or controlling systems in order to optimize the combustion process. Our goal is to identify and optimize the material system that would potentially function as the active sensing material for such a device that monitors oxygen partial pressure in these systems. We have used thin film samaria doped ceria (SDC) as the sensing material for the sensor operation, exploiting the fact that at high temperatures, oxygen vacancies generated due to samarium doping act as conducting medium for oxygen ions which hop through the vacancies from one side to the other contributing to an electrical signal. We have recently established that 6 atom % Sm doping in ceria films has optimum conductivity. Based on this observation, we have studied the variation in the overall conductivity of 6 atom % samaria doped ceria thin films as a function of thickness in the range of 50 nm to 300 nm at a fixed bias voltage of 2 volts. A direct proportionality in the increase in the overall conductivity is observed with the increase in sensing film thickness. For a range of oxygen pressure values from 1 mTorr to 100 Torr, a tolerable hysteresis error, good dynamic response and a response time of less than 10 seconds was observed

  1. The main factors influencing the O vacancy formation on the Ir doped ceria surface: A DFT+U study

    NASA Astrophysics Data System (ADS)

    Yang, Z. X.; Ma, D. W.; Yu, X. H.; Hermansson, K.

    2010-10-01

    The effects of Ir doping on the oxygen vacancy formation energy have been investigated using the DFT+U method, i.e., first-principles density functional theory calculations with the inclusion of the on-site Coulomb interaction. The main factors influencing the reducibility of Ir-doped ceria are studied carefully. It is found that, although the Ir doping induces gap states (MIGS) as do other noble metals (Pd, Pt, Rh), the structural relaxation (instead of the electronic structure relaxation) is the main factor responsible for the decrease of the oxygen vacancy formation energy, i.e., the Ir doping makes structural distortions much more exothermic for the reduced ceria.

  2. Study of gadolinia-doped ceria solid electrolyte surface by XPS

    SciTech Connect

    Datta, Pradyot Majewski, Peter; Aldinger, Fritz

    2009-02-15

    Gadolinia-doped ceria (CGO) is an important material to be used as electrolyte for solid oxide fuel cell for intermediate temperature operation. Ceria doped with 10 mol% gadolinia (Ce{sub 0.9}Gd{sub 0.1}O{sub 1.95}) was prepared by conventional solid state synthesis and found to be single phase by room temperature X-ray diffraction (XRD). The chemical states of the surface of the prepared sample were analyzed by X-ray photoelectron spectroscopy (XPS). Though Gd was present in its characteristic chemical state, Ce was found in both Ce{sup 4+} and Ce{sup 3+} states. Presence of Ce{sup 3+} state was ascribed to the differential yield of oxygen atoms in the sputtering process.

  3. Lattice thermal expansion and solubility limits of neodymium-doped ceria

    NASA Astrophysics Data System (ADS)

    Zhang, Jinhua; Ke, Changming; Wu, Hongdan; Yu, Jishun; Wang, Jingran

    2016-11-01

    NdxCe1-xO2-0.5x (x=0-1.0) powders were prepared by reverse coprecipitation-calcination method and characterized by XRD. The crystal structure of product powders transformed from single fluorite structure to the complex of fluorite and C-type cubic structure, and finally to trigonal structure with the increase of x-value. An empirical equation simulating the lattice parameter of neodymium doped ceria was established based on the experimental data. The lattice parameters of the fluorite structure solid solutions increased with extensive adoption of Nd3+, and the heating temperature going up. The average thermal expansion coefficients of neodymium doped ceria with fluorite structure are higher than 13.5×10-6 °C-1 from room temperature to 1200 °C.

  4. Lanthanide Ion Doped Upconverting Nanoparticles: Synthesis, Structure and Properties.

    PubMed

    Yan, Chenglin; Zhao, Haiguang; Perepichka, Dmitrii F; Rosei, Federico

    2016-08-01

    Lanthanide doped upconverting nanoparticles (UCNPs) have emerged as a new class of luminescent materials, with major discoveries and overall significant progress during the last decade. Unlike multiphoton absorption in organic dyes or semiconductor quantum dots, lanthanide doped UCNPs involve real intermediate quantum states and convert infrared (IR) into visible light via sequential electronic excitation. The relatively high efficiency of this process even at low radiation flux makes UCNPs particularly attractive for many current and emerging areas of technology. The aim of this article is to highlight several recent advances in this rapidly growing field, emphasizing the relationships between structure and properties of UCNPs. Additionally, various strategies developed for the synthesis of UCNPs with a focus on the various synthetic approaches that yield high-quality monodisperse samples with controlled size, shape and crystalline phase are reviewed. Emerging synthetic approaches towards designed structure to improve the optical and electronic properties of UCNPs are discussed. Finally, recent examples of applications of UCNPs in biomedical and optoelectronics research, giving our own perspectives on future directions and emerging possibilities of the field are described. PMID:27345736

  5. Oxygen nonstoichiometry and thermodynamic characterization of Zr doped ceria in the 1573-1773 K temperature range.

    PubMed

    Takacs, M; Scheffe, J R; Steinfeld, A

    2015-03-28

    This work encompasses the thermodynamic characterization and critical evaluation of Zr(4+) doped ceria, a promising redox material for the two-step solar thermochemical splitting of H2O and CO2 to H2 and CO. As a case study, we experimentally examine 5 mol% Zr(4+) doped ceria and present oxygen nonstoichiometry measurements at elevated temperatures ranging from 1573 K to 1773 K and oxygen partial pressures ranging from 4.50 × 10(-3) atm to 2.3 × 10(-4) atm, yielding higher reduction extents compared to those of pure ceria under all conditions investigated, especially at the lower temperature range and at higher pO2. In contrast to pure ceria, a simple ideal solution model accounting for the formation of isolated oxygen vacancies and localized electrons accurately describes the defect chemistry. Thermodynamic properties are determined, namely: partial molar enthalpy, entropy, and Gibbs free energy. In general, partial molar enthalpy and entropy values of Zr(4+) doped ceria are lower. The equilibrium hydrogen yields are subsequently extracted as a function of the redox conditions for dopant concentrations as high as 20%. Although reduction extents increase greatly with dopant concentration, the oxidation of Zr(4+) doped ceria is thermodynamically less favorable compared to pure ceria. This leads to substantially larger temperature swings between reduction and oxidation steps, ultimately resulting in lower theoretical solar energy conversion efficiencies compared to ceria under most conditions. In effect, these results point to the importance of considering oxidation thermodynamics in addition to reduction when screening potential redox materials.

  6. Nickel-doped ceria nanoparticles for promoting catalytic activity of Pt/C for ethanol electrooxidation

    NASA Astrophysics Data System (ADS)

    Tan, Qiang; Du, Chunyu; Sun, Yongrong; Du, Lei; Yin, Geping; Gao, Yunzhi

    2014-10-01

    This paper reports the facile synthesis of monodispersed nickel-doped ceria nanoparticles by a thermal decomposition method, which is used to promote catalytic properties of Pt/C. The Pt/Ni-doped CeO2/C catalyst obtained exhibits remarkably high activity and stability towards the ethanol electrooxidation in acidic media. This is attributed to higher oxygen releasing capacity and stronger interaction of Ni-doped CeO2 with Pt than pure CeO2 nanoparticles that contribute positively to the removal of poisoning intermediates. We believe that the design concept and synthetic strategy of metal doped oxides used for fuel cell catalysts can be potentially extended to other catalytic fields.

  7. Combustion synthesis and optical properties of ceria doped gadolinium-oxide nanopowder

    NASA Astrophysics Data System (ADS)

    Tamrakar, Raunak Kumar; Bisen, D. P.

    2013-06-01

    The Ceria doped Gadolinium (Gd2O3) nanopowder was synthesized by combustion synthesis by using urea as a fuel. The combustion synthesis method which is reported here is advantageous from the perspectives of small size of the nanoparticle. The structural and photoluminescence (PL) property of sample was studies. Gd2O3:Ce3+ nanoparticles exhibit green emission around 543 nm. The result of XRD show that synthesized sample has cubic structure. The average size of particle is found to be 45 nm. The surface morphology of the films is also presented.

  8. Polycrystalline nanowires of gadolinium-doped ceria via random alignment mediated by supercritical carbon dioxide

    PubMed Central

    Kim, Sang Woo; Ahn, Jae-Pyoung

    2013-01-01

    This study proposes a seed/template-free method that affords high-purity semiconducting nanowires from nanoclusters, which act as basic building blocks for nanomaterials, under supercritical CO2 fluid. Polycrystalline nanowires of Gd-doped ceria (Gd-CeO2) were formed by CO2-mediated non-oriented attachment of the nanoclusters resulting from the dissociation of single-crystalline aggregates. The unique formation mechanism underlying this morphological transition may be exploited for the facile growth of high-purity polycrystalline nanowires. PMID:23572061

  9. Size-dependent Strain in Epitaxial (001)Gadolinium-doped Ceria Nanoislands

    SciTech Connect

    V Solovyov; M Gibert; T Puig; X Obradors

    2011-12-31

    We report size-dependent strain in epitaxial gadolinium doped ceria nanoislands, which was determined by synchrotron x-ray diffraction. Reciprocal space sections of symmetric, (004) and asymmetric, (224) reflections are approximated by a model assuming size-dependent strain of the islands using real-space size distribution obtained by atomic force microscopy. We show that the islands smaller than 40 nm are subjected to a high level of lateral tensile strain and normal compression. The lateral to normal strain ratio determined from the reciprocal map analysis suggests that lateral tension is the primary stress generator, possibly due to oxygen vacancy ordering on the island-substrate interface.

  10. Engineering of Lanthanide-Doped Upconversion Nanoparticles for Optical Encoding.

    PubMed

    Huang, Kai; Idris, Niagara Muhammad; Zhang, Yong

    2016-02-17

    Lanthanide-doped upconversion nanoparticles (UCNPs) are an emerging class of luminescent materials that emit UV or visible light under near infra-red (NIR) excitations, thereby possessing a large anti-Stokes shift property. Due to their sharp excitation and emission bands, excellent photo- and chemical stability, low autofluorescence, and high tissue penetration depth of the NIR light used for excitation, UCNPs have surpassed conventional fluorophores in many bioapplications. A better understanding of the mechanism of upconversion, as well as the development of better approaches to preparing UCNPs, have provided more opportunities to explore their use for optical encoding, which has the potential for applications in multiplex detection and imaging. With the current ability to precisely control the microstructure and properties of UCNPs to produce particles of tunable emission, excitation, luminescence lifetime, and size, various strategies for optical encoding based on UCNPs can now be developed. These optical properties of UCNPs (such as emission and excitation wavelengths, ratiometric intensity, luminescence lifetime, and multicolor patterns), and the strategies employed to engineer these properties for optical encoding of UCNPs through homogeneous ion doping, heterogeneous structure fabrication and microbead encapsulation are reviewed. The challenges and potential solutions faced by UCNP optical encoding are also discussed. PMID:26681103

  11. Calcium-doped ceria/titanate tabular functional nanocomposite by layer-by-layer coating method

    SciTech Connect

    Liu, Xiang W.; Devaraju, M.K.; Yin, Shu; Sato, Tsugio

    2010-07-15

    Ca-doped ceria (CDC)/tabular titanate (K{sub 0.8}Li{sub 0.27}Ti{sub 1.73}O{sub 4}, TT) UV-shielding functional nanocomposite with fairly uniform CDC coating layers was prepared through a polyelectrolyte-associated layer-by-layer (LbL) coating method. TT with lepidocrocite-like layered structure was used as the substrate, poly (diallyldimethylammonium chloride) (PDDA) was used as a coupling agent, CDC nanoparticles were used as the main UV-shielding component. CDC/TT nanocomposites with various coating layers of CDC were obtained through a multistep coating process. The phases were studied by X-ray diffraction. The morphology and coating quality were studied by scanning electron microscopy and element mapping of energy dispersive X-ray analysis. The oxidation catalytic activity, UV-shielding ability and using comfort were characterized by Rancimat test, UV-vis spectra and dynamic friction test, respectively. CDC/TT nanocomposites with low oxidation catalytic activity, high UV-shielding ability and good using comfort were finally obtained. - Graphical abstract: Through the control of surface charge of particles calcium-doped ceria/titanate composites with low oxidation catalytic activity, higher UV-shielding ability and excellent comfort was obtained by a facile layer-by-layer coating method.

  12. Influence of gadolinium doping on the structure and defects of ceria under fuel cell operating temperature

    SciTech Connect

    Acharya, S. A. Gaikwad, V. M.; Sathe, V.; Kulkarni, S. K.

    2014-03-17

    Correlation between atomic positional shift, oxygen vacancy defects, and oxide ion conductivity in doped ceria system has been established in the gadolinium doped ceria system from X-ray diffraction (XRD) and Raman spectroscopy study at operating temperature (300–600 °C) of Intermediate Temperature Solid Oxide Fuel Cell (IT-SOFC). High temperature XRD data are used to quantify atomic positional shift from mean position with temperature. The Raman spectroscopy study shows additional vibration modes related to ordering of defect spaces (Gd{sub Ce}{sup ′}−V{sub o}{sup ••}){sup *} and (2Gd{sub Ce}{sup ′}−V{sub o}{sup ••}){sup x} generated due to association of oxygen vacancies and reduced cerium or dopant cations site (Gd{sup 3+}), which disappear at 450 °C; indicating oxygen vacancies dissociation from the defect complex. The experimental evidences of cation-anion positional shifting and oxygen vacancies dissociation from defect complex in the IT-SOFC operating temperature are discussed to correlate with activation energy for ionic conductivity.

  13. Reduction Dynamics of Doped Ceria, Nickel Oxide, and Cermet Composites Probed Using In Situ Raman Spectroscopy

    PubMed Central

    Shearing, Paul R.; Brightman, Edward; Brett, Dan J. L.; Brandon, Nigel P.; Cohen, Lesley F.

    2016-01-01

    The redox properties of gadolinium doped ceria (CGO) and nickel oxide (NiO) composite cermets underpin the operation of solid oxide electrochemical cells. Although these systems have been widely studied, a full comprehension of the reaction dynamics at the interface of these materials is lacking. Here, in situ Raman spectroscopic monitoring of the redox cycle is used to investigate the interplay between the dynamic and competing processes of hydrogen spillover and water dissociation on the doped ceria surface. In order to elucidate these mechanisms, the redox process in pure CGO and NiO is studied when exposed to wet and dry hydrogen and is compared to the cermet behavior. In dry hydrogen, CGO reduces relatively rapidly via a series of intermediate phases, while NiO reduces via a single‐step process. In wet reducing atmospheres, however, the oxidation state of pure CGO is initially stabilized due to the dissociation of water by reduced Ce(III) and subsequent incorporation of oxygen into the structure. In the reduction process involving the composite cermet, the close proximity of the NiO improves the efficiency and speed of the composite reduction process. Although NiO is already incorporated into working cells, these observations suggest direct routes to further improve cell performance. PMID:27595058

  14. Reduction Dynamics of Doped Ceria, Nickel Oxide, and Cermet Composites Probed Using In Situ Raman Spectroscopy

    PubMed Central

    Shearing, Paul R.; Brightman, Edward; Brett, Dan J. L.; Brandon, Nigel P.; Cohen, Lesley F.

    2016-01-01

    The redox properties of gadolinium doped ceria (CGO) and nickel oxide (NiO) composite cermets underpin the operation of solid oxide electrochemical cells. Although these systems have been widely studied, a full comprehension of the reaction dynamics at the interface of these materials is lacking. Here, in situ Raman spectroscopic monitoring of the redox cycle is used to investigate the interplay between the dynamic and competing processes of hydrogen spillover and water dissociation on the doped ceria surface. In order to elucidate these mechanisms, the redox process in pure CGO and NiO is studied when exposed to wet and dry hydrogen and is compared to the cermet behavior. In dry hydrogen, CGO reduces relatively rapidly via a series of intermediate phases, while NiO reduces via a single‐step process. In wet reducing atmospheres, however, the oxidation state of pure CGO is initially stabilized due to the dissociation of water by reduced Ce(III) and subsequent incorporation of oxygen into the structure. In the reduction process involving the composite cermet, the close proximity of the NiO improves the efficiency and speed of the composite reduction process. Although NiO is already incorporated into working cells, these observations suggest direct routes to further improve cell performance.

  15. Synthesis of nanocrystalline yttria doped ceria powder by urea-formaldehyde polymer gel auto-combustion process

    SciTech Connect

    Biswas, M.; Prabhakaran, K. . E-mail: kp2952002@yahoo.co.uk; Gokhale, N.M.; Sharma, S.C.

    2007-04-12

    Nanocrystalline yttria doped ceria powder has been prepared by auto-combustion of a transparent gel formed by heating an aqueous acidic solution containing methylol urea, urea, cerium(III) nitrate and yttrium(III) nitrate. The TGA and DSC studies showed the combustion reaction of the gel initiated at 225 deg. C and completed within a short period of time. XRD spectrum of the combustion product reveals the formation of phase pure cubic yttria doped ceria during the combustion process. Loose agglomerate of yttria doped ceria particle obtained by the combustion reaction could be easily deagglomerated by planetary ball milling and the powder obtained contains particles in the size range of 0.05-3.3 {mu}m with D {sub 50} value of 0.13 {mu}m. The powder particles are aggregate of nanocrystallites with a wide size range of 14-105 nm. Pellets prepared by pressing the yttria doped ceria powder sintered to 95.2% TD at 1400 deg. C.

  16. Microstructure of Yttria-Doped Ceria as a Function of Oxalate Co-Precipitation Synthesis Conditions

    NASA Astrophysics Data System (ADS)

    Brissonneau, Laurent; Mathieu, Aurore; Tormos, Brigitte; Martin-Garin, Anna

    2016-06-01

    In sodium fast reactors (SFR), dissolved oxygen in sodium can be monitored via potentiometric sensors with an yttria-doped thoria electrolyte. Yttria-doped ceria (YDC) was chosen as a surrogate material to validate the process of such sensors. The material must exhibit high density and a fine grain microstructure to be resistant to the corrosion by liquid sodium and thermal shocks. Thus, the oxalic co-precipitation route was chosen to avoid milling steps that could bring impurity incorporation which is suspected to induce grain boundary corrosion in sodium. The powder and sintered pellets examination show that the synthesis conditions are of primary importance on the process yield, the oxalate powder microstructure and, eventually, on the ceramic density and microstructure. The impurity content was limited by controlling the synthesis, calcination, and sintering steps.

  17. Ultrasmall lanthanide-doped nanoparticles as multimodal platforms

    NASA Astrophysics Data System (ADS)

    Yust, Brian G.; Pedraza, Francisco J.; Sardar, Dhiraj K.

    2014-03-01

    Recently, there has been a great amount of interest in nanoparticles which are able to provide a platform with high contrast for multiple imaging modalities in order to advance the tools available to biomedical researchers and physicians. However, many nanoparticles do not have ideal properties to provide high contrast in different imaging modes. In order to address this, ultrasmall lanthanide doped oxide and fluoride nanoparticles with strong NIR to NIR upconversion fluorescence and a strong magnetic response for magnetic resonance imaging (MRI) have been developed. Specifically, these nanoparticles incorporate gadolinium, dysprosium, or a combination of both into the nano-crystalline host to achieve the magnetic properties. Thulium, erbium, and neodymium codopants provide the strong NIR absorption and emission lines that allow for deeper tissue imaging since near infrared light is not strongly absorbed or scattered by most tissues within this region. This also leads to better image quality and lower necessary excitation intensities. As a part of the one pot synthesis, these nanoparticles are coated with peg, pmao, or d-glucuronic acid to make them water soluble, biocompatible, and bioconjugable due to the available carboxyl or amine groups. Here, the synthesis, morphological characterization, magnetic response, NIR emission, and the quantum yield will be discussed. Cytotoxicity tested through cell viability at varying concentrations of nanoparticles in growth media will also be discussed.

  18. Realizing up-conversion fluorescence tuning in lanthanide-doped nanocrystals by femtosecond pulse shaping method

    PubMed Central

    Zhang, Shian; Yao, Yunhua; Shuwu, Xu; Liu, Pei; Ding, Jingxin; Jia, Tianqing; Qiu, Jianrong; Sun, Zhenrong

    2015-01-01

    The ability to tune color output of nanomaterials is very important for their applications in laser, optoelectronic device, color display and multiplexed biolabeling. Here we first propose a femtosecond pulse shaping technique to realize the up-conversion fluorescence tuning in lanthanide-doped nanocrystals dispersed in the glass. The multiple subpulse formation by a square phase modulation can create different excitation pathways for various up-conversion fluorescence generations. By properly controlling these excitation pathways, the multicolor up-conversion fluorescence can be finely tuned. This color tuning by the femtosecond pulse shaping technique is realized in single material by single-color laser field, which is highly desirable for further applications of the lanthanide-doped nanocrystals. This femtosecond pulse shaping technique opens an opportunity to tune the color output in the lanthanide-doped nanocrystals, which may bring a new revolution in the control of luminescence properties of nanomaterials. PMID:26290391

  19. Iron-ceria Aerogels Doped with Palladium as Water-gas Shift Catalysts for the Production of Hydrogen

    SciTech Connect

    Bali, S.; Huggins, F; Ernst, R; Pugmire, R; Huffman, G; Eyring, E

    2010-01-01

    Mixed 4.5% iron oxide-95.5% cerium oxide aerogels doped with 1% and 2% palladium (Pd) by weight have been synthesized, and their activities for the catalysis of water-gas shift (WGS) reaction have been determined. The aerogels were synthesized using propylene oxide as the proton scavenger for the initiation of hydrolysis and polycondensation of a homogeneous alcoholic solution of cerium(III) chloride heptahydrate and iron(III) chloride hexahydrate precursor. Palladium was doped onto some of these materials by gas-phase incorporation (GPI) using ({eta}{sup 3}-allyl)({eta}{sup 5}-cyclopentadienyl)palladium as the volatile Pd precursor. Water-gas shift catalytic activities were evaluated in a six-channel fixed-bed reactor at atmospheric pressure and reaction temperatures ranging from 150 to 350 C. Both 1% and 2% Pd-doped 4.5% iron oxide-95.5% cerium oxide aerogels showed WGS activities that increased significantly from 150 to 350 C. The activities of 1% Pd-doped 4.5% iron oxide-95.5% cerium oxide aerogels were also compared with that of the 1% Pd-doped ceria aerogel without iron. The WGS activity of 1% Pd on 4.5% iron oxide-95.5% cerium oxide aerogels is substantially higher (5 times) than the activity of 1% Pd-doped ceria aerogel without iron. The gas-phase incorporation results in a better Pd dispersion. Ceria aerogel provides a nonrigid structure wherein iron is not significantly incorporated inside the matrix, thereby resulting in better contact between the Fe and Pd and thus enhancing the WGS activity. Further, neither Fe nor Pd is reduced during the ceria-aerogel-catalyzed WGS reaction. This behavior contrasts with that noted for other Fe-based WGS catalysts, in which the original ferric oxide is typically reduced to a nonstoichiometric magnetite form.

  20. Electrochemical properties of dual phase neodymium-doped ceria alkali carbonate composite electrolytes in intermediate temperature

    NASA Astrophysics Data System (ADS)

    Kim, Ji-Tae; Lee, Tae-Hee; Park, Ka-Young; Seo, Yongho; Kim, Ki Buem; Song, Sun-Ju; Park, Byoungnam; Park, Jun-Young

    2015-02-01

    Composite electrolyte materials composed of neodymium-doped ceria (Nd0.2Ce0.8O1.9; NDC) and (Li-0.5Na)2CO3 are investigated to understand the unique behaviors of their multi-ionic conduction. In the intermediate temperature, the NDC-based carbonate composite electrolytes exhibit a much higher conductivity compared to pure NDC. It has been claimed that the oxide ions are transported in the doped-ceria phase via oxygen vacancies and the protons are conducted through the second carbonate phase, thereby resulting in an enhanced ionic conductivity. However, it has not been experimentally demonstrated if the proton conduction within the carbonate phase aided in improving the conductivity of oxygen ions in the composite system. Hence, the primary objective of this work is to cultivate a deeper insight into the conduction property of these composites as an attempt to clarify the ionic transport phenomenon responsible for enhanced conductivity. Electrical conductivities of NDC and NDC/carbonate materials are investigated as a function of oxygen partial pressure and vapor pressure of water to understand transport properties of composite electrolytes. The ionic and electronic transference numbers of composite electrolytes are measured by the oxygen- and hydrogen-concentration cells containing water. The dominant charge carriers are identified quantitatively through the analysis of the partial conductivity of proton, oxygen ions, and electrons (holes). Understanding the transport properties and transference numbers of composite electrolytes can contribute to the development of commercial solid oxide fuel cells, which can be done by reducing the operating temperature using a highly ionic conductive NDC/carbonate composite electrolyte at the intermediate temperature.

  1. Energetic, electronic and optical properties of lanthanide doped TiO2: An ab initio LDA+U study

    NASA Astrophysics Data System (ADS)

    Mulwa, Winfred M.; Ouma, Cecil N. M.; Onani, Martin O.; Dejene, Francis B.

    2016-05-01

    Substitutional energies, thermodynamic charge transition levels and optical properties of lanthanide doped anatase TiO2 has been investigated using local density approximation with the Hubbard U correction (LDA+U) within the density functional theory formalism. All the lanthanides apart from La introduced impurity states in the host band gap on doping. The calculated substitutional energies indicate that it is possible to dope TiO2 with lanthanide ions. The optimal doping percentage was predicted to be ~3% and dopant levels resulting from Ce, Nd, Sm, Gd and Tm doping were found to possess negative U characteristics. In addition the calculated thermodynamic transition levels predicted Lu as not having any possible charge transitions within the host band gap. The calculated optical absorption coefficients indicate that lanthanide doping led to optical absorption in the visible regime.

  2. Anode-supported microtubular cells fabricated with gadolinia-doped ceria nanopowders

    NASA Astrophysics Data System (ADS)

    Gil, V.; Gurauskis, J.; Campana, R.; Merino, R. I.; Larrea, A.; Orera, V. M.

    Anode-supported microtubular SOFCs based on ceria 3 ± 0.2 mm diameter and about 100 mm in length have been prepared using gadolinia-doped ceria (GDC) nanopowders. Nanometric Ce 0.9Gd 0.1O 1.95 (GDC) powders were deposited on NiO-Ce 0.9Gd 0.1O 1.95 (NiO-GDC) anode supports by dip-coating technique. Fabrication conditions to obtain dense and gas tight electrolyte layers on porous microtubular supports were studied. Three different dispersing agents: commercial Beycostat C213 (CECA, France) and short chain monomer (≤4 carbon atoms) with alcohol or carboxylic acid functional groups were evaluated. By optimizing colloidal dispersion parameters and sintering process, gas tight and dense GDC layers were obtained. Significantly lower sintering temperatures than reported previously (≤1300 °C) were employed to reach ≥98% values of theoretical density within electrolyte layers of ∼10 μm in thickness. A composite cathode, LSCF-GDC 50 wt.% with about 50 μm thickness was dip coated on the co-fired half-cell and then sintered at 1050 °C for 1 h. The electrochemical performance of these cells has been tested. In spite of electronic conduction due to partial reduction of the thin-electrolyte layer, the I- V measurements show power densities of 66 mW cm -2 at 0.45 V at temperatures as low as 450 °C (using 100% H 2 as fuel in the anodic compartment and air in the cathodic chamber).

  3. Platinum-doped ceria based biosensor for in vitro and in vivo monitoring of lactate during hypoxia.

    PubMed

    Sardesai, Naimish P; Ganesana, Mallikarjunarao; Karimi, Anahita; Leiter, James C; Andreescu, Silvana

    2015-03-01

    Measurements of lactate concentrations in blood and tissues are an important indication of the adequacy of tissue oxygenation and could be useful for monitoring the state and progress of a variety of diseases. This paper describes the fabrication, analytical characterization, and physiological application of an amperometric microbiosensor based on lactate oxidase and oxygen-rich platinum doped ceria (Pt-ceria) nanoparticles for monitoring lactate levels during hypoxic conditions. The Pt-ceria nanoparticles provided electrocatalytic amplification for the detection of the enzymatically produced hydrogen peroxide and acted as an internal oxygen source for the enzyme, enabling lactate monitoring in an oxygen depleted tissue. In vitro evaluation of the biosensor demonstrated high selectivity against physiological levels of ascorbic acid, a storage stability of 3 weeks, a fast response time of 6 s, and good, linear sensitivity over a wide concentration range. In vivo experiments performed by placing the biosensor in the hippocampus of anesthetized rats demonstrated the feasibility of continuous lactate monitoring over 2 h ischemia and reperfusion. The results demonstrate that Pt-ceria is a versatile material for use in implantable enzyme bioelectrodes, which may be used to assess the pathophysiology of tissue hypoxia. In addition to measurements in hypoxic conditions, the detection limit of this biosensor was low, 100 pM, and the materials used to fabricate this biosensor can be particularly useful in ultrasensitive devices for monitoring lactate levels in a variety of conditions. PMID:25627400

  4. Kinetic lattice Monte Carlo model for oxygen vacancy diffusion in praseodymium doped ceria: Applications to materials design

    SciTech Connect

    Dholabhai, Pratik P.; Anwar, Shahriar; Adams, James B.; Crozier, Peter; Sharma, Renu

    2011-04-15

    Kinetic lattice Monte Carlo (KLMC) model is developed for investigating oxygen vacancy diffusion in praseodymium-doped ceria. The current approach uses a database of activation energies for oxygen vacancy migration, calculated using first-principles, for various migration pathways in praseodymium-doped ceria. Since the first-principles calculations revealed significant vacancy-vacancy repulsion, we investigate the importance of that effect by conducting simulations with and without a repulsive interaction. Initially, as dopant concentrations increase, vacancy concentration and thus conductivity increases. However, at higher concentrations, vacancies interfere and repel one another, and dopants trap vacancies, creating a 'traffic jam' that decreases conductivity, which is consistent with the experimental findings. The modeled effective activation energy for vacancy migration slightly increased with increasing dopant concentration in qualitative agreement with the experiment. The current methodology comprising a blend of first-principle calculations and KLMC model provides a very powerful fundamental tool for predicting the optimal dopant concentration in ceria related materials. -- graphical abstract: Ionic conductivity in praseodymium doped ceria as a function of dopant concentration calculated using the kinetic lattice Monte Carlo vacancy-repelling model, which predicts the optimal composition for achieving maximum conductivity. Display Omitted Research highlights: {yields} KLMC method calculates the accurate time-dependent diffusion of oxygen vacancies. {yields} KLMC-VR model predicts a dopant concentration of {approx}15-20% to be optimal in PDC. {yields} At higher dopant concentration, vacancies interfere and repel one another, and dopants trap vacancies. {yields} Activation energy for vacancy migration increases as a function of dopant content

  5. Synthesis of La{sup 3+} doped nanocrystalline ceria powder by urea-formaldehyde gel combustion route

    SciTech Connect

    Biswas, M.; Bandyopadhyay, S.

    2012-03-15

    Highlights: Black-Right-Pointing-Pointer Nano LC synthesized by gel combustion, using urea-formaldehyde fuel for first time. Black-Right-Pointing-Pointer Largely single crystals were produced in average range of 20-30 nm. Black-Right-Pointing-Pointer La{sup 3+} doping increases cell dimension linearly. Black-Right-Pointing-Pointer La{sup 3+} doping introduces ionic point defects but does not change electronic band gap. Black-Right-Pointing-Pointer Presence of Ce{sup 3+} indicates that this synthesis route produces reactive powders. -- Abstract: Nanocrystalline ceria powders doped with various concentrations of lanthanum oxide have been prepared following gel combustion route using for the first time urea-formaldehyde as fuel. The synthesized products were characterized by XRD, FESEM, TEM, PL and UV-vis spectroscopy. Peak positions of XRD were refined and the lattice parameters were obtained by applying Cohen's method. Unit cell parameter increases with concentration of La{sup 3+} ion and the variation is consistently linear. XRD calculations showed the dependence of crystallite size on dopant concentrations at lower level. TEM observation revealed unagglomerated particles to be single crystals in the average range of 20-30 nm. Band gap of the La{sup 3+} doped ceria materials does not change with doping. Spectroscopic experiments proved the existence of Ce{sup 3+} in the formed powder.

  6. Leaching effect in gadolinia-doped ceria aqueous suspensions for ceramic processes

    NASA Astrophysics Data System (ADS)

    Caldarelli, A.; Mercadelli, E.; Presto, S.; Viviani, M.; Sanson, A.

    2016-09-01

    Gadolinium doped ceria (CGO) is a commonly used electrolytic material for Solid Oxide Fuel Cells (SOFCs) and for this reason different shaping methods for its deposition are reported in literature. Most of these processes are based on the use of organic-based CGO suspensions, but water-based processes are acquiring increasingly interest for their economical and environmental friendly properties. In this paper we reported how the components of water-based suspension and some unexpected process parameters can deeply affect the functional properties of the final powder. In particular, we observed that CGO powders are strongly affected by ionic leaching induced by furoic acid used as dispersant: the extent of this leaching was related to the dispersant concentration and suspension's ball-milling-time; the phenomenon was confirmed by ICP-AES analyses on suspensions surnatant. Most importantly, ionic leaching affected the electrical properties of CGO: leached powder showed a higher ionic conductivity as a consequence of a partial removal of Gd ions at the grain boundaries. This work is therefore pointing out that when considering water-based suspensions, it is extremely important to carefully consider all the process parameters, including the organic components of the ceramic suspension, as these could lead to unexpected effects on the properties of the powder, affecting the performance of the final shaped material.

  7. Redox behaviour of Gd-doped ceria-nickel oxide composites

    NASA Astrophysics Data System (ADS)

    Gil, V.; Larrea, A.; Merino, R. I.; Orera, V. M.

    Reduction kinetics of NiO-gadolinium-doped ceria (GDC) composites was studied. NiO-GDC ceramic rods were fabricated by cold isostatic pressing of powders of nanometer size obtained by chemical synthesis. The rods were sintered in air at the maximum contraction temperature, 1350 °C, and treated in reducing atmosphere at different temperatures and reduction times. Progress of the reduction process was followed by the gravimetric method. By adjusting the data obtained from weight loss during the isothermal reduction at temperatures between 500 and 700 °C to standard diffusion models for a cylinder, it was possible to obtain effective diffusion coefficients for the material. The process activation energy was 0.9 ± 0.2 eV indicating that, in the whole temperature range studied, the reduction kinetics is controlled by the diffusion of O 2- throughout the ceramic matrix of GDC. SEM studies in reduced, partially reduced and completely reduced samples reveal a submicrometric microstructure with a uniform distribution of Ni phase surrounded by pores within ceramic GDC matrix. This microstructure is suitable for IT-SOFC anodes.

  8. Massive Dirac Fermion Observed in Lanthanide-Doped Topological Insulator Thin Films

    PubMed Central

    Harrison, S. E.; Collins-McIntyre, L. J.; Schönherr, P.; Vailionis, A.; Srot, V.; van Aken, P. A.; Kellock, A. J.; Pushp, A.; Parkin, S. S. P.; Harris, J. S.; Zhou, B.; Chen, Y. L.; Hesjedal, T.

    2015-01-01

    The breaking of time reversal symmetry (TRS) in three-dimensional (3D) topological insulators (TIs), and thus the opening of a ‘Dirac-mass gap’ in the linearly dispersed Dirac surface state, is a prerequisite for unlocking exotic physical states. Introducing ferromagnetic long-range order by transition metal doping has been shown to break TRS. Here, we present the study of lanthanide (Ln) doped Bi2Te3, where the magnetic doping with high-moment lanthanides promises large energy gaps. Using molecular beam epitaxy, single-crystalline, rhombohedral thin films with Ln concentrations of up to ~35%, substituting on Bi sites, were achieved for Dy, Gd, and Ho doping. Angle-resolved photoemission spectroscopy shows the characteristic Dirac cone for Gd and Ho doping. In contrast, for Dy doping above a critical doping concentration, a gap opening is observed via the decreased spectral intensity at the Dirac point, indicating a topological quantum phase transition persisting up to room-temperature. PMID:26503435

  9. Ceria Doped Zinc Oxide Nanoflowers Enhanced Luminol-Based Electrochemiluminescence Immunosensor for Amyloid-β Detection.

    PubMed

    Wang, Jing-Xi; Zhuo, Ying; Zhou, Ying; Wang, Hai-Jun; Yuan, Ruo; Chai, Ya-Qin

    2016-05-25

    In this work, ceria doped ZnO nanomaterials with flower-structure (Ce:ZONFs) were prepared to construct a luminol-based electrochemiluminescence (ECL) immunosensor for amyloid-β protein (Aβ) detection. Herein, carboxyl groups (-COOH) covered Ce:ZONFs were synthesized by a green method with lysine as reductant. After that, Ce:ZONFs-based ECL nanocomposite was prepared by combining the luminophore of luminol and Ce:ZONFs via amidation and physical absorption. Luminol modified on Ce:ZONFs surface could generate a strong ECL signal under the assistance of reactive oxygen species (ROSs) (such as OH(•) and O2(•-)), which were produced by a catalytic reaction between Ce:ZONFs and H2O2. It was worth noticing that a quick Ce(4+) ↔ Ce(3+) reaction in this doped material could increase the rate of electron transfer to realize the signal amplification. Subsequently, the luminol functionalized Ce:ZONFs (Ce:ZONFs-Lum) were covered by secondary antibody (Ab2) and glucose oxidase (GOD), respectively, to construct a novel Ab2 bioconjugate (Ab2-GOD@Ce:ZONFs-Lum). The wire-structured silver-cysteine complex (AgCys NWs) with a large number of -COOH, which was synthesized by AgNO3 and l-cysteine, was used as substrate of the immunosensor to capture the primary antibody (Ab1). Under the optimal conditions, this proposed ECL immunosensor had exhibited high sensitivity for Aβ detection with a wide linear range from 80 fg/mL to 100 ng/mL and an ultralow detection limit of 52 fg/mL. Meanwhile, this biosensor had good specificity for Aβ, indicating that the provided strategy had a promising potential in the detection of Aβ. PMID:27145690

  10. Lanthanide-doped nanocrystals: synthesis, optical-magnetic properties, and applications.

    PubMed

    Wang, Guofeng; Peng, Qing; Li, Yadong

    2011-05-17

    Because of the potential applications of lanthanide-doped nanocrystals in display devices, optical communication, solid-state lasers, catalysis, and biological labeling, the controlled synthesis of these new nanomaterials has sparked considerable interest. Nanosized phosphorescent or optoelectronic devices usually exhibit novel properties, depending on their structures, shapes, and sizes, such as tunable wavelengths, rapid responses, and high efficiencies. Thus, the development of facile synthetic methods towards high-quality lanthanide-doped nanocrystals with uniform size and shape appears to be of key importance both for the exploration of their materials properties and for potential applications. This Account focuses on the recent development in our laboratory of the synthesis and applications of lanthanide-doped nanocrystals. Since 2005, when we proposed a general strategy for nanocrystal synthesis via a liquid-solid-solution process, a range of monodisperse and colloidal lanthanide-doped fluoride, oxide, hydroxide, orthovanadate, thiooxide, borate, and phosphate nanocrystals have been successfully prepared. By rationally tuning the reaction conditions, we have readily synthesized nanostructures, such as hollow microspheres, nanorods, nanowires, hexagonal nanoplates, and nanobelts. By adjusting the different colloidal nanocrystal mixtures, we fabricated unique binary nanostructures with novel dual-mode luminescence properties through a facile ultrasonic method. By tridoping with lanthanide ions that had different electronic structures, we successfully achieved β-NaYF(4) nanorods that were paramagnetic with tuned upconversion luminescence. We have also used NaYF(4):Yb(3+)/Er(3+) conbined with magnetite nanoparticles as a sensitive detection system for DNA: NaYF(4):Yb(3+)/Er(3+) and Fe(3)O(4) nanoparticles were modified with two different DNA sequences. Then, the modified NaYF(4):Yb(3+)/Er(3+) nanoparticles were conjugated to the modified Fe(3)O(4) nanoparticles

  11. Multicolour synthesis in lanthanide-doped nanocrystals through cation exchange in water

    PubMed Central

    Han, Sanyang; Qin, Xian; An, Zhongfu; Zhu, Yihan; Liang, Liangliang; Han, Yu; Huang, Wei; Liu, Xiaogang

    2016-01-01

    Meeting the high demand for lanthanide-doped luminescent nanocrystals across a broad range of fields hinges upon the development of a robust synthetic protocol that provides rapid, just-in-time nanocrystal preparation. However, to date, almost all lanthanide-doped luminescent nanomaterials have relied on direct synthesis requiring stringent controls over crystal nucleation and growth at elevated temperatures. Here we demonstrate the use of a cation exchange strategy for expeditiously accessing large classes of such nanocrystals. By combining the process of cation exchange with energy migration, the luminescence properties of the nanocrystals can be easily tuned while preserving the size, morphology and crystal phase of the initial nanocrystal template. This post-synthesis strategy enables us to achieve upconversion luminescence in Ce3+ and Mn2+-activated hexagonal-phased nanocrystals, opening a gateway towards applications ranging from chemical sensing to anti-counterfeiting. PMID:27698348

  12. Multicolour synthesis in lanthanide-doped nanocrystals through cation exchange in water

    NASA Astrophysics Data System (ADS)

    Han, Sanyang; Qin, Xian; An, Zhongfu; Zhu, Yihan; Liang, Liangliang; Han, Yu; Huang, Wei; Liu, Xiaogang

    2016-10-01

    Meeting the high demand for lanthanide-doped luminescent nanocrystals across a broad range of fields hinges upon the development of a robust synthetic protocol that provides rapid, just-in-time nanocrystal preparation. However, to date, almost all lanthanide-doped luminescent nanomaterials have relied on direct synthesis requiring stringent controls over crystal nucleation and growth at elevated temperatures. Here we demonstrate the use of a cation exchange strategy for expeditiously accessing large classes of such nanocrystals. By combining the process of cation exchange with energy migration, the luminescence properties of the nanocrystals can be easily tuned while preserving the size, morphology and crystal phase of the initial nanocrystal template. This post-synthesis strategy enables us to achieve upconversion luminescence in Ce3+ and Mn2+-activated hexagonal-phased nanocrystals, opening a gateway towards applications ranging from chemical sensing to anti-counterfeiting.

  13. [Terahertz spectroscopic investigation of lanthanide-doped nano-TiO2].

    PubMed

    Feng, Xiu-Jun; Huang, Wan-Xia; Shi, Qi-Wu; Zhang, Yu-Bo; Luo, Yi; Zhang, Ya-Xin

    2011-10-01

    Lanthanide-doped nano-TiO2 samples with different Ti/Ln (Ln = Ce, Nd, and Sm) were synthesized by sol-gel method. The samples were characterized by X-ray diffraction(XRD), Fourier transform infrared spectroscopy(FTIR), X-ray photoelectron spectroscopy (XPS) and terahertz time-domain spectroscopy (THz-TDS). The results indicate that Ce, Nd, and Sm ions were uniformly dispersed into the TiO2; and the infrared activities of lanthanide-deped nano-TiO2 were much stronger than Undoped nano-TiO2, the refractive index of anatase TiO2 declines with frequency increasing in the frequency range of 0.2-1.70 THz at room temperature, and it exhibits anomalous dispersion. Unique characteristic absorption peaks at 1.35 and 1.58 THz were observed from Ce-doped nano-TiO2. Compared with undoped nano-TiO2, the absorption edges of Ce-doped nano-TiO2 were red-shifted remarkably and those of Nd and Sm ions doped nano-TiO2 were blue-shifted. Sm-doped nano-TiO2 has induced the least dielectric losses in the frequency range of 0.2-1.7 THz, and the average value is 0.05.

  14. Computational discovery of lanthanide doped and Co-doped Y{sub 3}Al{sub 5}O{sub 12} for optoelectronic applications

    SciTech Connect

    Choudhary, Kamal; Chernatynskiy, Aleksandr; Phillpot, Simon R.; Sinnott, Susan B.; Mathew, Kiran; Bucholz, Eric W.; Hennig, Richard G.

    2015-09-14

    We systematically elucidate the optoelectronic properties of rare-earth doped and Ce co-doped yttrium aluminum garnet (YAG) using hybrid exchange-correlation functional based density functional theory. The predicted optical transitions agree with the experimental observations for single doped Ce:YAG, Pr:YAG, and co-doped Er,Ce:YAG. We find that co-doping of Ce-doped YAG with any lanthanide except Eu and Lu lowers the transition energies; we attribute this behavior to the lanthanide-induced change in bonding environment of the dopant atoms. Furthermore, we find infrared transitions only in case of the Er, Tb, and Tm co-doped Ce:YAG and suggest Tm,Ce:YAG and Tb,Ce:YAG as possible functional materials for efficient spectral up-conversion devices.

  15. Lanthanide doped nanoparticles as remote sensors for magnetic fields.

    PubMed

    Chen, Ping; Zhang, Junpei; Xu, Beibei; Sang, Xiangwen; Chen, Weibo; Liu, Xiaofeng; Han, Junbo; Qiu, Jianrong

    2014-10-01

    We report the effect of magnetic fields (MFs) on emission Eu-doped NaYF4 nanoparticles. A notable shift in the position of emission bands and the suppressed emission intensity are observed with the MF. These magnetic-optical interactions are explained in terms of the Zeeman effect, enhanced cross-relaxation rate and change of site symmetry. PMID:25123099

  16. Ethyl Acetate Abatement on Copper Catalysts Supported on Ceria Doped with Rare Earth Oxides.

    PubMed

    Carabineiro, Sónia Alexandra Correia; Konsolakis, Michalis; Marnellos, George Emmanouil-Nontas; Asad, Muhammad Faizan; Soares, Olívia Salomé Gonçalves Pinto; Tavares, Pedro Bandeira; Pereira, Manuel Fernando Ribeiro; Órfão, José Joaquim de Melo; Figueiredo, José Luís

    2016-01-01

    Different lanthanide (Ln)-doped cerium oxides (Ce0.5Ln0.5O1.75, where Ln: Gd, La, Pr, Nd, Sm) were loaded with Cu (20 wt. %) and used as catalysts for the oxidation of ethyl acetate (EtOAc), a common volatile organic compound (VOC). For comparison, both Cu-free (Ce-Ln) and supported Cu (Cu/Ce-Ln) samples were characterized by N₂ adsorption at -196 °C, scanning/transmission electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy and temperature programmed reduction in H₂. The following activity sequence, in terms of EtOAc conversion, was found for bare supports: CeO₂ ≈ Ce0.5Pr0.5O1.75 > Ce0.5Sm0.5O1.75 > Ce0.5Gd0.5O1.75 > Ce0.5Nd0.5O1.75 > Ce0.5La0.5O1.75. Cu addition improved the catalytic performance, without affecting the activity order. The best catalytic performance was obtained for Cu/CeO₂ and Cu/Ce0.5Pr0.5O1.75 samples, both achieving complete EtOAc conversion below ca. 290 °C. A strong correlation was revealed between the catalytic performance and the redox properties of the samples, in terms of reducibility and lattice oxygen availability. Νo particular correlation between the VOC oxidation performance and textural characteristics was found. The obtained results can be explained in terms of a Mars-van Krevelen type redox mechanism involving the participation of weakly bound (easily reduced) lattice oxygen and its consequent replenishment by gas phase oxygen.

  17. Ethyl Acetate Abatement on Copper Catalysts Supported on Ceria Doped with Rare Earth Oxides.

    PubMed

    Carabineiro, Sónia Alexandra Correia; Konsolakis, Michalis; Marnellos, George Emmanouil-Nontas; Asad, Muhammad Faizan; Soares, Olívia Salomé Gonçalves Pinto; Tavares, Pedro Bandeira; Pereira, Manuel Fernando Ribeiro; Órfão, José Joaquim de Melo; Figueiredo, José Luís

    2016-01-01

    Different lanthanide (Ln)-doped cerium oxides (Ce0.5Ln0.5O1.75, where Ln: Gd, La, Pr, Nd, Sm) were loaded with Cu (20 wt. %) and used as catalysts for the oxidation of ethyl acetate (EtOAc), a common volatile organic compound (VOC). For comparison, both Cu-free (Ce-Ln) and supported Cu (Cu/Ce-Ln) samples were characterized by N₂ adsorption at -196 °C, scanning/transmission electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy and temperature programmed reduction in H₂. The following activity sequence, in terms of EtOAc conversion, was found for bare supports: CeO₂ ≈ Ce0.5Pr0.5O1.75 > Ce0.5Sm0.5O1.75 > Ce0.5Gd0.5O1.75 > Ce0.5Nd0.5O1.75 > Ce0.5La0.5O1.75. Cu addition improved the catalytic performance, without affecting the activity order. The best catalytic performance was obtained for Cu/CeO₂ and Cu/Ce0.5Pr0.5O1.75 samples, both achieving complete EtOAc conversion below ca. 290 °C. A strong correlation was revealed between the catalytic performance and the redox properties of the samples, in terms of reducibility and lattice oxygen availability. Νo particular correlation between the VOC oxidation performance and textural characteristics was found. The obtained results can be explained in terms of a Mars-van Krevelen type redox mechanism involving the participation of weakly bound (easily reduced) lattice oxygen and its consequent replenishment by gas phase oxygen. PMID:27196886

  18. Thermochemical compatibility between selected (La,Sr)(Co,Fe,Ni)O 3 cathodes and rare earth doped ceria electrolytes

    NASA Astrophysics Data System (ADS)

    Zając, Wojciech; Świerczek, Konrad; Molenda, Janina

    In this paper the results of thermal expansion coefficient measurements of different singly and doubly doped ceria electrolytes, together with results for selected cathode materials from (La,Sr)(Co,Fe,Ni)O 3 system are given. A high temperature chemical stability of the cathode-electrolyte interface was measured on 1:1 wt. mixtures of previously characterized ceria and perovskite powders. The samples were heated at 800, 1000 or at 1200 °C in air for 6 or 100 h. Chemical reactivity investigations were conducted using XRD with Rietveld analysis. For all heated samples the crystal structure of both components were preserved. However, their lattice parameters evolved to a different extent, suggesting the existence of cation exchange. A formation of the solid state solution between Ce 1- xRE xO 2- x/2 and La(Co,Fe,Ni)O 3- δ was found, with mobile La cation. On the basis of the obtained results a qualitative mechanism of the observed reaction was proposed.

  19. Lanthanide-doped luminescent nano-bioprobes: from fundamentals to biodetection

    NASA Astrophysics Data System (ADS)

    Liu, Yongsheng; Tu, Datao; Zhu, Haomiao; Ma, En; Chen, Xueyuan

    2013-01-01

    Trivalent lanthanide (Ln3+)-doped luminescent inorganic nanoparticles (NPs), characterized by long-lived luminescence, large Stokes and/or anti-Stokes shifts, narrow emission bands and high photochemical stability, are considered to be promising candidates as luminescent bioprobes in biomedicine and biotechnology. In this feature article, we provide a brief overview of the most recent advances in Ln3+-doped luminescent inorganic NPs as sensors, which covers from their chemical and physical fundamentals to biodetection, such as controlled synthesis methodology, surface modification chemistry, optical physics, and their promising applications in diverse bioassays, with an emphasis on heterogeneous and homogeneous in vitro biodetection. Finally, some of the most important emerging trends and future efforts toward this active research field are also proposed.

  20. Lanthanide-doped luminescent nano-bioprobes for the detection of tumor markers

    NASA Astrophysics Data System (ADS)

    Chen, Zhuo; Zheng, Wei; Huang, Ping; Tu, Datao; Zhou, Shanyong; Huang, Mingdong; Chen, Xueyuan

    2015-02-01

    Sensitive and specific biodetection of tumor markers is essential for early-stage cancer diagnosis and therapy, and will ultimately increase the patient survival rate. As a new generation of luminescent bioprobes, lanthanide (Ln3+)-doped inorganic luminescent nanoparticles have attracted considerable interest for a variety of biomedical applications due to their superior physicochemical properties. In this feature article, we provide a brief overview of the most recent advances in the development of Ln3+-doped luminescent nano-bioprobes and their promising applications for in vitro detection of tumor markers with an emphasis on the establishment of state-of-the-art assay techniques, such as heterogeneous time-resolved (TR) luminescent bioassay, dissolution-enhanced luminescent bioassay, upconversion (UC) luminescent bioassay, homogeneous TR Förster resonance energy transfer (TR-FRET) and UC-FRET bioassays. Some future prospects and efforts towards this emerging field are also envisioned.

  1. In-situ extended X-ray absorption fine structure study of electrostriction in Gd doped ceria

    SciTech Connect

    Korobko, Roman; Wachtel, Ellen; Lubomirsky, Igor; Lerner, Alyssa; Li, Yuanyuan; Frenkel, Anatoly I.

    2015-01-26

    Studying electric field-induced structural changes in ceramics is challenging due to the very small magnitude of the atomic displacements. We used differential X-ray absorption spectroscopy, an elementally specific and spatially sensitive method, to detect such changes in Gd-doped ceria, recently shown to exhibit giant electrostriction. We found that the large electrostrictive stress generation can be associated with a few percent of unusually short Ce-O chemical bonds that change their length and degree of order under an external electric field. The remainder of the lattice is reduced to the role of passive spectator. This mechanism is fundamentally different from that in electromechanically active materials currently in use.

  2. High Resolution Fluorescence Imaging of Cancers Using Lanthanide Ion-Doped Upconverting Nanocrystals

    PubMed Central

    Naccache, Rafik; Rodríguez, Emma Martín; Bogdan, Nicoleta; Sanz-Rodríguez, Francisco; de la Cruz, Maria del Carmen Iglesias; de la Fuente, Ángeles Juarranz; Vetrone, Fiorenzo; Jaque, Daniel; Solé, José García; Capobianco, John A.

    2012-01-01

    During the last decade inorganic luminescent nanoparticles that emit visible light under near infrared (NIR) excitation (in the biological window) have played a relevant role for high resolution imaging of cancer. Indeed, semiconductor quantum dots (QDs) and metal nanoparticles, mostly gold nanorods (GNRs), are already commercially available for this purpose. In this work we review the role which is being played by a relatively new class of nanoparticles, based on lanthanide ion doped nanocrystals, to target and image cancer cells using upconversion fluorescence microscopy. These nanoparticles are insulating nanocrystals that are usually doped with small percentages of two different rare earth (lanthanide) ions: The excited donor ions (usually Yb3+ ion) that absorb the NIR excitation and the acceptor ions (usually Er3+, Ho3+ or Tm3+), that are responsible for the emitted visible (or also near infrared) radiation. The higher conversion efficiency of these nanoparticles in respect to those based on QDs and GNRs, as well as the almost independent excitation/emission properties from the particle size, make them particularly promising for fluorescence imaging. The different approaches of these novel nanoparticles devoted to “in vitro” and “in vivo” cancer imaging, selective targeting and treatment are examined in this review. PMID:24213500

  3. A palladium-doped ceria@carbon core-sheath nanowire network: a promising catalyst support for alcohol electrooxidation reactions

    NASA Astrophysics Data System (ADS)

    Tan, Qiang; Du, Chunyu; Sun, Yongrong; Du, Lei; Yin, Geping; Gao, Yunzhi

    2015-08-01

    A novel palladium-doped ceria and carbon core-sheath nanowire network (Pd-CeO2@C CSNWN) is synthesized by a template-free and surfactant-free solvothermal process, followed by high temperature carbonization. This hierarchical network serves as a new class of catalyst support to enhance the activity and durability of noble metal catalysts for alcohol oxidation reactions. Its supported Pd nanoparticles, Pd/(Pd-CeO2@C CSNWN), exhibit >9 fold increase in activity toward the ethanol oxidation over the state-of-the-art Pd/C catalyst, which is the highest among the reported Pd systems. Moreover, stability tests show a virtually unchanged activity after 1000 cycles. The high activity is mainly attributed to the superior oxygen-species releasing capability of Pd-doped CeO2 nanowires by accelerating the removal of the poisoning intermediate. The unique interconnected one-dimensional core-sheath structure is revealed to facilitate immobilization of the metal catalysts, leading to the improved durability. This core-sheath nanowire network opens up a new strategy for catalyst performance optimization for next-generation fuel cells.A novel palladium-doped ceria and carbon core-sheath nanowire network (Pd-CeO2@C CSNWN) is synthesized by a template-free and surfactant-free solvothermal process, followed by high temperature carbonization. This hierarchical network serves as a new class of catalyst support to enhance the activity and durability of noble metal catalysts for alcohol oxidation reactions. Its supported Pd nanoparticles, Pd/(Pd-CeO2@C CSNWN), exhibit >9 fold increase in activity toward the ethanol oxidation over the state-of-the-art Pd/C catalyst, which is the highest among the reported Pd systems. Moreover, stability tests show a virtually unchanged activity after 1000 cycles. The high activity is mainly attributed to the superior oxygen-species releasing capability of Pd-doped CeO2 nanowires by accelerating the removal of the poisoning intermediate. The unique

  4. Aluminum-doped ceria-zirconia solid solutions with enhanced thermal stability and high oxygen storage capacity

    PubMed Central

    2012-01-01

    A facile solvothermal method to synthesize aluminum-doped ceria-zirconia (Ce0.5Zr0.5-xAlxO2-x/2, x = 0.1 to 0.4) solid solutions was carried out using Ce(NH4)2(NO3)6, Zr(NO3)3·2H2O Al(NO3)3·9H2O, and NH4OH as the starting materials at 200°C for 24 h. The obtained solid solutions from the solvothermal reaction were calcined at 1,000°C for 20 h in air atmosphere to evaluate the thermal stability. The synthesized Ce0.5Zr0.3Al0.2O1.9 particle was characterized for the oxygen storage capacity (OSC) in automotive catalysis. For the characterization, X-ray diffraction, transmission electron microscopy, and the Brunauer-Emmet-Teller (BET) technique were employed. The OSC values of all samples were measured at 600°C using thermogravimetric-differential thermal analysis. Ce0.5Zr0.3Al0.2O1.9 solid solutions calcined at 1,000°C for 20 h with a BET surface area of 18 m2 g−1 exhibited a considerably high OSC of 427 μmol-O g−1 and good OSC performance stability. The same synthesis route was employed for the preparation of the CeO2 and Ce0.5Zr0.5O2. The incorporation of aluminum ion in the lattice of ceria-based catalyst greatly enhanced the thermal stability and OSC. PMID:23025588

  5. La2NiO4+δ infiltrated into gadolinium doped ceria as novel solid oxide fuel cell cathodes: Electrochemical performance and impedance modelling

    NASA Astrophysics Data System (ADS)

    Nicollet, C.; Flura, A.; Vibhu, V.; Rougier, A.; Bassat, J. M.; Grenier, J. C.

    2015-10-01

    This paper is devoted to the study of composite cathodes of La2NiO4+δ infiltrated into a Gd-doped ceria backbone. Porous Gd-doped ceria backbones are screen printed onto yttria-stabilized zirconia or Gd-doped ceria dense electrolytes, and infiltrated with a La and Ni nitrate solution (2:1 stoichiometry ratio). The influence of the preparation parameters on the polarization resistance, such as the concentration of the infiltration solution, the amount of infiltrated phase, the annealing temperature, the thickness of the electrode, and the nature of the electrolyte, is characterized by impedance spectroscopy performed on symmetrical cells. The optimization of these parameters results in a decrease of the polarization resistance down to 0.15 Ω cm2 at 600 °C. Using the Adler-Lane-Steele model, the modelling of the impedance diagrams leads to the determination of the ionic conductivity as well as the surface exchange rate of the infiltrated electrode.

  6. Lanthanide co-doped paramagnetic spindle-like mesocrystals for imaging and autophagy induction.

    PubMed

    Xu, Yun-Jun; Lin, Jun; Lu, Yang; Zhong, Sheng-Liang; Wang, Lei; Dong, Liang; Wu, Ya-Dong; Peng, Jun; Zhang, Li; Pan, Xiao-Feng; Zhou, Wei; Zhao, Yang; Wen, Long-Ping; Yu, Shu-Hong

    2016-07-21

    We synthesized two novel lanthanide doped spindle-like mesocrystals, YF3:Ce,Eu,Gd and YF3:Ce,Tb,Gd (abbreviated as YEG and YTG mesospindles, respectively). Both of them possess paramagnetic and fluorescent properties, and their excellent cyto-compatibility and low haemolysis are further confirmed. Therefore, they could act as dual mode contrast agents for magnetic resonance imaging (MRI) and fluorescence imaging. Furthermore, YEG and YTG mesospindles induce dose and time dependent autophagy by activating the PI3K signaling pathway. The autophagy induced by YEG and YTG mesocrystals is confirmed by enhanced autophagosome formation, normal cargo degradation, and no disruption of lysosomal function. This work is important to illustrate how rare-earth mesocrystals affect the autophagic pathway, indicating the potential of the YEG and YTG mesospindles in diagnosis and therapy. PMID:27346838

  7. Plasmon-enhanced energy transfer for improved upconversion of infrared radiation in doped-lanthanide nanocrystals.

    PubMed

    Sun, Qi-C; Mundoor, Haridas; Ribot, Josep C; Singh, Vivek; Smalyukh, Ivan I; Nagpal, Prashant

    2014-01-01

    Upconversion of infrared radiation into visible light has been investigated for applications in photovoltaics and biological imaging. However, low conversion efficiency due to small absorption cross-section for infrared light (Yb(3+)), and slow rate of energy transfer (to Er(3+) states) has prevented application of upconversion photoluminescence (UPL) for diffuse sunlight or imaging tissue samples. Here, we utilize resonant surface plasmon polaritons (SPP) waves to enhance UPL in doped-lanthanide nanocrystals. Our analysis indicates that SPP waves not only enhance the electromagnetic field, and hence weak Purcell effect, but also increase the rate of resonant energy transfer from Yb(3+) to Er(3+) ions by 6 fold. While we do observe strong metal mediated quenching (14-fold) of green fluorescence on flat metal surfaces, the nanostructured metal is resonant in the infrared and hence enhances the nanocrystal UPL. This strong Coulombic effect on energy transfer can have important implications for other fluorescent and excitonic systems too.

  8. Lanthanide-doped upconversion nanoparticles electrostatically coupled with photosensitizers for near-infrared-triggered photodynamic therapy

    NASA Astrophysics Data System (ADS)

    Wang, Meng; Chen, Zhuo; Zheng, Wei; Zhu, Haomiao; Lu, Shan; Ma, En; Tu, Datao; Zhou, Shanyong; Huang, Mingdong; Chen, Xueyuan

    2014-06-01

    Lanthanide-doped upconversion nanoparticles (UCNPs) have recently shown great promise in photodynamic therapy (PDT). Herein, we report a facile strategy to fabricate an efficient NIR-triggered PDT system based on LiYF4:Yb/Er UCNPs coupled with a photosensitizer of a β-carboxyphthalocyanine zinc (ZnPc-COOH) molecule via direct electrostatic interaction. Due to the close proximity between UCNPs and ZnPc-COOH, we achieved a high energy transfer efficiency of 96.3% from UCNPs to ZnPc-COOH, which facilitates a large production of cytotoxic singlet oxygen and thus an enhanced PDT efficacy. Furthermore, we demonstrate the high efficacy of such a NIR-triggered PDT agent for the inhibition of tumor growth both in vitro and in vivo, thereby revealing the great potential of the UCNP-based PDT systems as noninvasive NIR-triggered PDT agents for deep cancer therapy.Lanthanide-doped upconversion nanoparticles (UCNPs) have recently shown great promise in photodynamic therapy (PDT). Herein, we report a facile strategy to fabricate an efficient NIR-triggered PDT system based on LiYF4:Yb/Er UCNPs coupled with a photosensitizer of a β-carboxyphthalocyanine zinc (ZnPc-COOH) molecule via direct electrostatic interaction. Due to the close proximity between UCNPs and ZnPc-COOH, we achieved a high energy transfer efficiency of 96.3% from UCNPs to ZnPc-COOH, which facilitates a large production of cytotoxic singlet oxygen and thus an enhanced PDT efficacy. Furthermore, we demonstrate the high efficacy of such a NIR-triggered PDT agent for the inhibition of tumor growth both in vitro and in vivo, thereby revealing the great potential of the UCNP-based PDT systems as noninvasive NIR-triggered PDT agents for deep cancer therapy. Electronic supplementary information (ESI) available: Tables S1 and S2 and Fig. S1-S13. See DOI: 10.1039/c4nr01826e

  9. Lanthanide co-doped paramagnetic spindle-like mesocrystals for imaging and autophagy induction

    NASA Astrophysics Data System (ADS)

    Xu, Yun-Jun; Lin, Jun; Lu, Yang; Zhong, Sheng-Liang; Wang, Lei; Dong, Liang; Wu, Ya-Dong; Peng, Jun; Zhang, Li; Pan, Xiao-Feng; Zhou, Wei; Zhao, Yang; Wen, Long-Ping; Yu, Shu-Hong

    2016-07-01

    We synthesized two novel lanthanide doped spindle-like mesocrystals, YF3:Ce,Eu,Gd and YF3:Ce,Tb,Gd (abbreviated as YEG and YTG mesospindles, respectively). Both of them possess paramagnetic and fluorescent properties, and their excellent cyto-compatibility and low haemolysis are further confirmed. Therefore, they could act as dual mode contrast agents for magnetic resonance imaging (MRI) and fluorescence imaging. Furthermore, YEG and YTG mesospindles induce dose and time dependent autophagy by activating the PI3K signaling pathway. The autophagy induced by YEG and YTG mesocrystals is confirmed by enhanced autophagosome formation, normal cargo degradation, and no disruption of lysosomal function. This work is important to illustrate how rare-earth mesocrystals affect the autophagic pathway, indicating the potential of the YEG and YTG mesospindles in diagnosis and therapy.We synthesized two novel lanthanide doped spindle-like mesocrystals, YF3:Ce,Eu,Gd and YF3:Ce,Tb,Gd (abbreviated as YEG and YTG mesospindles, respectively). Both of them possess paramagnetic and fluorescent properties, and their excellent cyto-compatibility and low haemolysis are further confirmed. Therefore, they could act as dual mode contrast agents for magnetic resonance imaging (MRI) and fluorescence imaging. Furthermore, YEG and YTG mesospindles induce dose and time dependent autophagy by activating the PI3K signaling pathway. The autophagy induced by YEG and YTG mesocrystals is confirmed by enhanced autophagosome formation, normal cargo degradation, and no disruption of lysosomal function. This work is important to illustrate how rare-earth mesocrystals affect the autophagic pathway, indicating the potential of the YEG and YTG mesospindles in diagnosis and therapy. Electronic supplementary information (ESI) available: Size distribution, HRTEM image and additional cellular data. See DOI: 10.1039/c6nr03171d

  10. Biogas as a fuel for solid oxide fuel cells and synthesis gas production: effects of ceria-doping and hydrogen sulfide on the performance of nickel-based anode materials.

    PubMed

    Laycock, Christian J; Staniforth, John Z; Ormerod, R Mark

    2011-05-28

    Numerous investigations have been carried out into the conversion of biogas into synthesis gas (a mixture of H(2) + CO) over Ni/YSZ anode cermet catalysts. Biogas is a variable mixture of gases consisting predominantly of methane and carbon dioxide (usually in a 2 : 1 ratio, but variable with source), with other constituents including sulfur-containing gases such as hydrogen sulfide, which can cause sulfur poisoning of nickel catalysts. The effect of temperature on carbon deposition and sulfur poisoning of 90 : 10 mol% Ni/YSZ under biogas conversion conditions has been investigated by carrying out a series of catalytic reactions of methane-rich (2 : 1) CH(4)/CO(2) mixtures in the absence and presence of H(2)S over the temperature range 750-1000 °C. The effect of ceria-doping on carbon dioxide reforming, carbon deposition and sulfur tolerance has also been investigated by carrying out a similar series of reactions over ceria-doped Ni/YSZ. Ceria was doped at 5 mol% of the nickel content to give an anode catalyst composition of 85.5 : 4.5 : 10 mol% Ni/CeO(2)/YSZ. Reactions were followed using quadrupolar mass spectrometry (QMS) and the amount of carbon deposition was analysed by subjecting the reacted catalyst samples to a post-reaction temperature programmed oxidation (TPO). On undoped Ni/YSZ, carbon deposition occurred predominantly through thermal decomposition of methane. Ceria-doping significantly suppressed methane decomposition and at high temperatures simultaneously promoted the reverse Boudouard reaction, significantly lowering carbon deposition. Sulfur poisoning of Ni/YSZ occurred in two phases, the first of which caused the most activity loss and was accelerated on increasing the reaction temperature, while the second phase had greater stability and became more favourable with increasing reaction temperature. Adding H(2)S significantly inhibited methane decomposition, resulting in much less carbon deposition. Ceria-doping significantly increased the sulfur

  11. Biogas as a fuel for solid oxide fuel cells and synthesis gas production: effects of ceria-doping and hydrogen sulfide on the performance of nickel-based anode materials.

    PubMed

    Laycock, Christian J; Staniforth, John Z; Ormerod, R Mark

    2011-05-28

    Numerous investigations have been carried out into the conversion of biogas into synthesis gas (a mixture of H(2) + CO) over Ni/YSZ anode cermet catalysts. Biogas is a variable mixture of gases consisting predominantly of methane and carbon dioxide (usually in a 2 : 1 ratio, but variable with source), with other constituents including sulfur-containing gases such as hydrogen sulfide, which can cause sulfur poisoning of nickel catalysts. The effect of temperature on carbon deposition and sulfur poisoning of 90 : 10 mol% Ni/YSZ under biogas conversion conditions has been investigated by carrying out a series of catalytic reactions of methane-rich (2 : 1) CH(4)/CO(2) mixtures in the absence and presence of H(2)S over the temperature range 750-1000 °C. The effect of ceria-doping on carbon dioxide reforming, carbon deposition and sulfur tolerance has also been investigated by carrying out a similar series of reactions over ceria-doped Ni/YSZ. Ceria was doped at 5 mol% of the nickel content to give an anode catalyst composition of 85.5 : 4.5 : 10 mol% Ni/CeO(2)/YSZ. Reactions were followed using quadrupolar mass spectrometry (QMS) and the amount of carbon deposition was analysed by subjecting the reacted catalyst samples to a post-reaction temperature programmed oxidation (TPO). On undoped Ni/YSZ, carbon deposition occurred predominantly through thermal decomposition of methane. Ceria-doping significantly suppressed methane decomposition and at high temperatures simultaneously promoted the reverse Boudouard reaction, significantly lowering carbon deposition. Sulfur poisoning of Ni/YSZ occurred in two phases, the first of which caused the most activity loss and was accelerated on increasing the reaction temperature, while the second phase had greater stability and became more favourable with increasing reaction temperature. Adding H(2)S significantly inhibited methane decomposition, resulting in much less carbon deposition. Ceria-doping significantly increased the sulfur

  12. A SnO2-samarium doped ceria additional anode layer in a direct carbon fuel cell

    NASA Astrophysics Data System (ADS)

    Yu, Baolong; Zhao, Yicheng; Li, Yongdan

    2016-02-01

    The role of a SnO2-samarium doped ceria (SDC) additional anode layer in a direct carbon fuel cell (DCFC) with SDC-(Li0.67Na0.33)2CO3 composite electrolyte and lithiated NiO-SDC-(Li0.67Na0.33)2CO3 composite cathode is investigated and compared with a NiO-SDC extra anode layer. Catalytic grown carbon fiber mixed with (Li0.67Na0.33)2CO3 is used as a fuel. At 750 °C, the maximum power outputs of 192 and 143 mW cm-2 are obtained by the cells with SnO2-SDC and NiO-SDC layers, respectively. In the SnO2-SDC layer, the reduction of SnO2 and the oxidation of Sn happen simultaneously during the cell operation, and the Sn/SnO2 redox cycle provides an additional route for fuel conversion. The formation of an insulating dense interlayer between the anode and electrolyte layers, which usually happens in DCFCs with metal anodes, is avoided in the cell with the SnO2-SDC layer, and the stability of the cell is improved consequently.

  13. Role of associated defects in oxygen ion conduction and surface exchange reaction for epitaxial samaria-doped ceria thin films as catalytic coatings

    DOE PAGES

    Yang, Nan; Shi, Yanuo; Schweiger, Sebastian; Strelcov, Evgheni; Foglietti, Vittorio; Orgiani, Pasquale; Balestrino, Giuseppe; Kalinin, Sergei V.; Jennifer L. M. Rupp; Aruta, Carmela; et al

    2016-05-18

    Samaria-doped ceria (SDC) thin films are particularly important for energy and electronic applications such as micro-solid oxide fuel cells, electrolysers, sensors and memristors. In this paper we report a comparative study investigating ionic conductivity and surface reactions for well-grown epitaxial SDC films varying the samaria doping concentration. With increasing doping above 20 mol% of samaria, an enhancement in the defect association was observed by Raman spectroscopy. The role of such defect associates on the films` oxygen ion transport and exchange was investigated by electrochemical impedance spectroscopy and electrochemical strain microscopy (ESM). The measurements reveal that the ionic transport has amore » sharp maximum in ionic conductivity and drop in its activation energy down to 0.6 eV for 20 mol% doping. Increasing the doping concentration further up to 40 mol%, raises the activation energy substantially by a factor of two. We ascribe the sluggish transport kinetics to the "bulk" ionic-near ordering in case of the heavily doped epitaxial films. Analysis of the ESM first order reversal curve measurements indicate that these associated defects may have a beneficial role by lowering the activation of the oxygen exchange "surface" reaction for heavily doped 40 mol% of samaria. We reveal in a model experiment through a solid solution series of samaria doped ceria epitaxial films that the occurrence of associate defects in the bulk affects the surface charging state of the films to increase the exchange rates. Lastly, the implication of these findings are the design of coatings with tuned oxygen surface exchange by control of bulk associate clusters for future electro-catalytic applications.« less

  14. Raman and absorption spectrophotometric studies of selected lanthanide, californium-doped lanthanide, and actinide trihalides in the solid state

    SciTech Connect

    Wilmarth, W.R.

    1988-03-01

    The solid-state absorption spectra of Cf(III) ions as a dopant in lanthanide trihalide hosts (LnCl/sub 3/: Ln = Ce, Sm, and Y; LnBr/sub 3/: Ln = Ce, Sm, Tb, and Y; LnI/sub 3/: Ln = Ce and Y) have been recorded. The spectra of Cf(III) have been correlated with the various crystal structures. The phonon Raman spectra and solid-state absorption spectra of PmF/sub 3/, PmCl/sub 3/, PmBr/sub 3/, and two crystal modifications of PmI/sub 3/ have been recorded. Symmetry assignments have been made for the Raman-active bands for these trihalides and also the sesquioxide. The room-temperature absorption spectra have been correlated to crystal field effects. The symmetry assignments of the Raman-active phonon modes have been made based on polarized Raman spectra from single crystals of YF/sub 3/-type orthorhombic TbF/sub 3/ and PuBr/sub 3/-type orthorhombic NdBr/sub 3/. Raman spectra of other isostructural lanthanide compounds have been recorded and compared. Symmetry assignments for these compounds have been made by analogy to the single-crystal assignments. Raman spectra have been obtained and catalogued for a number of actinide compounds. Symmetry assignments have been made for the observed Raman-active phonon bands in this work based on the assignments made for isostructural lanthanide compounds. 29 figs., 22 tabs.

  15. Electrochemical characteristics of samaria-doped ceria infiltrated strontium-doped LaMnO3 cathodes with varied thickness for yttria-stabilized zirconia electrolytes

    NASA Astrophysics Data System (ADS)

    Ding, Dong; Gong, Mingyang; Xu, Chunchuan; Baxter, Nicholas; Li, Yihong; Zondlo, John; Gerdes, Kirk; Liu, Xingbo

    2011-03-01

    Samaria-doped ceria (SDC) infiltrated into strontium-doped LaMnO3 (LSM) cathodes with varied cathode thickness on yttria-stabilized zirconia (YSZ) were investigated via symmetrical cell, half cell, and full cell configurations. The results of the symmetrical cells showed that the interfacial polarization resistance (RP) decreased with increasing electrode thickness up to ∼30 μm, and further increases in the thickness of the cathode did not cause significant variation of electrode performance. At 800 °C, the minimum RP was around 0.05 Ω cm2. The impedance spectra indicated that three main electrochemical processes existed, possibly corresponding to the oxygen ion incorporation, surface diffusion of oxygen species and oxygen adsorption and dissociation. The DC polarization on the half cells and characterization of the full cells also demonstrated a similar correlation between the electrode performance and the electrode thickness. The peak power densities of the single cells with the 10, 30, and 50-μm thick electrodes were 0.63, 1.16 and 1.11 W cm-2, respectively. The exchange current densities under moderate polarization are calculated and possible rate-determining steps are discussed.

  16. Reduction of FCCI effects in lanthanide-iron diffusion couples by doping with palladium

    NASA Astrophysics Data System (ADS)

    Egeland, G. W.; Mariani, R. D.; Hartmann, T.; Porter, D. L.; Hayes, S. L.; Kennedy, J. R.

    2013-09-01

    Fast-reactor metallic fuels produce lanthanide fission products which have been shown to diffuse to the fuel periphery. Lanthanides interacting with the cladding is one cause of fuel-cladding chemical interaction. To test the viability of reducing the interaction by pinning these lanthanides, palladium was chosen as a fuel dopant based on the lanthanide-palladium intermetallic thermodynamic stability and fuel compatibility. Three lanthanides were tested, neodymium, cerium, and praseodymium, along with their 1:1 palladium compounds, against iron using diffusion couples. These experiments show the direct contact effect on iron of each lanthanide and its respective palladium compound at temperatures from 580 °C to 700 °C for 100 h.

  17. Nano-granulization of gadolinia-doped ceria electrolyte surface by aerosol-assisted chemical vapor deposition for low-temperature solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Kim, Jun Woo; Jang, Dong Young; Kim, Manjin; Choi, Hyung Jong; Shim, Joon Hyung

    2016-01-01

    We have fabricated nano-scale gadolinia-doped ceria (GDC) at the electrode-electrolyte boundary by aerosol-assisted chemical vapor deposition (AACVD) for high-performance solid oxide fuel cells (SOFCs) working at low temperatures below 500 °C. In AACVD, temperature is the key factor affecting the grain size. We have confirmed that by nano-granulizing the electrolyte surface using optimized AACVD, the power output of the SOFC is 50% higher than that of the bare GDC SOFC. From the impedance analysis, significant enhancement of the cathodic oxygen reduction reaction is identified from the AACVD-GDC nano-grain surface treatment.

  18. Metal electrode dependent field effect transistors made of lanthanide ion-doped DNA crystals

    NASA Astrophysics Data System (ADS)

    Reddy Dugasani, Sreekantha; Hwang, Taehyun; Kim, Jang Ah; Gnapareddy, Bramaramba; Kim, Taesung; Park, Sung Ha

    2016-03-01

    We fabricated lanthanide ion (Ln3+, e.g. Dy3+, Er3+, Eu3+, and Gd3+)-doped self-assembled double-crossover (DX) DNA crystals grown on the surface of field effect transistors (FETs) containing either a Cr, Au, or Ni electrode. Here we demonstrate the metal electrode dependent FET characteristics as a function of various Ln3+. The drain-source current (I ds), controlled by the drain-source voltage (V ds) of Ln3+-doped DX DNA crystals with a Cr electrode on an FET, changed significantly under various gate voltages (V g) due to the relative closeness of the work function of Cr to the energy band gap of Ln3+-DNA crystals compared to those of Au and Ni. For Ln3+-DNA crystals on an FET with either a Cr or Ni electrode at a fixed V ds, I ds decreased with increasing V g ranging from  -2 to 0 V and from 0 to  +3 V in the positive and negative regions, respectively. By contrast, I ds for Ln3+-DNA crystals on an FET with Au decreased with increasing V g in only the positive region due to the greater electronegativity of Au. Furthermore, Ln3+-DNA crystals on an FET exhibited behaviour sensitive to V g due to the appreciable charge carriers generated from Ln3+. Finally, we address the resistivity and the mobility of Ln3+-DNA crystals on an FET with different metal electrodes obtained from I ds-V ds and I ds-V g curves. The resistivities of Ln3+-DNA crystals on FETs with Cr and Au electrodes were smaller than those of pristine DNA crystals on an FET, and the mobility of Ln3+-DNA crystals on an FET with Cr was relatively higher than that associated with other electrodes.

  19. Electrochemical behavior of thin-film Sm-doped ceria: insights from the point-contact configuration.

    PubMed

    Oh, Tae-Sik; Haile, Sossina M

    2015-05-28

    The electrochemical behavior of chemical vapor deposition (CVD) grown porous films of Sm-doped ceria (SDC) for hydrogen oxidation has been evaluated by impedance spectroscopy using a point contact geometry at a temperature of 650 °C. Porous SDC films, 950 nm in thickness, were deposited on both sides of single-crystal YSZ(100). Pt paste was applied over the surface of one SDC layer to create a high-activity counter electrode. Ni wire was contacted to the surface of the other SDC layer to create a limited contact-area working electrode. The active area of contact at the working electrode was determined using the Newman equation and the electrolyte constriction impedance. The radius of this area varied from 5 to 18 μm, depending on gas composition and bias. The area-normalized electrode impedance (where the area was that determined as described above) varied from 0.03 to 0.17 Ω cm(2) and generally decreased with cathodic bias and decreasing oxygen partial pressure. From an analysis of the dimensions of the active area with bias, it was found that the majority of the overpotential occurred at the SDC|gas interface rather than the SDC|YSZ interface. Overall, the anode overpotential is found to be extremely small, competitive with the best oxide anodes reported in the literature. Nevertheless, the impedance falls in line with expected values based on extrapolations of the properties of dense, flat SDC model electrodes grown by pulsed laser deposition (Chueh et al., Nat. Mater., 2012). The results demonstrate that, with suitable fabrication approaches, exceptional activity can be achieved with SDC for hydrogen electrooxidation even in the absence of metal-oxide-gas triple phase boundaries.

  20. Electrochemical behavior of thin-film Sm-doped ceria: insights from the point-contact configuration.

    PubMed

    Oh, Tae-Sik; Haile, Sossina M

    2015-05-28

    The electrochemical behavior of chemical vapor deposition (CVD) grown porous films of Sm-doped ceria (SDC) for hydrogen oxidation has been evaluated by impedance spectroscopy using a point contact geometry at a temperature of 650 °C. Porous SDC films, 950 nm in thickness, were deposited on both sides of single-crystal YSZ(100). Pt paste was applied over the surface of one SDC layer to create a high-activity counter electrode. Ni wire was contacted to the surface of the other SDC layer to create a limited contact-area working electrode. The active area of contact at the working electrode was determined using the Newman equation and the electrolyte constriction impedance. The radius of this area varied from 5 to 18 μm, depending on gas composition and bias. The area-normalized electrode impedance (where the area was that determined as described above) varied from 0.03 to 0.17 Ω cm(2) and generally decreased with cathodic bias and decreasing oxygen partial pressure. From an analysis of the dimensions of the active area with bias, it was found that the majority of the overpotential occurred at the SDC|gas interface rather than the SDC|YSZ interface. Overall, the anode overpotential is found to be extremely small, competitive with the best oxide anodes reported in the literature. Nevertheless, the impedance falls in line with expected values based on extrapolations of the properties of dense, flat SDC model electrodes grown by pulsed laser deposition (Chueh et al., Nat. Mater., 2012). The results demonstrate that, with suitable fabrication approaches, exceptional activity can be achieved with SDC for hydrogen electrooxidation even in the absence of metal-oxide-gas triple phase boundaries. PMID:25932615

  1. Ultra-low Doping on Two-Dimensional Transition Metal Dichalcogenides using DNA Nanostructure Doped by a Combination of Lanthanide and Metal Ions

    PubMed Central

    Kang, Dong-Ho; Dugasani, Sreekantha Reddy; Park, Hyung-Youl; Shim, Jaewoo; Gnapareddy, Bramaramba; Jeon, Jaeho; Lee, Sungjoo; Roh, Yonghan; Park, Sung Ha; Park, Jin-Hong

    2016-01-01

    Here, we propose a novel DNA-based doping method on MoS2 and WSe2 films, which enables ultra-low n- and p-doping control and allows for proper adjustments in device performance. This is achieved by selecting and/or combining different types of divalent metal and trivalent lanthanide (Ln) ions on DNA nanostructures, using the newly proposed concept of Co-DNA (DNA functionalized by both divalent metal and trivalent Ln ions). The available n-doping range on the MoS2 by Ln-DNA is between 6 × 109 and 2.6 × 1010 cm−2. The p-doping change on WSe2 by Ln-DNA is adjusted between −1.0 × 1010 and −2.4 × 1010 cm−2. In Eu3+ or Gd3+-Co-DNA doping, a light p-doping is observed on MoS2 and WSe2 (~1010 cm−2). However, in the devices doped by Tb3+ or Er3+-Co-DNA, a light n-doping (~1010 cm−2) occurs. A significant increase in on-current is also observed on the MoS2 and WSe2 devices, which are, respectively, doped by Tb3+- and Gd3+-Co-DNA, due to the reduction of effective barrier heights by the doping. In terms of optoelectronic device performance, the Tb3+ or Er3+-Co-DNA (n-doping) and the Eu3+ or Gd3+-Co-DNA (p-doping) improve the MoS2 and WSe2 photodetectors, respectively. We also show an excellent absorbing property by Tb3+ ions on the TMD photodetectors. PMID:26838524

  2. Ultra-low Doping on Two-Dimensional Transition Metal Dichalcogenides using DNA Nanostructure Doped by a Combination of Lanthanide and Metal Ions

    NASA Astrophysics Data System (ADS)

    Kang, Dong-Ho; Dugasani, Sreekantha Reddy; Park, Hyung-Youl; Shim, Jaewoo; Gnapareddy, Bramaramba; Jeon, Jaeho; Lee, Sungjoo; Roh, Yonghan; Park, Sung Ha; Park, Jin-Hong

    2016-02-01

    Here, we propose a novel DNA-based doping method on MoS2 and WSe2 films, which enables ultra-low n- and p-doping control and allows for proper adjustments in device performance. This is achieved by selecting and/or combining different types of divalent metal and trivalent lanthanide (Ln) ions on DNA nanostructures, using the newly proposed concept of Co-DNA (DNA functionalized by both divalent metal and trivalent Ln ions). The available n-doping range on the MoS2 by Ln-DNA is between 6 × 109 and 2.6 × 1010 cm-2. The p-doping change on WSe2 by Ln-DNA is adjusted between -1.0 × 1010 and -2.4 × 1010 cm-2. In Eu3+ or Gd3+-Co-DNA doping, a light p-doping is observed on MoS2 and WSe2 (~1010 cm-2). However, in the devices doped by Tb3+ or Er3+-Co-DNA, a light n-doping (~1010 cm-2) occurs. A significant increase in on-current is also observed on the MoS2 and WSe2 devices, which are, respectively, doped by Tb3+- and Gd3+-Co-DNA, due to the reduction of effective barrier heights by the doping. In terms of optoelectronic device performance, the Tb3+ or Er3+-Co-DNA (n-doping) and the Eu3+ or Gd3+-Co-DNA (p-doping) improve the MoS2 and WSe2 photodetectors, respectively. We also show an excellent absorbing property by Tb3+ ions on the TMD photodetectors.

  3. Effects of gallia addition on sintering behavior and electrical conductivity of yttria-doped ceria

    NASA Astrophysics Data System (ADS)

    Seo, Seung-Woo; Park, Ji-Hoon; Park, Min-Woo; Koo, Ji-Hoon; Lee, Ki-Tae; Lee, Joo-Sin

    2014-07-01

    The densification behavior and electrical conductivity of Ce0.8Y0.2O1.9 ceramics with gallia concentrations ranging from 0 to 5 mol. % were investigated. The sintered density was found to increase with increasing Ga2O3 content up to 1 mol. % and then to decrease upon further Ga2O3 addition. Dense Ce0.8Y0.2O1.9 ceramics with 94% of the theoretical density could be obtained by sintering the milled mixture with 1 mol. % Ga2O3 addition at 1400°C for 5 h. The conductivity of the 1 mol. % Ga2O3-added specimen showed a maximum value of 1.37 × 10-2 Ω-1· cm-1 at 700°C. Pure Ce0.8Y0.2O1.9 ceramics needed to be sintered at 1550°C in order to obtain an equivalent theoretical density and conductivity. The introduction of Ga2O3 doping had a good effect on the sintering properties and electrical conductivities of Y2O3-doped CeO2.

  4. Intermediate-Temperature Solid-Oxide Fuel Cells with a Gadolinium-Doped Ceria Anodic Functional Layer Deposited via Radio-Frequency Sputtering.

    PubMed

    Tanveer, Waqas Hassan; Ji, Sanghoon; Yu, Wonjong; Cho, Gu Young; Lee, Yoon Ho; Cha, Suk Won

    2015-11-01

    We investigated the effects of the insertion of a gadolinium-doped ceria (GDC) anodic functional layer (AFL) on the electrochemical performance of intermediate-temperature solid-oxide fuel cells (SOFCs). Fully stabilized yttria-stabilized zirconia (YSZ) was used as an oxygen-ion-conducting and support material. Nickel-Samaria-doped ceriathin film was used as an anode material, while screen-printed lanthanum strontium magnetite served as a cathode material. In order to enhance the interfacial reaction on the anode side, a GDC-AFL with a thickness of about 140 nm, deposited via radio-frequency sputtering, was inserted into the anode-electrolyte interface. SOFCs with and without a GDC-AFL were electrochemically characterized. In an intermediate temperature range of about 700 - 800 degrees C, the application of the GDC-AFL led to an increase in the peak power density of approximately 16%.

  5. Doped Yttrium Chromite-Ceria Composite as a Redox-Stable and Sulfur-Tolerant Anode for Solid Oxide Fuel Cells

    SciTech Connect

    Yoon, Kyung J.; Coyle, Christopher A.; Marina, Olga A.

    2011-12-11

    A Ca- and Co-doped yttrium chromite (YCCC) - samaria-doped ceria (SDC) composite was studied in relation to a potential use as a solid oxide fuel cell (SOFC) anode material. Tests performed using the yttria-stabilized zirconia (YSZ) electrolyte-supported cells revealed that the electrocatalytic activity of the YCCC-SDC anode towards hydrogen oxidation at 800 C was comparable to that of the Ni-YSZ anode. In addition, the YCCC-SDC anode exhibited superior sulfur tolerant characteristics showing less than 10% increase in a polarization resistance, fully reversible, upon exposure to 20 ppm H2S at 800 C. No performance degradation was observed during multiple reduction-oxidation (redox) cycles when the anode was intentionally exposed to the air environment followed by the reduction in hydrogen. The redox tolerance of the YCCC-SDC anode was attributed to the dimensional and chemical stability of the YCCC exhibiting minimal isothermal chemical expansion upon redox cycling.

  6. Lanthanide-doped NaScF4 nanoprobes: crystal structure, optical spectroscopy and biodetection

    NASA Astrophysics Data System (ADS)

    Ai, Yu; Tu, Datao; Zheng, Wei; Liu, Yongsheng; Kong, Jintao; Hu, Ping; Chen, Zhuo; Huang, Mingdong; Chen, Xueyuan

    2013-06-01

    Trivalent lanthanide ions (Ln3+)-doped inorganic nanoparticles (NPs) as potential luminescent bioprobes have been attracting tremendous interest because of their unique upconversion (UC) and downconversion (DC) luminescence properties. NaScF4, as an important host material, has been rarely reported and its crystal structure remains unclear. Herein, based on the single crystal X-ray diffraction, the space group of NaScF4 crystals was determined to be P31 containing multiple sites of Sc3+ with crystallographic site symmetry of C1, which was verified by high-resolution photoluminescence spectroscopy of Eu3+ at low temperature (10 K). Furthermore, monodisperse and size-controllable NaScF4:Ln3+ NPs were synthesized via a facile thermal decomposition method. The biotinylated NaScF4:Er3+/Yb3+ NPs were demonstrated for their applications as a heterogeneous UC luminescence bioprobe to detect avidin with a detection limit of 180 pM. After bioconjugation with amino-terminal fragment (ATF) of urokinase plasminogen activator (uPA), NaScF4:Ln3+ NPs also exhibited specific recognition of cancer cells overexpressed with uPA receptor (uPAR, an important marker of tumor biology and metastasis), showing great potentials in tumor-targeted bioimaging.Trivalent lanthanide ions (Ln3+)-doped inorganic nanoparticles (NPs) as potential luminescent bioprobes have been attracting tremendous interest because of their unique upconversion (UC) and downconversion (DC) luminescence properties. NaScF4, as an important host material, has been rarely reported and its crystal structure remains unclear. Herein, based on the single crystal X-ray diffraction, the space group of NaScF4 crystals was determined to be P31 containing multiple sites of Sc3+ with crystallographic site symmetry of C1, which was verified by high-resolution photoluminescence spectroscopy of Eu3+ at low temperature (10 K). Furthermore, monodisperse and size-controllable NaScF4:Ln3+ NPs were synthesized via a facile thermal

  7. MD simulations of a doped ceria surface very large surface ion motion

    NASA Astrophysics Data System (ADS)

    Baudin, Micael; Wojcik, Mark; Hermansson, Kersti; Palmqvist, Anders E. C.; Muhammed, Mamoun

    2001-03-01

    Mean-square displacements (MSDs) and individual-ion square-displacements (ISDs) for the different constituents in Ca-doped CeO 2(0 1 1) slabs at 300 K have been studied as a function of depth from the surface. Constant pressure-constant temperature MD simulations were used. The MSDs are 2-3 times larger at the surface than in the bulk, but ISDs as large as ca. 150 times the surface MSD value were observed during short-time periods for anions next to an anion vacancy at the surface. The chemical implications of this kind of motion are important, since transient structural distortions of this magnitude will lead to large electron re-distributions.

  8. Redox properties of nanostructured lanthanide-doped ceria spheres prepared by microwave assisted hydrothermal homogeneous co-precipitation.

    PubMed

    Muñoz, F F; Acuña, L M; Albornoz, C A; Leyva, A G; Baker, R T; Fuentes, R O

    2015-01-01

    In this work, nanostructured LnxCe(1-x)O2-δ (Ln: Gd and Pr; x = 0.1 and 0.2) spheres were synthesized by microwave assisted hydrothermal homogeneous co-precipitation and their properties were characterized by synchrotron radiation XRD, X-ray absorption near-edge spectroscopy (XANES) and scanning and high-resolution electron microscopy (SEM and HRTEM). In situ XRD and XANES experiments were carried out under reducing and oxidizing conditions in order to investigate the redox behaviour of these materials. The nanostructured mixed oxide spheres were found to have a cubic crystal structure (Fm3m space group). The spheres were composed of nanoparticles with an average crystallite size of about 10 nm. The Ln(0.1)Ce(0.9)O2-δ compositions exhibited the highest specific surface area (∼ 60 m(2) g(-1)). In situ XRD experiments showed an increase in lattice parameters upon reduction, which was attributed to the reduction of Ce(4+) and Pr(4+) cations to Ce(3+) and Pr(3+), which have larger radii, and to the associated increase in VO concentration. This increase in lattice parameters was considerably more pronounced for PrDC than GDC, and was explained by the considerably larger change in ionic radius for Pr upon reduction. XANES absorption experiments at the Ce and Pr L3-edge showed that the changes observed upon reduction of the Pr-containing samples resulted mostly from the formation of Pr(3+) rather than Ce(3+), and supported the previously reported proposal that Pr(3+) has a stabilizing effect on Ce(4+).

  9. Redox properties of nanostructured lanthanide-doped ceria spheres prepared by microwave assisted hydrothermal homogeneous co-precipitation

    NASA Astrophysics Data System (ADS)

    Muñoz, F. F.; Acuña, L. M.; Albornoz, C. A.; Leyva, A. G.; Baker, R. T.; Fuentes, R. O.

    2014-11-01

    In this work, nanostructured LnxCe1-xO2-δ (Ln: Gd and Pr; x = 0.1 and 0.2) spheres were synthesized by microwave assisted hydrothermal homogeneous co-precipitation and their properties were characterized by synchrotron radiation XRD, X-ray absorption near-edge spectroscopy (XANES) and scanning and high-resolution electron microscopy (SEM and HRTEM). In situ XRD and XANES experiments were carried out under reducing and oxidizing conditions in order to investigate the redox behaviour of these materials. The nanostructured mixed oxide spheres were found to have a cubic crystal structure (Fm3m space group). The spheres were composed of nanoparticles with an average crystallite size of about 10 nm. The Ln0.1Ce0.9O2-δ compositions exhibited the highest specific surface area (~60 m2 g-1). In situ XRD experiments showed an increase in lattice parameters upon reduction, which was attributed to the reduction of Ce4+ and Pr4+ cations to Ce3+ and Pr3+, which have larger radii, and to the associated increase in VO concentration. This increase in lattice parameters was considerably more pronounced for PrDC than GDC, and was explained by the considerably larger change in ionic radius for Pr upon reduction. XANES absorption experiments at the Ce and Pr L3-edge showed that the changes observed upon reduction of the Pr-containing samples resulted mostly from the formation of Pr3+ rather than Ce3+, and supported the previously reported proposal that Pr3+ has a stabilizing effect on Ce4+.In this work, nanostructured LnxCe1-xO2-δ (Ln: Gd and Pr; x = 0.1 and 0.2) spheres were synthesized by microwave assisted hydrothermal homogeneous co-precipitation and their properties were characterized by synchrotron radiation XRD, X-ray absorption near-edge spectroscopy (XANES) and scanning and high-resolution electron microscopy (SEM and HRTEM). In situ XRD and XANES experiments were carried out under reducing and oxidizing conditions in order to investigate the redox behaviour of these materials. The nanostructured mixed oxide spheres were found to have a cubic crystal structure (Fm3m space group). The spheres were composed of nanoparticles with an average crystallite size of about 10 nm. The Ln0.1Ce0.9O2-δ compositions exhibited the highest specific surface area (~60 m2 g-1). In situ XRD experiments showed an increase in lattice parameters upon reduction, which was attributed to the reduction of Ce4+ and Pr4+ cations to Ce3+ and Pr3+, which have larger radii, and to the associated increase in VO concentration. This increase in lattice parameters was considerably more pronounced for PrDC than GDC, and was explained by the considerably larger change in ionic radius for Pr upon reduction. XANES absorption experiments at the Ce and Pr L3-edge showed that the changes observed upon reduction of the Pr-containing samples resulted mostly from the formation of Pr3+ rather than Ce3+, and supported the previously reported proposal that Pr3+ has a stabilizing effect on Ce4+. Electronic supplementary information (ESI) available: Structural parameters and standard Rietveld agreement factors for nanostructured LnDC spheres are presented in Tables S1-S4, SR-XRD patterns in the vicinity of the 111 reflection for nanostructured LnDC spheres are exhibited in Fig. S1-S4 and the Ce L3-edge XANES spectra of the nanostructured GDC10, GDC20, and PrDC20 spheres at 500 °C under reducing (5% H2/He, 20 mL min-1) and oxidizing (synthetic air: 21% O2/N2, 50 ml min-1) conditions, and their corresponding fits are shown in Fig. S5a-f. See DOI: 10.1039/c4nr05630b

  10. Influence of the process parameters on the spray pyrolysis technique, on the synthesis of gadolinium doped-ceria thin film

    SciTech Connect

    Halmenschlager, C.M.; Neagu, R.; Rose, L.; Malfatti, C.F.

    2013-02-15

    Graphical abstract: Gas-tight CGO made by spray pyrolysis suitable to be used as SOFC electrolyte. Display Omitted Highlights: ► Dense and crystalline CGO films deposited by spray pyrolysis on various substrates. ► Solvent did not have a strong influence on the film microstructure, defect concentration or thickness. ► The substrate did not have a strong influence on the film microstructure, defect concentration or thickness. ► Films with at least 2.5 μm of thickness presented high impermeability. ► The films obtained are suitable to use as a SOFC electrolyte. -- Abstract: This work presents the results of a process of optimization applied to gadolinia-doped ceria (Ce{sub 0.8}Gd{sub 0.2}O{sub 1.9−x}, or CGO) thin films, deposited by spray pyrolysis (SP). Spray pyrolysis is a high thermal deposition method that combines material deposition and heat treatment. This combination is advantageous since the post-deposition heat treatment step is not necessary. However, stresses are solidified in the coating during the deposition, which may lead to the initiation of a crack in the coating. The aim of this work was to achieve thin, dense, and continuous CGO coatings, which may be used as gas separation membranes and as a solid state electrochemical interfaces. Dense, flat, low-defect substrates such as silica slides, silicon mono crystal wafers, and porous substrates were used as substrates in this work. Cerium ammonium nitrate and gadolinium acetylacetonate were dissolved in ethanol and butyl carbitol to form a precursor solution that was sprayed on the heated substrates. Process parameters such as solvent composition, deposition rate and different heating regimes were analyzed. The microstructure was analyzed by secondary electron microscopy (SEM) and was found that thin, dense, and defect-free films could be produced on dense and porous substrates. The results obtained show that it is possible to obtain a CGO dense film deposited by spray pyrolysis. X

  11. A study of gadolinia-doped ceria electrolyte by electrochemical impedance spectroscopy

    NASA Astrophysics Data System (ADS)

    Zhang, Lei; Liu, Feng; Brinkman, Kyle; Reifsnider, Kenneth L.; Virkar, Anil V.

    2014-02-01

    Samples of Gd2O3-doped CeO2 (GDC) were fabricated by sintering of powder compacts. Impedance spectra were measured from 400 °C to 675 °C in air by electrochemical impedance spectroscopy (EIS). Above ∼500 °C, high frequency arc was not semicircular but could be fitted with a constant phase element (CPE). Above ∼625 °C, high frequency arc could not be resolved due to a significant contribution from the inductive load. The impedance spectra were described using a simple equivalent circuit which included the leads/instrument impedance. The leads/instrument impedance was measured over a range of frequencies and temperatures. The high frequency part of the impedance after subtracting leads/instrument impedance could be resolved even at the highest measurement temperature and was described by a semicircle representative of transport across grain boundaries. From these measurements, grain and grain boundary resistivities were determined. The corresponding activation energies were 0.69 eV and 1.11 eV, respectively. The grain boundary capacitance was nearly independent of temperature. The present results show that grain boundary effects can be described by a resistor and a capacitor. Relevant equivalent circuit parameters were obtained from intercepts, maxima and minima in impedance diagrams.

  12. A Ratiometric Luminescent Thermometer Co-doped with Lanthanide and Transition Metals.

    PubMed

    Li, Zhiqiang; Hou, Zhaohui; Ha, Denghui; Li, Huanrong

    2015-12-01

    Herein, we report the fabrication of a sensitive ratiometric and colorimetric luminescent thermometer with a wide operating-temperature range, from cryogenic temperatures up to high temperatures, through the combination of lanthanide and transition metal complexes. Benefiting from the transition metal complex as a self-reference, the lanthanide content in the mixed-coordination complex, Eu0.05(Mebip-mim bromine)0.15Zn0.95(Mebip-mim bromine)1.9, was lowered to 5%.

  13. Lanthanide-doped Sr2YF7 nanoparticles: controlled synthesis, optical spectroscopy and biodetection

    NASA Astrophysics Data System (ADS)

    Yang, Yuhan; Tu, Datao; Zheng, Wei; Liu, Yongsheng; Huang, Ping; Ma, En; Li, Renfu; Chen, Xueyuan

    2014-09-01

    Sr2YF7, as an important matrix for trivalent lanthanide (Ln3+) ions to fabricate upconversion (UC) or downshifting (DS) phosphors, has been rarely reported. Herein, monodisperse and size-controllable tetragonal-phase Ln3+-doped Sr2YF7 nanoparticles (NPs) were synthesized via a facile thermal decomposition method. Upon excitation at 980 nm, UC luminescence properties of Sr2YF7:Ln3+/Yb3+ (Ln = Tm, Er) NPs were systematically surveyed. Particularly, after coating an inert Sr2YF7 shell, the UC luminescence intensities of Sr2YF7:Tm3+/Yb3+ and Sr2YF7:Er3+/Yb3+ NPs were enhanced by ~22 and 4 times, respectively. Furthermore, intense multicolor DS luminescence was also achieved in Ce3+/Tb3+ or Eu3+ doped Sr2YF7 NPs, with absolute quantum yields of 55.1% (Tb3+) and 11.2% (Eu3+). The luminescence lifetimes of 5D4 (Tb3+) and 5D0 (Eu3+) were determined to be 3.7 and 8.1 ms, respectively. By utilizing the long-lived luminescence of Ln3+ in these Sr2YF7 NPs, we demonstrated their application as sensitive heterogeneous time-resolved photoluminescence bioprobes to detect the protein of avidin and the tumor marker of the carcinoembryonic antigen (CEA) with their limits of detection down to 40.6 and 94.9 pM, and thus reveal the great potential of these Sr2YF7:Ln3+ nanoprobes in cancer diagnosis.Sr2YF7, as an important matrix for trivalent lanthanide (Ln3+) ions to fabricate upconversion (UC) or downshifting (DS) phosphors, has been rarely reported. Herein, monodisperse and size-controllable tetragonal-phase Ln3+-doped Sr2YF7 nanoparticles (NPs) were synthesized via a facile thermal decomposition method. Upon excitation at 980 nm, UC luminescence properties of Sr2YF7:Ln3+/Yb3+ (Ln = Tm, Er) NPs were systematically surveyed. Particularly, after coating an inert Sr2YF7 shell, the UC luminescence intensities of Sr2YF7:Tm3+/Yb3+ and Sr2YF7:Er3+/Yb3+ NPs were enhanced by ~22 and 4 times, respectively. Furthermore, intense multicolor DS luminescence was also achieved in Ce3+/Tb3+ or Eu3

  14. Making sense of lanthanide luminescence.

    PubMed

    Werts, Martinus H V

    2005-01-01

    The luminescence of trivalent lanthanide ions has found applications in lighting, lasers, optical telecommunications, medical diagnostics, and various other fields. This introductory review presents the basics of organic and inorganic luminescent materials containing lanthanide ions, their applications, and some recent developments. After a brief history of the discovery, purification and early spectroscopic studies of the lanthanides, the radiative and nonradiative transitions of the 4f electrons in lanthanide ions are discussed. Lanthanide-doped phosphors, glasses and crystals as well as luminescent lanthanide complexes with organic ligands receive attention with respect to their preparation and their applications. Finally, two recent developments in the field of luminescent materials are addressed: near-infrared luminescent lanthanide complexes and lanthanide-doped nano-particles.

  15. Catalytic modification of Ni-Sm-doped ceria anodes with copper for direct utilization of dry methane in low-temperature solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Wang, Zhicheng; Weng, Wenjian; Cheng, Kui; Du, Piyi; Shen, Ge; Han, Gaorong

    2008-05-01

    A Cu/Ni/Sm-doped ceria (SDC) anode has been designed for direct utilization of dry methane in low-temperature anode-supported solid oxide fuel cells. The anode is prepared by the impregnation method, whereby a small amount of Cu is incorporated into the previously prepared Ni/SDC porous matrix. After reduction, Cu nanoparticles adhere to and are uniformly distributed on the surface of the Ni/SDC matrix. For the resulting Cu/Ni/SDC anode-supported cell, maximum power density of 317 mW cm-2 is achieved at 600 °C. The power density shows only ∼2% loss after 12-h operation. The results demonstrate that the Cu/Ni/SDC anode effectively suppresses carbon deposition by decreasing the Ni surface area available and the level of carbon monoxide disproportionation. This combination of effects results in very low-power density loss over the operating time.

  16. Relationship Between Particle and Plasma Properties and Coating Characteristics of Samaria-Doped Ceria Prepared by Atmospheric Plasma Spraying for Use in Solid Oxide Fuel Cells

    NASA Astrophysics Data System (ADS)

    Cuglietta, Mark; Kesler, Olivera

    2012-06-01

    Samaria-doped ceria (SDC) has become a promising material for the fabrication of high-performance, intermediate-temperature solid oxide fuel cells (SOFCs). In this study, the in-flight characteristics, such as particle velocity and surface temperature, of spray-dried SDC agglomerates were measured and correlated to the resulting microstructures of SDC coatings fabricated using atmospheric plasma spraying, a manufacturing technique with the capability of producing full cells in minutes. Plasmas containing argon, nitrogen and hydrogen led to particle surface temperatures higher than those in plasmas containing only argon and nitrogen. A threshold temperature for the successful deposition of SDC on porous stainless steel substrates was calculated to be 2570 °C. Coating porosity was found to be linked to average particle temperature, suggesting that plasma conditions leading to lower particle temperatures may be most suitable for fabricating porous SOFC electrode layers.

  17. Effects of some rare earth and carbonate-based co-dopants on structural and electrical properties of samarium doped ceria (SDC) electrolytes for solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Anwar, Mustafa; Khan, Zuhair S.; Mustafa, Kamal; Rana, Akmal

    2015-09-01

    In the present study, samarium doped ceria (SDC) and SDC-based composite with the addition of K2CO3 were prepared by co-precipitation route and effects of pH of the solution and calcination temperature on microstructure of SDC and SDC-K2CO3, respectively, were investigated. Furthermore, experimentation was performed to investigate into the ionic conductivity of pure SDC by co-doping with yttrium i.e., YSDC, XRD and SEM studies show that the crystallite size and particle size of SDC increases with the increase in pH. The SEM images of all the samples of SDC synthesized at different pH values showed the irregular shaped and dispersed particles. SDC-K2CO3 was calcined at 600∘C, 700∘C and 800∘C for 4 h and XRD results showed that crystallite size increases while lattice strain, decreases with the increase in calcination temperature and no peaks were detected for K2CO3 as it is present in an amorphous form. The ionic conductivity of the electrolytes increases with the increase in temperature and SDC-K2CO3 shows the highest value of ionic conductivity as compared to SDC and YSDC. Chemical compatibility tests were performed between the co-doped electrolyte and lithiated NiO cathode at high temperature. It revealed that the couple could be used up to the temperature of 700∘C.

  18. Semi-emprical and ab initio study of lanthanide and transition metal ions doped in hexagonol beta-NaYF4

    NASA Astrophysics Data System (ADS)

    Yao, Ge

    Lanthanide and transition metal doped hexagonal beta-NaYF4 nanocrystals have a wide variety of applications in bioimaging, solar concentrators, display panel technology, photodynamic therapy, and security printing. This dissertation research employed two complementary approaches to characterizing the photoactive properties of lanthanides and transition metals doped in beta-NaYF 4. One approach was a semi-empirical method, based on Judd-Ofelt theory, used to calculate the optical transition intensity parameters for Er 3+ doped in beta-phase NaYF4:Yb3+ from measured emission intensity ratios and the diffuse reflectance spectrum. The second approach was based on first-principles density functional theory, investigating the effect of doping on the electronic structure of the materials of interest. In this latter approach, models of beta-NaYF4 with different numbers of atoms in supercells were built, where supercells were reproduced through translational symmetry creating periodic boundary conditions. The models were tested for convergence of local structure and energy as a function of supercell size. First, a converged model for the un-doped "parent" structure of the host material was developed using the Perdew-Burke-Ernzerhof (PBE) functional. Then, a systematic investigation of the optimized geometry and electronic structure of the doped beta-NaYF4: Ln3+ nanocrystals, was conducted using both spin-polarized DFT and non-collinear-spin DFT. For transition metal doping, the relationship between site symmetry and spin state with different doping concentrations was also demonstrated.

  19. Ionic liquid assisted microwave synthesis route towards color-tunable luminescence of lanthanide- doped BiPO4

    SciTech Connect

    Cybinska, Joanna; Lorbeer, Chantal; Mudring, Anja -Verena

    2015-07-08

    Ln3+-doped (Ln=Sm, Eu, Tb, Dy) nanoparticles of BiPO4 with a particle size below 10 nm were synthesized in a straightforward manner from the appropriate mixture of the respective metal acetates and the task-specific ionic liquids choline or butylammonium dihydrogen-phosphate by conversion in a laboratory microwave (120 °C, 10 min). The ionic liquid acts not only as a solvent and microwave susceptor, but also as the reaction partner and nanoparticle stabilizer. The materials were thoroughly characterized not only with respect to their optical properties but also by PXRD, FT-IR, TEM techniques. Furthermore, depending on the lanthanide, the nanomaterial shows intense luminescence of different colors such as: orange (Sm3+), red (Eu3+), green (Tb3+) or even white (Dy3+).

  20. Ionic liquid assisted microwave synthesis route towards color-tunable luminescence of lanthanide- doped BiPO4

    DOE PAGES

    Cybinska, Joanna; Lorbeer, Chantal; Mudring, Anja -Verena

    2015-07-08

    Ln3+-doped (Ln=Sm, Eu, Tb, Dy) nanoparticles of BiPO4 with a particle size below 10 nm were synthesized in a straightforward manner from the appropriate mixture of the respective metal acetates and the task-specific ionic liquids choline or butylammonium dihydrogen-phosphate by conversion in a laboratory microwave (120 °C, 10 min). The ionic liquid acts not only as a solvent and microwave susceptor, but also as the reaction partner and nanoparticle stabilizer. The materials were thoroughly characterized not only with respect to their optical properties but also by PXRD, FT-IR, TEM techniques. Furthermore, depending on the lanthanide, the nanomaterial shows intense luminescencemore » of different colors such as: orange (Sm3+), red (Eu3+), green (Tb3+) or even white (Dy3+).« less

  1. A visual and reversible assay for temperature using thioflavin T-doped lanthanide/nucleotide coordination polymers.

    PubMed

    Li, Yan-Yun; Jiang, Xiao-Qin; Zhang, Min; Shi, Guoyue

    2016-04-21

    In this work, we prepared a type of thioflavin T (ThT)-doped lanthanide/nucleotide coordination polymer by the self-assembly of ThT, europium ions (Eu(3+)) and nucleotides (guanosine monophosphate, GMP) in aqueous solution (i.e. ThT/Eu/GMP). The Eu/GMP coordination polymers show excellent adaptive inclusion properties for ThT in a convenient one-step approach, which can readily enhance the fluorescence of ThT via the restricted effect. Moreover, the as-prepared hydrophilic ThT/Eu/GMP coordination polymers have the capability to act as a temperature-sensitive, visual and reversible sensor in aqueous solution under the irradiation of visible light. Our proposed design is cost-effective and simple to prepare without chemical modification or fluorescence labeling. PMID:27010102

  2. Proton-conducting Micro-solid Oxide Fuel Cells with Improved Cathode Reactions by a Nanoscale Thin Film Gadolinium-doped Ceria Interlayer

    PubMed Central

    Li, Yong; Wang, Shijie; Su, Pei-Chen

    2016-01-01

    An 8 nm-thick gadolinium-doped ceria (GDC) layer was inserted as a cathodic interlayer between the nanoscale proton-conducting yttrium-doped barium zirconate (BZY) electrolyte and the porous platinum cathode of a micro-solid oxide fuel cell (μ-SOFC), which has effectively improved the cathode reaction kinetics and rendered high cell power density. The addition of the GDC interlayer significantly reduced the cathodic activation loss and increased the peak power density of the μ-SOFC by 33% at 400 °C. The peak power density reached 445 mW/cm2 at 425 °C, which is the highest among the reported μ-SOFCs using proton-conducting electrolytes. The impressive performance was attributed to the mixed protonic and oxygen ionic conducting properties of the nano-granular GDC, and also to the high densities of grain boundaries and lattice defects in GDC interlayer that favored the oxygen incorporation and transportation during the oxygen reduction reaction (ORR) and the water evolution reaction at cathode. PMID:26928192

  3. Proton-conducting Micro-solid Oxide Fuel Cells with Improved Cathode Reactions by a Nanoscale Thin Film Gadolinium-doped Ceria Interlayer

    NASA Astrophysics Data System (ADS)

    Li, Yong; Wang, Shijie; Su, Pei-Chen

    2016-02-01

    An 8 nm-thick gadolinium-doped ceria (GDC) layer was inserted as a cathodic interlayer between the nanoscale proton-conducting yttrium-doped barium zirconate (BZY) electrolyte and the porous platinum cathode of a micro-solid oxide fuel cell (μ-SOFC), which has effectively improved the cathode reaction kinetics and rendered high cell power density. The addition of the GDC interlayer significantly reduced the cathodic activation loss and increased the peak power density of the μ-SOFC by 33% at 400 °C. The peak power density reached 445 mW/cm2 at 425 °C, which is the highest among the reported μ-SOFCs using proton-conducting electrolytes. The impressive performance was attributed to the mixed protonic and oxygen ionic conducting properties of the nano-granular GDC, and also to the high densities of grain boundaries and lattice defects in GDC interlayer that favored the oxygen incorporation and transportation during the oxygen reduction reaction (ORR) and the water evolution reaction at cathode.

  4. Controllable synthesis and upconversion emission of ultrasmall lanthanide-doped Sr2GdF7 nanocrystals

    NASA Astrophysics Data System (ADS)

    Xiang, Lijun; Ren, Guozhong; Mao, Yifu; He, Jin; Su, Rui

    2015-11-01

    The effect of rare-earth ions content on the phase structure, crystal size and morphology of SrF2-GdF3 system were studied under solvothermal conditions. By tuning the molar ratio of reactants, tetragonal phase Sr2GdF7 nanocrystals (NCs) were synthesized via solvothermal method using oleic acid as capping ligands. The effects of reaction conditions on the phase structure, crystal size, morphology, and upconversion (UC) emission properties of the products were investigated. The results reveal that apropos Gd3+ ions content (0.30-0.45 mmol) is favorable to the formation of pure phase Sr2GdF7 NCs with more uniform size distribution. The average crystalline size of the products can be controlled less than 10 nm. The energy transfer UC mechanisms for the fluorescent intensity were also investigated. Following Yb3+, Er3+, Tm3+ and Ho3+ ions doping, the Sr2GdF7 NCs show intense green, yellow, and white-color UC emission under the excitation of a 980 nm laser, and the doping concentration of lanthanide ions was optimized, which makes the NCs show maximum intensities under the excitation of a 980 nm laser.

  5. Oxygen nonstoichiometry and thermodynamic characterization of Zr doped ceria in the 1573–1773 K temperature range† †Electronic supplementary information (ESI) available: XRD patterns and SEM images. See DOI: 10.1039/c4cp04916k Click here for additional data file.

    PubMed Central

    Takacs, M.; Steinfeld, A.

    2015-01-01

    This work encompasses the thermodynamic characterization and critical evaluation of Zr4+ doped ceria, a promising redox material for the two-step solar thermochemical splitting of H2O and CO2 to H2 and CO. As a case study, we experimentally examine 5 mol% Zr4+ doped ceria and present oxygen nonstoichiometry measurements at elevated temperatures ranging from 1573 K to 1773 K and oxygen partial pressures ranging from 4.50 × 10–3 atm to 2.3 × 10–4 atm, yielding higher reduction extents compared to those of pure ceria under all conditions investigated, especially at the lower temperature range and at higher p O2. In contrast to pure ceria, a simple ideal solution model accounting for the formation of isolated oxygen vacancies and localized electrons accurately describes the defect chemistry. Thermodynamic properties are determined, namely: partial molar enthalpy, entropy, and Gibbs free energy. In general, partial molar enthalpy and entropy values of Zr4+ doped ceria are lower. The equilibrium hydrogen yields are subsequently extracted as a function of the redox conditions for dopant concentrations as high as 20%. Although reduction extents increase greatly with dopant concentration, the oxidation of Zr4+ doped ceria is thermodynamically less favorable compared to pure ceria. This leads to substantially larger temperature swings between reduction and oxidation steps, ultimately resulting in lower theoretical solar energy conversion efficiencies compared to ceria under most conditions. In effect, these results point to the importance of considering oxidation thermodynamics in addition to reduction when screening potential redox materials. PMID:25714616

  6. A systematic analysis of the spectra of the lanthanides doped into single crystal LaF/sub 3/

    SciTech Connect

    Carnall, W.T.; Goodman, G.L.; Rajnak, K.; Rana, R.S.

    1988-02-01

    The optical spectra of the lanthanides doped into single crystal LaF/sub 3/ have been interpreted in terms of transitions within 4f/sup N/ configurations. Energy-level calculations were based on a simultaneous diagonalization of the free-ion and crystal-field matrices using an approximate model with C/sub 2v/ site symmetry instead of the actual C/sub 2/ symmetry. Excellent correlations between experimental transition energies and the computed level structures were obtained; predicted levels are given for Pm/sup 3 +/. Previously unpublished experimental results for Nd/sup 3 +/ and Sm/sup 3 +/:LaF/sub 3/ are included in the tabulations. The spectroscopic data for each ion were analyzed independently, then the parameters of the effective-operator model were intercompared and systematic trends were identified. Since many of the 4f/sup N/ configurations extend well into the vacuum ultraviolet region, and thus beyond any presently available experimental observations, some of the free-ion (atomic) parameters were found to be only approximately defined by the accessible levels. However, the crystal-field parameters seem for the most part to be well established by fits to data at low energies. A new chart of the lanthanide ion 4f/sup N/ configuration energy level structures is presented. It was generated by including all of the computed crystal-field levels in the 0-50000 cm/sup -1/ range. In most cases, experimental analyses of individual ions extended to /approximately/40000 cm/sup /minus/1/. 94 refs., 23 figs., 10 tabs.

  7. Harnessing the Cancer Radiation Therapy by Lanthanide-Doped Zinc Oxide Based Theranostic Nanoparticles.

    PubMed

    Ghaemi, Behnaz; Mashinchian, Omid; Mousavi, Tayebeh; Karimi, Roya; Kharrazi, Sharmin; Amani, Amir

    2016-02-10

    In this paper, doping of europium (Eu) and gadolinium (Gd) as high-Z elements into zinc oxide (ZnO) nanoparticles (NPs) was designed to optimize restricted energy absorption from a conventional radiation therapy by X-ray. Gd/Eu-doped ZnO NPs with a size of 9 nm were synthesized by a chemical precipitation method. The cytotoxic effects of Eu/Gd-doped ZnO NPs were determined using MTT assay in L929, HeLa, and PC3 cell lines under dark conditions as well as exposure to ultraviolet, X-ray, and γ radiation. Doped NPs at 20 μg/mL concentration under an X-ray dose of 2 Gy were as efficient as 6 Gy X-ray radiation on untreated cells. It is thus suggested that the doped NPs may be used as photoinducers to increase the efficacy of X-rays within the cells, consequently, cancer cell death. The doped NPs also could reduce the received dose by normal cells around the tumor. Additionally, we evaluated the diagnostic efficacy of doped NPs as CT/MRI nanoprobes. Results showed an efficient theranostic nanoparticulate system for simultaneous CT/MR imaging and cancer treatment.

  8. Reduction enthalpy and charge distribution of substituted ferrites and doped ceria for thermochemical water and carbon dioxide splitting with DFT+U.

    PubMed

    Dimitrakis, D A; Tsongidis, N I; Konstandopoulos, A G

    2016-08-24

    The thermal reduction step of substituted ferrites (MFe2O4 where M = Fe, Ni, Co, Gd) and doped ceria (MxCe1-xO2, where M = Ce, Zr, Hf and x = 0.25) in two-step thermochemical cycles for H2O and CO2 splitting is investigated within the DFT+U framework. This thermal reduction step is described as the oxygen vacancy formation energy (reduction enthalpy), i.e. the energy required to create an oxygen vacancy in the crystal lattice. Oxides with a lower oxygen vacancy creation energy are easier to reduce. A Bader charge analysis of the reduction mechanism is carried out providing the charge distribution of the bulk and reduced ions, enabling interrelations of the substitute ions and the resulting reduction energies. Based on the approach presented here, interesting solar fuels producing materials are CoFe2O4, NiFe2O4 and Hf0.25Ce0.75O2.

  9. High temperature structural study of Gd-doped ceria by synchrotron X-ray diffraction (673 K ≤ T ≤ 1073 K).

    PubMed

    Artini, Cristina; Pani, Marcella; Lausi, Andrea; Masini, Roberto; Costa, Giorgio A

    2014-10-01

    The crystallographic features of Gd-doped ceria were investigated at the operating temperature of solid oxides fuel cells, where these materials are used as solid electrolytes. (Ce(1-x)Gd(x))O(2-x/2) samples (x = 0.1, 0.3, 0.5, 0.7) were prepared by coprecipitation of mixed oxalates, treated at 1473 K in air, and analyzed by synchrotron X-ray diffraction in the temperature range 673 K ≤ T ≤ 1073 K at the Elettra synchrotron radiation facility located in Trieste, Italy. In the whole temperature span a boundary was found at x ∼ 0.2 between a CeO2-based solid solution (for x ≤ 0.2) and a structure where Gd2O3 microdomains grow within the CeO2 matrix, taking advantage of the similarity between Gd(3+) and Ce(4+) sizes; the existence of the boundary at x ∼ 0.2 was confirmed also by measurements of ionic conductivity performed by impedance spectroscopy. Similar to what observed at room temperature, the trend of the cell parameter shows the presence of a maximum; with increasing temperature, the composition corresponding to the maximum moves toward lower Gd content. This evidence can be explained by analyzing the behavior of the coefficient of thermal expansion as a function of composition.

  10. Slurry spin coating of thin film yttria stabilized zirconia/gadolinia doped ceria bi-layer electrolytes for solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Kim, Hyun Joong; Kim, Manjin; Neoh, Ke Chean; Han, Gwon Deok; Bae, Kiho; Shin, Jong Mok; Kim, Gyu-Tae; Shim, Joon Hyung

    2016-09-01

    Thin ceramic bi-layered membrane comprising yttria-stabilized zirconia (YSZ) and gadolinia-doped ceria (GDC) is fabricated by the cost-effective slurry spin coating technique, and it is evaluated as an electrolyte of solid oxide fuel cells (SOFCs). It is demonstrated that the slurry spin coating method is capable of fabricating porous ceramic films by adjusting the content of ethyl-cellulose binders in the source slurry. The porous GDC layer deposited by spin coating under an optimal condition functions satisfactorily as a cathode-electrolyte interlayer in the test SOFC stack. A 2-μm-thick electrolyte membrane of the spin-coated YSZ/GDC bi-layer is successfully deposited as a dense and stable film directly on a porous NiO-YSZ anode support without any interlayers, and the SOFC produces power output over 200 mW cm-2 at 600 °C, with an open circuit voltage close to 1 V. Electrochemical impedance spectra analysis is conducted to evaluate the performance of the fuel cell components in relation with the microstructure of the spin-coated layers.

  11. Reduction enthalpy and charge distribution of substituted ferrites and doped ceria for thermochemical water and carbon dioxide splitting with DFT+U.

    PubMed

    Dimitrakis, D A; Tsongidis, N I; Konstandopoulos, A G

    2016-08-24

    The thermal reduction step of substituted ferrites (MFe2O4 where M = Fe, Ni, Co, Gd) and doped ceria (MxCe1-xO2, where M = Ce, Zr, Hf and x = 0.25) in two-step thermochemical cycles for H2O and CO2 splitting is investigated within the DFT+U framework. This thermal reduction step is described as the oxygen vacancy formation energy (reduction enthalpy), i.e. the energy required to create an oxygen vacancy in the crystal lattice. Oxides with a lower oxygen vacancy creation energy are easier to reduce. A Bader charge analysis of the reduction mechanism is carried out providing the charge distribution of the bulk and reduced ions, enabling interrelations of the substitute ions and the resulting reduction energies. Based on the approach presented here, interesting solar fuels producing materials are CoFe2O4, NiFe2O4 and Hf0.25Ce0.75O2. PMID:27507281

  12. Strength and phase stability of yttria-ceria-doped tetragonal zirconia/alumina composites sintered and hot isostatically pressed in argon-oxygen gas atmosphere

    SciTech Connect

    Hirano, M.; Inada, H. )

    1991-03-01

    Yttria-ceria-doped tetragonal zirconia ((Y,Ce)-TZP)/alumina (Al{sub 2}O{sub 3}) composites were fabricated by hot isostatic pressing at 1400{degrees} to 1450{degrees}C and 196 MPa in an Ar-O{sub 2} atmosphere using the fine powders prepared by hydrolysis of ZrOCl{sub 2} solution. The composites consisting of 25 wt% Al{sub 2}O{sub 3} and tetragonal zirconia with compositions 4 mol% YO{sub 1.5}{minus}4 mol% CeO{sub 2}-ZrO{sub 2} and 2.5 mol% YO{sub 1.5}{minus}5.5 mol% CeO{sub 2}-ZrO{sub 2} exhibited means fracture strength as high as 2000 MPa and were resistant to phase transformation under saturated water vapor pressure at 180{degrees}C (1 MPa). Postsintering hot isostatic pressing of (4Y, 4Ce)-TZP/Al{sub 2}O{sub 3} and (2.5Y, 5.5Ce)-TZP/Al{sub 2}O{sub 3} composites was useful to enhance the phase stability under hydrothermal conditions and strength.

  13. Effect of tar fractions from coal gasification on nickel-yttria stabilized zirconia and nickel-gadolinium doped ceria solid oxide fuel cell anode materials

    NASA Astrophysics Data System (ADS)

    Lorente, E.; Berrueco, C.; Millan, M.; Brandon, N. P.

    2013-11-01

    The allowable tar content in gasification syngas is one of the key questions for the exploitation of the full potential of fuel cell concepts with integrated gasification systems. A better understanding of the interaction between tars and the SOFC anodes which leads to carbon formation and deposition is needed in order to design systems where the extent of gas cleaning operations is minimized. Model tar compounds (toluene, benzene, naphthalene) have been used in experimental studies to represent those arising from biomass/coal gasification. However, the use of toluene as a model tar overestimates the negative impact of a real gasification tar on SOFC anode degradation associated with carbon formation. In the present work, the effect of a gasification tar and its distillation fractions on two commercially available fuel cell anodes, Ni/YSZ (yttria stabilized zirconia) and Ni/CGO (gadolinium doped ceria), is reported. A higher impact of the lighter tar fractions was observed, in terms of more carbon formation on the anodes, in comparison with the whole tar sample. The characterization of the recovered tars after contact with the anode materials revealed a shift towards a heavier molecular weight distribution, reinforcing the view that these fractions have reacted on the anode.

  14. Preperation and electrochemical characterization of Sm and Gd co-doped ceria/carbonate composite electrolytes for IT-SOFC applications

    NASA Astrophysics Data System (ADS)

    Dikmen, Sibel; Ozsakarya, Rabia; Dikmen, Erdal

    2014-03-01

    Sm and Gd co-doped ceria based composite electrolytes were prepared by mixing nanosized powders of Ce0.8Sm0.1Gd0.1O2-δ (SGDC) and alkaline carbonates (Na-Li)2CO3, (Li-K)2CO3,and(Na-K)2CO3 at a weight ratio of 4:1. Structure of the samples was characterized by powder X-ray diffraction. The microstructure and morphology were examined by SEM. Impedance spectroscopy was used to perform electrochemical characterization. The conductivities of the samples increase as the temperature increases and for the composite electrolytes SGDC(Na-Li)2CO3,andSGDC(Li-K)2CO3, there is a sharp increase in conductivity at around 475 and 450oC, respectively. This sudden change in the conductivity refers to superionic phase transition in the interfaces between SGDC phase and salt phase. The single cell power density reached a maximum of 1056, 826, and 565 mWcm-2 for SGDC/ (Na-Li)2CO3, SGDC/(Li-K)2CO3,andSGDC/(Na-K)2CO3 as the electrolytes, respectively. This work was funded by TUB?TAK 106T536, SDU-BAP 3231-YL1-12.

  15. STRUCTURAL ANALYSIS OF THE COMBUSTION SYNTHESIZED Y3+ DOPED CERIA (Ce0.9Y0.1O1.95)

    NASA Astrophysics Data System (ADS)

    Jeyanthi, C. Esther; Siddheswaran, R.; Kumar, Pushpendra; Mangalaraja, R. V.; Siva Shankar, V.; Rajarajan, K.

    2013-07-01

    Y3+ doped CeO2 nanopowders (Ce0.9Y0.1O1.95, abbreviated as YDC) were synthesized by citrate-nitrate-auto combustion process using cerium nitrate hexahydrate, yttrium nitrate hexahydrate and citric acid. The as-synthesized powders were calcined at 700°C and converted into dense bodies followed by sintering at 1200°C. The microstructure of the synthesized powders and sintered bodies were examined by scanning electron microscopy (SEM). The surface morphology of the nanoparticles and clusters were also analysed by transmission electron microscopy (TEM). The particles size of the YDC was found to be in the range from 10 to 30 nm, which is in good agreement with the crystallite size calculated from X-ray peak broadening method. Also, the X-ray diffraction confirmed that the Ce0.9Y0.1O1.95 crystallizes as the cubic fluorite structure of pure ceria. The optical absorption by functional molecules, impurities and oxygen vacancies were analysed by FTIR and Raman spectroscopic studies. From the FTIR spectrum, the absorption peak found at 530 cm-1 is attributed to the vibrations of metal-oxygen bonds. The characteristic Raman peak was found to be 468 cm-1, and the minute absorption of oxygen vacancies were observed in the region 500-640 cm-1.

  16. Controllable Synthesis of Monodisperse Er3+-Doped Lanthanide Oxyfluorides Nanocrystals with Intense Mid-Infrared Emission

    NASA Astrophysics Data System (ADS)

    He, Huilin; Liu, Qiang; Yang, Dandan; Pan, Qiwen; Qiu, Jianrong; Dong, Guoping

    2016-10-01

    Monodisperse lanthanide oxyfluorides LnOF (Ln = Gd, Y) with mid-infrared emissions were controllably synthesized via a mild co-precipitation route and a subsequent heat-treatment. The detailed composition and morphology were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and high resolution transmission electron microscopy (HRTEM). The results showed that monodisperse GdOF:Er3+ were nano-riced shape with length about 350 nm and width about 120 nm, while the quasi-spherical YOF:Er3+ were uniform nanocrystals with an average size around 100 nm. The influence of calcination temperature on the size and phase transition of LnOF nanocrystals was also investigated. The photoluminescence (PL) spectra indicated that the 2.7 μm emission of Er3+ had achieved in both GdOF and YOF nanocrystals, which were calcined at different temperatures. In addition, the decay time of both 4I13/2 and 4I13/2 energy levels corresponding to Er3+ in YOF nanocrystals were also studied in detail. The results suggested that both rice-shaped GdOF nanocrystals and YOF nanocrystals could provide suitable candidate materials for nanocrystals-glass composites, which could be a step forward to the realization of mid-infrared laser materials.

  17. Controllable Synthesis of Monodisperse Er3+-Doped Lanthanide Oxyfluorides Nanocrystals with Intense Mid-Infrared Emission

    PubMed Central

    He, Huilin; Liu, Qiang; Yang, Dandan; Pan, Qiwen; Qiu, Jianrong; Dong, Guoping

    2016-01-01

    Monodisperse lanthanide oxyfluorides LnOF (Ln = Gd, Y) with mid-infrared emissions were controllably synthesized via a mild co-precipitation route and a subsequent heat-treatment. The detailed composition and morphology were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and high resolution transmission electron microscopy (HRTEM). The results showed that monodisperse GdOF:Er3+ were nano-riced shape with length about 350 nm and width about 120 nm, while the quasi-spherical YOF:Er3+ were uniform nanocrystals with an average size around 100 nm. The influence of calcination temperature on the size and phase transition of LnOF nanocrystals was also investigated. The photoluminescence (PL) spectra indicated that the 2.7 μm emission of Er3+ had achieved in both GdOF and YOF nanocrystals, which were calcined at different temperatures. In addition, the decay time of both 4I13/2 and 4I13/2 energy levels corresponding to Er3+ in YOF nanocrystals were also studied in detail. The results suggested that both rice-shaped GdOF nanocrystals and YOF nanocrystals could provide suitable candidate materials for nanocrystals-glass composites, which could be a step forward to the realization of mid-infrared laser materials. PMID:27748411

  18. Functionally graded doped lanthanum cobalt ferrite and ceria-based composite interlayers for advancing the performance stability in solid oxide fuel cell

    NASA Astrophysics Data System (ADS)

    Ghosh, Koyel Banerjee; Mukhopadhyay, Jayanta; Basu, Rajendra N.

    2016-10-01

    Functionally graded composite interlayer based on 50% of La0.54Sr0.4Co0.2Fe0.8O3-δ and 50% of La0.54Sr0.4Fe0.2Co0.8O3-δ (CF-1) and cobalt and gadolinium doped ceria (CoCGO) is synthesized varying the mass ratio as CF-1:CoCGO = 80:20(L80-C20), 50:50(L50-C50) and 20:80(L20-C80). Detail study using impedance spectroscopy of symmetrical cell fabricated with CoCGO as electrolyte reveals the lowest electrode polarization 0.04 Ω cm2 at 800 °C for L80-C20 composite. Electrode and ohmic polarization is also evaluated configuring the symmetric cell as CF-1/L80-C20||CoCGO||L80-C20/CF-1. Symmetric cell with varying composition of the composite interlayer (L80-C20/L50-C50/L20-C80||CoCGO||L20-C80/L50-C50/L80-C20) shows considerably low electrode polarization of 0.067 Ω cm2 at 800 °C with activation energy 1.19 eV. Electrochemical performances evaluated using single cell configuration Ni-YSZ||YSZ||CoCGO/L20-C80/L50-C50/L80-C20/CF-1 shows power density as high as 2.03 W cm-2 at 800 °C at 0.7 V. Addition of composite interlayers increases the stability significantly and the voltage degradation is found negligible (0.9%) for first 300 h at a constant load of 0.5 A cm-2 which is further increased to 2.9% for next 300 h. The cell stability is clinically correlated with layer wise elemental 'Sr' mapping in the applied quad interlayers.

  19. Samaria-doped Ceria Modified Ni/YSZ Anode for Direct Methane Fuel in Tubular Solid Oxide Fuel Cells by Impregnation Method

    NASA Astrophysics Data System (ADS)

    Zhang, Long-shan; Gao, Jian-feng; Tian, Rui-fen; Xia, Chang-rong

    2009-08-01

    A porous NiO/yttria-stabilized zirconia anode substrate for tubular solid oxide fuel cells was prepared by gel casting technique. Nano-scale samaria-doped ceria (SDC) particles were formed onto the anode substrate to modify the anode microstructure by the impregnation of solution of Sm(NO3)3 and Ce(NO3)3. Electrochemical impedance spectroscopy, current-voltage and current-powder curves of the cells were measured using an electrochemical workstation. Scanning electron microcopy was used to observe the microstructure. The results indicate that the stability of the performance of the cell operated on humidified methane can be significantly improved by incorporating the nano-structured SDC particles, compared with the unmodified cell. This verifies that the coated SDC electrodes are very effective in suppressing catalytic carbon formation by blocking methane from approaching the Ni, which is catalytically active towards methane pyrolysis. In addition, it was found that a small amount of deposited carbon is beneficial to the performance of the anode. The cell showed a peak power density of 225 mW/cm2 when it was fed with H2 fuel at 700 °C, but the power density increased to 400 mW/cm2 when the fuel was switched from hydrogen to methane at the same flow rate. Methane conversion achieved about 90%, measured by gas chromatogram with a 10.0 mL/min flow rate of fuel at 700 °C. Although the carbon deposition was not suppressed absolutely, some deposited carbon was beneficial for performance improvement.

  20. Recent advances in lanthanide-doped upconversion nanomaterials: synthesis, nanostructures and surface modification

    NASA Astrophysics Data System (ADS)

    Qiu, Peiyu; Zhou, Na; Chen, Hengyu; Zhang, Chunlei; Gao, Guo; Cui, Daxiang

    2013-11-01

    Owing to their unique photo-physical properties, rare-earth ions-doped upconversion nanoparticles (UCNPs) have attracted extensive attention in recent years. UCNPs have many special merits, such as a long luminescence lifetime, narrow emission band widths, high quantum yields and low toxicity, which allows their potential applications in bio-medical field, biological luminescent labels and drug delivery carriers. Compared with traditional fluorescence labels exited by UV (ultraviolet), such as organic dyes and quantum dots, UCNPs can transfer near-infrared (NIR) light into visible light, which is commonly called upconversion luminescence (UCL). This paper reviews the recent advances of several typical synthesis methods of UCNPs in detail as well as the fabrication and optimization of the particle morphology, and the latest advances of UCNPs for multimode imaging, surface passivation and functionalization are also described.

  1. Preparation of Sm-doped ceria (SDC) nanowires and tubes by gas-liquid co-precipitation at room temperature

    SciTech Connect

    Gu Lina Meng Guangyao

    2008-06-03

    Sm-doped cerium dioxide (SDC) with fcc structure was formed using a gas-liquid chemical co-precipitation process at room temperature. Morphology and structure of the as-prepared samples were characterized using TG, XRD, TEM, HRTEM and SAED techniques. Under our specific experimental conditions, two kinds of 1D nano-structures SDC have been mainly obtained. SDC nanowires are 0.3-1.2 {mu}m in lengths and 5-20 nm in diameters. SDC nanotubes have outer diameters in 10-40 nm with lengths up to 2 {mu}m. The as-prepared SDC shows very strong UV absorption ability and the maximum absorption peak redshifts compared with that of SDC nanoparticles.

  2. Tuning Crystal Phase and Emission Properties of Upconversion Nanocrystals Through Lanthanide Doping.

    PubMed

    Luo, L; Liu, H B; Yao, L L; Dong, G S; Zhang, W; Wang, Y H; Qiu, Z R; Chen, J

    2016-01-01

    Infrared-to-visible upconversion fluorescent nanocrystals of Yb³⁺/Er³⁺-codoped NaYF₄ and Yb³⁺/Er³⁺/Gd³⁺-tridoped NaYF₄ were synthesized using a modified coprecipitation process. X-ray diffraction and transmission electron diffraction scans of the nanocrystals confirmed that Gd³⁺ doping caused a phase transition to occur in the nanocrystals, changing them from a cubic to a hexagonal phase. Hexagonal phase Yb³⁺/Er³⁺/Gd³⁺-tridoped NaYF₄ nanocrystals displayed much stronger and sharper upconversion luminescence, and larger intensity ratios of red over green emissions relative to their cubic phase counterparts. The influence of the crystal phase on the upconversion emission properties was explored by use of excitation power dependence curves, dynamic fluorescence and Raman spectra. The results suggest that the cubic-to-hexagonal phase transition decreases the crystal field symmetry, and then enhances upconversion luminescence intensity by relaxing forbidden selection rules. The conversion into the hexagonal phase also increases the number of phonon modes, and consequently improves the phonon-assisted energy transfer efficiency from Yb³⁺ to Er³⁺, thus facilitating the output of red emissions. PMID:27398498

  3. Secret lanthanides.

    PubMed

    Sturza, C M

    2014-09-15

    Lanthanides are a group of 15 chemical elements which, together with their salts, have come to be used in the last decade as homoeopathic remedies. The effective introduction of lanthanides and their salts into the clinical use, as homoeopathic remedies was based on the idea of Jan Scholten, MD to relate their physicochemical properties shown in the periodic table of elements to their homoeopathic potential. The lanthanides and their salts were prepared as homoeopathic remedies by Pharmacist Robert Münz.

  4. Secret lanthanides.

    PubMed

    Sturza, C M

    2014-09-15

    Lanthanides are a group of 15 chemical elements which, together with their salts, have come to be used in the last decade as homoeopathic remedies. The effective introduction of lanthanides and their salts into the clinical use, as homoeopathic remedies was based on the idea of Jan Scholten, MD to relate their physicochemical properties shown in the periodic table of elements to their homoeopathic potential. The lanthanides and their salts were prepared as homoeopathic remedies by Pharmacist Robert Münz. PMID:25408760

  5. ICP-MS Analysis of Lanthanide-Doped Nanoparticles as a Non-Radiative, Multiplex Approach to Quantify Biodistribution and Blood Clearance

    PubMed Central

    Crayton, Samuel H.; Elias, Andrew; Al-Zaki, Ajlan; Cheng, Zhiliang; Tsourkas, Andrew

    2011-01-01

    Recent advances in material science and chemistry have led to the development of nanoparticles with diverse physicochemical properties, e.g. size, charge, shape, and surface chemistry. Evaluating which physicochemical properties are best for imaging and therapeutic studies is challenging not only because of the multitude of samples to evaluate, but also because of the large experimental variability associated with in vivo studies (e.g. differences in tumor size, injected dose, subject weight, etc.). To address this issue, we have developed a lanthanide-doped nanoparticle system and analytical method that allows for the quantitative comparison of multiple nanoparticle compositions simultaneously. Specifically, superparamagnetic iron oxide (SPIO) with a range of different sizes and charges were synthesized, each with a unique lanthanide dopant. Following the simultaneous injection of the various SPIO compositions into tumor-bearing mice, inductively coupled plasma mass spectroscopy (ICP-MS) was used to quantitatively and orthogonally assess the concentration of each SPIO composition in serial blood samples and the resected tumor and organs. The method proved generalizable to other nanoparticle platforms, including dendrimers, liposomes, and polymersomes. This approach provides a simple, cost-effective, and non-radiative method to quantitatively compare tumor localization, biodistribution, and blood clearance of more than 10 nanoparticle compositions simultaneously, removing subject-to-subject variability. PMID:22100983

  6. Strong blue and white photoluminescence emission of BaZrO{sub 3} undoped and lanthanide doped phosphor for light emitting diodes application

    SciTech Connect

    Romero, V.H.; De la Rosa, E.; Salas, P.; Velazquez-Salazar, J.J.

    2012-12-15

    In this paper, we report the obtained strong broadband blue photoluminescence (PL) emission centered at 427 nm for undoped BaZrO{sub 3} observed after 266 nm excitation of submicron crystals prepared by hydrothermal/calcinations method. This emission is enhanced with the introduction of Tm{sup 3+} ions and is stronger than the characteristic PL blue emission of such lanthanide. The proposed mechanism of relaxation for host lattice emission is based on the presence of oxygen vacancies produced during the synthesis process and the charge compensation due to the difference in the electron valence between dopant and substituted ion in the host. Brilliant white light emission with a color coordinate of (x=0.29, y=0.32) was observed by combining the blue PL emission from the host with the green and red PL emission from Tb{sup 3+} and Eu{sup 3+} ions, respectively. The color coordinate can be tuned by changing the ratio between blue, green and red band by changing the concentration of lanthanides. - Graphical abstract: Strong blue emission from undoped BaZrO{sub 3} phosphor and white light emission by doping with Tb{sup 3+} (green) and Eu{sup 3+} (red) after 266 nm excitation. Highlights: Black-Right-Pointing-Pointer Blue emission from BaZrO{sub 3} phosphor. Black-Right-Pointing-Pointer Blue emission enhanced with Tm{sup 3+}. Black-Right-Pointing-Pointer White light from BaZrO{sup 3+} phosphor.

  7. Secret Lanthanides

    PubMed Central

    Sturza, CM

    2014-01-01

    Abstract Lanthanides are a group of 15 chemical elements which, together with their salts, have come to be used in the last decade as homoeopathic remedies. The effective introduction of lanthanides and their salts into the clinical use, as homoeopathic remedies was based on the idea of Jan Scholten, MD to relate their physicochemical properties shown in the periodic table of elements to their homoeopathic potential. The lanthanides and their salts were prepared as homoeopathic remedies by Pharmacist Robert Münz. PMID:25408760

  8. Lanthanide Contraction Effect In Magnetic Thermoelectric Materials Of Rare Earth-doped Bi1.5Pb0.5Ca2Co2O8

    NASA Astrophysics Data System (ADS)

    Sutjahja, Inge Magdalena; Akbar, Taufik; Nugroho, Agung

    2010-12-01

    We report in this paper the result of synthesis and crystal structure characterization of magnetic thermoelectric materials of rare-earth-doped Bi1.5Pb0.5Ca2Co2O8, namely Bi1.5Pb0.5Ca1.9RE0.1Co2O8 (RE = La, Pr, Sm, Eu, Gd, Ho). Single phase samples have been prepared by solid state reaction process using precursors of Bi2O3, PbO, CaCO3, RE2O3, and Co3O4. The precursors were pulverized, calcinated, and sintered in air at various temperatures for several hours. Analysis of XRD data shows that Bi1.5Pb0.5Ca1.9RE0.1Co2O8 compound is a layered system consisting of an alternate stack of CoO2 layer and Bi2Sr2O4 block along the c-axis. The misfit structure along b-direction is revealed from the difference of the b-axis length belonging to two sublattices, namely hexagonal CdI2-type CoO2 layer and rock-salt (RS) NaCl-type Bi2Sr2O4 block, while they possess the common a- and c-axis lattice parameters and β angles. The overall crystal structure parameters (a, b, and c) increases with type of doping from La to Ho, namely by decreasing the ionic radii of rare-earth ion. We discuss this phenomenon in terms of the lanthanide contraction, an effect commonly found in the rare-earth compound, results from poor shielding of nuclear charge by 4f electrons. In addition, the values of b-lattice parameters in these rare-earth doped samples are almost the same with those belongs to undoped parent compound (Bi1.5Pb0.5Sr2Co2O8) and its related Y-doped (Bi1.5Pb0.5Ca1.9Y0.1Co2O8) samples, while the c-values reduced significantly in rare-earth doped samples, with opposite trend with those of variation of a-axis length. Morevover, the misfit degree in rare-earth doped compound is higher in compared to parent compound and Y-doped samples. We argue that these structural changes induced by rare-earth doping may provide information for the variation of electronic structure of Co-ions (Co3+ and Co4+), in particular their different spin states of low-spin, intermediate-spin, and high-spin. This, in

  9. Poly(acrylic acid) modified lanthanide-doped GdVO4 hollow spheres for up-conversion cell imaging, MRI and pH-dependent drug release.

    PubMed

    Kang, Xiaojiao; Yang, Dongmei; Dai, Yunlu; Shang, Mengmeng; Cheng, Ziyong; Zhang, Xiao; Lian, Hongzhou; Ma, Ping'an; Lin, Jun

    2013-01-01

    In this study, multifunctional poly(acrylic acid) modified lanthanide-doped GdVO(4) nanocomposites [PAA@GdVO(4): Ln(3+) (Ln = Yb/Er, Yb/Ho, Yb/Tm)] were constructed by filling PAA hydrogel into GdVO(4) hollow spheres via photoinduced polymerization. The up-conversion (UC) emission colors (green, red and blue) can be tuned by changing the codopant compositions in the matrices. The composites have potential applications as bio-probes for cell imaging. Meanwhile, the hybrid spheres can act as T(1) contrast agents for magnetic resonance imaging (MRI) owing to the existence of Gd(3+) ions on the surface of composites. Due to the nature of PAA, DOX-loaded PAA@GdVO(4):Yb(3+)/Er(3+) system exhibits pH-dependent drug releasing kinetics. A lower pH offers a faster drug release rate. Such character makes the loaded DOX easily released at cancer cells. The cell uptake process of drug-loaded composites was observed by using confocal laser scanning microscopy (CLSM). The results indicate the potential application of the multifunctional composites as theragnostics (effective bimodal imaging probes and pH-responsive drug carriers).

  10. Synthesis of transition-metal-doped KTiOPO{sub 4} and lanthanide-doped RbTiOAsO{sub 4} isomorphs that absorb visible light

    SciTech Connect

    Anderson M.T.; Phillips, M.L.F.; Sinclair, M.B.

    1996-01-01

    The authors have substituted aliovalent transition-metal (M = Cr, Fe, Ni, Cu, Co) and lanthanide (Ln = Er) ions that absorb visible light onto the titanium sites of the nonlinear optical materials KTiOPO{sub 4} (KTP) and RbTiOAsO{sub 4} (RTA). The substitution formally creates a charge deficiency on the Ti site. To compensate for this, the authors have substituted aliovalent counterions on the titanium (Nb), phosphorus (S, Se, Cr, Mo, W, Re) oxygen (F), or potassium (Ca, Sr, Ba, Pb) sites. The resulting new materials expand the KTiOPO{sub 4} structure field for partial replacement of one or more ions. The M and Ln ions alter the optical absorption and second harmonic properties of the materials. The ions reduce the second harmonic intensities of the isomorphs and second harmonic radiation to be phase matched at slightly shorter wavelengths than in the undoped host.

  11. The stable and water-soluble neodymium-doped lanthanide fluoride nanoparticles for near infrared probing of copper ion.

    PubMed

    Xue, Fang-Min; Wang, He-Fang

    2012-09-15

    Neodymium (Nd(3+)) doped nanomaterials exhibited the unique near infrared (NIR) luminescence properties. However, the application of Nd-doped nanomaterials to chemosensors was rarely explored. Herein, the water-soluble 2-aminoethyl dihydrogen phosphate stabilized Nd-doped LaF(3) (ADP-Nd-LaF(3)) nanoparticles were explored as the NIR probe for chemosensors. The NIR emission intensity at 1061 nm of ADP-Nd-LaF(3) nanoparticles kept stable in the aqueous solution of various pH and coexisting of most common metal ions except copper ion, consequently, the ADP-Nd-LaF(3) nanoparticles were developed as a high selective NIR probe for Cu(II). The NIR emission of ADP-Nd-LaF(3) exhibits a linear quenching response to Cu(II) in the range 5-100 μM, with a detection limit of 0.8 μM. The precision of eleven replicate detections of 5 μM Cu(II) was 0.5% (RSD). The recovery of spiked Cu(II) in human urine and waste water samples ranged from 102 to 109%. The possible mechanism of Cu(II)-induced fluorescence quenching of ADP-Nd-LaF(3) nanoparticles was also discussed.

  12. Preparation of Lanthanide-Polymer Composite Material via Click Chemistry.

    PubMed

    Chen, Bin; Wen, Guian; Wu, Jiajie; Feng, Jiachun

    2015-10-01

    Covalently attaching lanthanide complexes to the polymer backbone can effectively reduce the clustering of lanthanides and thus become an important strategy to fully unleash their potential. In this Communication, a metal-free click reaction is used for the first time to link a lanthanide complex to the polymer matrix. A diene-bearing copolymer with anthracenylmethyl methacrylate as a monomer and a dienophile-bearing lanthanide complex with 5-maleimido-1,10-phenanthroline as the second ligand are synthesized and coupled together through a Diels-Alder cycloaddition (DA). A comparative investigation demonstrates that the composite material prepared by DA click reaction shows the highest quantum yields in the same lanthanide concentration as compared to materials prepared by widely used "directly doping" and "in situ coordinating lanthanide ions with macromolecular ligand" approaches. This work suggests that the "metal-free" DA click reaction can be a promising tool in the synthesis of high efficient lanthanide functionalized polymeric materials.

  13. Upconversion luminescence of lanthanide-doped mixed CaMoO4-CaWO4 micro-/nano-materials.

    PubMed

    Liu, Jing; Kaczmarek, Anna M; Billet, Jonas; Van Driessche, Isabel; Van Deun, Rik

    2016-08-14

    Uniform mixed CaMoO4-CaWO4 micro-/nano-materials have been successfully synthesised by a facile hydrothermal method. The morphology of these upconversion materials could be changed to different shapes and the size could also be decreased from the micro- to nano-scale by varying the type of surfactant used. It was observed that before heat treatment, the materials show relatively weak green light emission under excitation at 975 nm, whereas after heat treatment, the intensity of the upconversion luminescence increases dramatically while the intensity of the red component decreases relatively. By adjusting the molybdate/tungstate ratio, it was found that the samples with a higher molybdate content have stronger luminescence properties. XRD measurements have been done to investigate the structure of the mixed CaMoO4-CaWO4 upconversion materials. The effect of heat treatment at different temperatures on the emission spectra and XRD patterns has also been studied. TG-DTA was used to further confirm the most suitable temperature for heat treatment. The luminescence lifetimes and CIE coordinates for these samples were also determined. Additionally it was found that Gd(3+) co-doping could further increase the upconversion luminescence from these mixed CaMoO4-CaWO4 materials. Finally, monitoring the upconversion luminescence intensity as a function of laser pump power confirmed the upconversion process to be a two-photon absorption mechanism.

  14. Upconversion luminescence of lanthanide-doped mixed CaMoO4-CaWO4 micro-/nano-materials.

    PubMed

    Liu, Jing; Kaczmarek, Anna M; Billet, Jonas; Van Driessche, Isabel; Van Deun, Rik

    2016-08-14

    Uniform mixed CaMoO4-CaWO4 micro-/nano-materials have been successfully synthesised by a facile hydrothermal method. The morphology of these upconversion materials could be changed to different shapes and the size could also be decreased from the micro- to nano-scale by varying the type of surfactant used. It was observed that before heat treatment, the materials show relatively weak green light emission under excitation at 975 nm, whereas after heat treatment, the intensity of the upconversion luminescence increases dramatically while the intensity of the red component decreases relatively. By adjusting the molybdate/tungstate ratio, it was found that the samples with a higher molybdate content have stronger luminescence properties. XRD measurements have been done to investigate the structure of the mixed CaMoO4-CaWO4 upconversion materials. The effect of heat treatment at different temperatures on the emission spectra and XRD patterns has also been studied. TG-DTA was used to further confirm the most suitable temperature for heat treatment. The luminescence lifetimes and CIE coordinates for these samples were also determined. Additionally it was found that Gd(3+) co-doping could further increase the upconversion luminescence from these mixed CaMoO4-CaWO4 materials. Finally, monitoring the upconversion luminescence intensity as a function of laser pump power confirmed the upconversion process to be a two-photon absorption mechanism. PMID:27396395

  15. Parametric Study of Up-Conversion Efficiency in Er-Doped Lanthanide Hosts Under 780 nm/980 nm Excitation Wavelengths

    NASA Astrophysics Data System (ADS)

    Samir, E.; Shehata, N.; Aldacher, M.; Kandas, I.

    2016-06-01

    Up-conversion is a process of converting low energy light photons to higher energy ones, which can be extensively used in many applications. This paper presents a detailed parametric study of the up-conversion process under different wavelength excitations—780 nm and 980 nm—showing the optical conversion mechanisms that affect the emitted light quantum yield efficiencies. The studied material is erbium-doped β-NaYF4 material, which is one of the most recently studied materials due to its low phonon energy. The studied simulation considers most processes and possible transitions that can take place between Er3+ ions. Einstein coefficients, which are the main parameters that are responsible for the transitions probabilities, are discussed in detail using Judd-Ofelt analysis. In addition, the effect of changing some parametric values is discussed, showing their optimum values that could improve the quantum yield efficiency. This model is very promising, and generic, and can be applied for any host material under any excitation wavelengths by varying the material-dependent parameters.

  16. Electrochemically Deposited Ceria Structures for Advanced Solid Oxide Fuel Cells

    NASA Astrophysics Data System (ADS)

    Brown, Evan C.

    As the pursuit towards emissions reduction intensifies with growing interest and nascent technologies, solid oxide fuel cells (SOFCs) remain an illustrious candidate for achieving our goals. Despite myriad advantages, SOFCs are still too costly for widespread deployment, even as unprecedented materials developments have recently emerged. This suggests that, in addition to informed materials selection, the necessary power output--and, thereby, cost-savings--gains must come from the fuel cell architecture. The work presented in this manuscript primarily investigates cathodic electrochemical deposition (CELD) as a scalable micro-/nanoscale fabrication tool for engineering ceria-based components in a SOFC assembly. Also, polymer sphere lithography was utilized to deposit fully connected, yet fully porous anti-dot metal films on yttira-stabilized zirconia (YSZ) with specific and knowable geometries, useful for mechanistic studies. Particular attention was given to anode structures, for which anti-dot metal films on YSZ served as composite substrates for subsequent CELD of doped ceria. By tuning the applied potential, a wide range of microstructures from high surface area coatings to planar, thin films was possible. In addition, definitive deposition was shown to occur on the electronically insulating YSZ surfaces, producing quality YSZ|ceria interfaces. These CELD ceria deposits exhibited promising electrochemical activity, as probed by A.C. Impedance Spectroscopy. In an effort to extend its usefulness as a SOFC fabrication tool, the CELD of ceria directly onto common SOFC cathode materials without a metallic phase was developed, as well as templated deposition schemes producing ceria nanowires and inverse opals.

  17. Silica-Ceria Hybrid Nanostructures

    SciTech Connect

    Munusamy, Prabhakaran; Sanghavi, Shail P.; Nachimuthu, Ponnusamy; Baer, Donald R.; Thevuthasan, Suntharampillai

    2012-04-25

    A new hybrid material system that consists of ceria attached silica nanoparticles has been developed. Because of the versatile properties of silica and versatile properties of silica and versatile properties of silica and versatile properties of silica and versatile properties of silica and versatile properties of silica and versatile properties of silica and versatile properties of silica and versatile properties of silica and versatile properties of silica and versatile properties of silica and versatile properties of silica and antioxidant properties of ceria nanoparticles, this material system is ideally suited for biomedical applications. The silica particles of size ~50nm were synthesized by the Stöber synthesis method and ceria nanoparticles of size ~2-3nm was attached to the silica surface using a hetrocoagulation method. The presence of silanol groups on the surface of silica particles mediated homogenous nucleation of ceria which were attached to silica surface by Si-O-Ce bonding. The formations of silica-ceria hybrid nanostructures were characterized by X-photoelectron spectroscopy (XPS) and high resolution transmission electron microscopy (HRTEM). The HRTEM image confirms the formation of individual crystallites of ceria nanoparticles attached to the silica surface. The XPS analysis indicates that ceria nanoparticles are chemically bonded to surface of silica and possess mixture of +3 and +4 chemical states.

  18. Characterization of ceria-based SOFCs

    SciTech Connect

    Doshi, R.; Routbort, J.; Krumpelt, M.

    1996-12-31

    Solid Oxide Fuel Cells (SOFCs) operating at low temperatures (500-700{degrees}C) offer many advantages over the conventional zirconia-based fuel cells operating at higher temperatures. Reduced operating temperatures result in: (1) Application of metallic interconnects with reduced oxidation problems (2) Reduced time for start-up and lower energy consumption to reach operating temperatures (3) Increased thermal cycle ability for the cell structure due to lower thermal stresses of expansion mismatches. While this type of fuel cell may be applied to stationary applications, mobile applications require the ability for rapid start-up and frequent thermal cycling. Ceria-based fuel cells are currently being developed in the U.K. at Imperial College, Netherlands at ECN, and U.S.A. at Ceramatec. The cells in each case are made from a doped ceria electrolyte and a La{sub 1-x}Sr{sub x}Co{sub 1-y}Fe{sub y}O{sub 3} cathode.

  19. Structural investigation and luminescence of nanocrystalline lanthanide doped NaNbO{sub 3} and Na{sub 0.5}K{sub 0.5}NbO{sub 3}

    SciTech Connect

    Pin, Sonia; Piccinelli, Fabio; Upendra Kumar, Kagola; Enzo, Stefano; Ghigna, Paolo; Cannas, Carla; Musinu, Anna; Mariotto, Gino; Bettinelli, Marco; Speghini, Adolfo

    2012-12-15

    Nd{sup 3+} and Eu{sup 3+} doped NaNbO{sub 3} and Na{sub 0.5}K{sub 0.5}NbO{sub 3} nanostructured multiferroics (nanoparticles or nanorods) were prepared by a sol-gel route. X-Ray powder diffraction results evidence that the sodium and mixed sodium-potassium niobates show orthorhombic (Pmc2{sub 1} space group), and monoclinic structure (Pm space group), respectively, confirmed by the Raman spectra. The local structure around the trivalent lanthanides was investigated with Extended X-ray Absorption Fine Structure spectroscopy at the Ln-K edge and luminescence spectroscopy. The Ln{sup 3+} ions enter the structure by substituting the alkali metals, with a 12-fold oxygen coordination, and inducing a large amount of static disorder. The visible emission bands of the Eu{sup 3+} ions indicate that multiple sites exist for the lanthanide ions, in agreement with the EXAFS results showing the largest amount of static disorder in these samples. A possible indication of clustering of oxygen vacancies around the Ln{sub Na} Double-Prime defect is obtained by VBS calculations. - Graphical Abstract: Ln{sup 3+} doped NaNbO{sub 3} and Na{sub 0.5}K{sub 0.5}NbO{sub 3} nanoparticles or nanorods can be prepared by a simple sol-gel procedure. The synergy of X-ray diffraction, EXAFS and luminescence spectroscopy gives important information on the Ln{sup 3+} local environment. Highlights: Black-Right-Pointing-Pointer Nd{sup 3+} and Eu{sup 3+} doped NaNbO{sub 3} and Na{sub 0.5}K{sub 0.5}NbO{sub 3} nanoparticles or nanorods are prepared by sol-gel. Black-Right-Pointing-Pointer EXAFS indicates that the Ln{sup 3+} ions substitutes the Na{sup +} and K{sup +} ions, inducing a large amount of static disorder. Black-Right-Pointing-Pointer The visible emission bands of the Eu{sup 3+} ions confirm that multiple sites exist for the lanthanide ions.

  20. Simple cerium-triethanolamine complex: Synthesis, characterization, thermal decomposition and its application to prepare ceria support for platinum catalysts used in methane steam reforming

    NASA Astrophysics Data System (ADS)

    Wattanathana, Worawat; Nootsuwan, Nollapan; Veranitisagul, Chatchai; Koonsaeng, Nattamon; Laosiripojana, Navadol; Laobuthee, Apirat

    2015-06-01

    Cerium-triethanolamine complex was synthesized by simple complexation method in 1-propanol solvent using cerium(III) chloride as a metal source and triethanolamine as a ligand. The structures of the prepared complex were proposed based on FT-IR, FT-Raman and ESI-MS results as equimolar of triethanolamine and cerium chelated complex having monomeric tricyclic structure with and without chloride anion as another coordinating group known as ceratrane. The complex was used as a precursor for ceria material done by thermal decomposition. XRD result revealed that when calcined at 600 °C for 2 h, the cerium complex was totally turned into pure ceria with cubic fluorite structure. The obtained ceria was then employed to synthesize platinum doped ceria catalysts for methane steam reforming. Various amounts of platinum i.e. 1, 3, 5 and 10 mol percents were introduced on the ceria support by microwave-assisted wetness impregnation using ammonium tetrachloroplatinate(II). The platinum-impregnated ceria powders were subjected to calcination in 10% hydrogen/helium atmosphere at 500 °C for 3 h to reduce platinum(II) to platinum(0). XRD patterns of the catalysts confirmed that the platinum particles doped on the ceria support were in the form of platinum(0). Catalytic activity test showed that the catalytic activities got higher as the amounts of platinum doped increased. Besides, the portions of coke formation on the surface of catalysts were reduced as the amounts of platinum doped increased.

  1. Microstructural characterization of terbium-doped ceria

    SciTech Connect

    Ye, F. . E-mail: fei.ye@nims.go.jp; Mori, Toshiyuki; Ou, D.R.; Zou Jin; Drennan, John

    2007-05-03

    The microstructures of Ce{sub 1-x}Tb {sub x}O{sub 2-{delta}} (0.10 {<=} x {<=} 0.50) sintered samples were studied systematically using transmission electron microscopy. The sintered samples consist of not only fluorite-structured matrix but also nano-sized precipitates. Correspondingly, diffuse scattering and extra reflections related to the precipitates were observed in the selected area diffraction patterns. The composition of the precipitates was studied quantitatively by electron energy-loss spectroscopy, indicating that the precipitates have higher Tb concentration than that of the matrix. Furthermore, Tb{sup 3+} and Ce{sup 3+} cations were observed to segregate in the precipitates.

  2. Kinetics of CO2 Reduction over Nonstoichiometric Ceria

    PubMed Central

    2015-01-01

    The kinetics of CO2 reduction over nonstoichimetric ceria, CeO2−δ, a material of high potential for thermochemical conversion of sunlight to fuel, has been investigated for a wide range of nonstoichiometries (0.02 ≤ δ ≤ 0.25), temperatures (693 ≤ T ≤ 1273 K), and CO2 concentrations (0.005 ≤ pCO2 ≤ 0.4 atm). Samples were reduced thermally at 1773 K to probe low nonstoichiometries (δ < 0.05) and chemically at lower temperatures in a H2 atmosphere to prevent particle sintering and probe the effect of higher nonstoichiometries (δ < 0.25). For extents greater than δ = 0.2, oxidation rates at a given nonstoichiometry are hindered for the duration of the reaction, presumably because of near-order changes, such as lattice compression, as confirmed via Raman Spectroscopy. Importantly, this behavior is reversible and oxidation rates are not affected at lower δ. Following thermal reduction at very low δ, however, oxidation rates are an order of magnitude slower than those of chemically reduced samples, and rates monotonically increase with the initial nonstoichiometry (up to δ = 0.05). This dependence may be attributed to the formation of stable defect complexes formed between oxygen vacancies and polarons. When the same experiments are performed with 10 mol % Gd3+ doped ceria, in which defect complexes are less prevalent than in pure ceria, this dependence is not observed. PMID:26693270

  3. Ionization Energies of Lanthanides

    ERIC Educational Resources Information Center

    Lang, Peter F.; Smith, Barry C.

    2010-01-01

    This article describes how data are used to analyze the pattern of ionization energies of the lanthanide elements. Different observed pathways of ionization between different ground states are discussed, and the effects of pairing, exchange, and orbital interactions on ionization energies of the lanthanides are evaluated. When all the above…

  4. Processing and characterization of nanocrystalline ceria

    NASA Astrophysics Data System (ADS)

    Zhou, Xiao-Dong

    Ceria and doped ceria have been extensively investigated and applied in various industrial fields, including automotive, energy, polishing media, paint additives and cosmetics. The use of high surface area, nanocrystalline CeO2 powder could benefit all of these applications. This is particularly true for processing dense components, since the high melting point (2400°C) of pure CeO2 makes it difficult to sinter. In this dissertation, a semi-batch reactor method was developed for directly synthesizing undoped and doped, nanometer-scale CeO2 particles at room temperature. Powders exhibited a surface area of ≈170 m 2/g, and could be decreased to 5 m2/g by thermal annealing at 1000°C. Control over the particle size, size distribution and state of agglomeration could be achieved through variation of the mixing conditions, and oxidation pathway. Modeling of the nucleation behavior yielded a surface energy for Ce(OH)3 to be in the range of 2.9--3.7 J/m 2. Size induced lattice relaxation was observed for nanoscale CeO2 single crystals with an average size from 4 to 60 nm. Results showed the finest crystallites exhibited no strain-induced line broadening, while high temperature annealing resulted in larger grain sizes and significant strains. Modeling revealed that the [V••o] was found to be ≈4 x 1020/cm 3 for the 4 nm crystallites, and decreased two orders of magnitude for larger 60 mn single crystals. The microstructural evolution and grain boundary influence on electrical properties of Ce0.90Gd0.10 O1.95 were also studied. The nanoscale powders synthesized from semi-batch reactor exhibited 50% green density and 92% sintering density at 1200°C (≈200°C less than previous studies). A series of impedance spectra as a function of temperature and grain size were analyzed. The Ce 0.90Gd0.10O1.95 with finest grain size possessed highest overall grain boundary resistance; this contribution was eliminated at T>600°C, regardless of grain size. The grain conductivity

  5. The Lanthanide Contraction Revisited

    SciTech Connect

    Seitz, Michael; Oliver, Allen G.; Raymond, Kenneth N.

    2007-04-19

    A complete, isostructural series of lanthanide complexes (except Pm) with the ligand TREN-1,2-HOIQO has been synthesized and structurally characterized by means of single-crystal X-ray analysis. All complexes are 1D-polymeric species in the solid state, with the lanthanide being in an eight-coordinate, distorted trigonal-dodecahedral environment with a donor set of eight unique oxygen atoms. This series constitutes the first complete set of isostructural lanthanide complexes with a ligand of denticity greater than two. The geometric arrangement of the chelating moieties slightly deviates across the lanthanide series, as analyzed by a shape parameter metric based on the comparison of the dihedral angles along all edges of the coordination polyhedron. The apparent lanthanide contraction in the individual Ln-O bond lengths deviates considerably from the expected quadratic decrease that was found previously in a number of complexes with ligands of low denticity. The sum of all bond lengths around the trivalent metal cation, however, is more regular, showing an almost ideal quadratic behavior across the entire series. The quadratic nature of the lanthanide contraction is derived theoretically from Slater's model for the calculation of ionic radii. In addition, the sum of all distances along the edges of the coordination polyhedron show exactly the same quadratic dependency as the Ln-X bond lengths. The universal validity of this coordination sphere contraction, concomitant with the quadratic decrease in Ln-X bond lengths, was confirmed by reexamination of four other, previously published, almost complete series of lanthanide complexes. Due to the importance of multidentate ligands for the chelation of rare-earth metals, this result provides a significant advance for the prediction and rationalization of the geometric features of the corresponding lanthanide complexes, with great potential impact for all aspects of lanthanide coordination.

  6. Lattice Strain Defects in a Ceria Nanolayer

    PubMed Central

    2016-01-01

    An ultrathin two-dimensional CeO2 (ceria) phase on a Cu(110) surface has been fabricated and fully characterized by high-resolution scanning tunneling microscopy, photoelectron spectroscopy, and density functional theory. The atomic lattice structure of the ceria/Cu(110) system is revealed as a hexagonal CeO2(111)-type monolayer separated from the Cu(110) surface by a partly disordered Cu–O intercalated buffer layer. The epitaxial coupling of the two-dimensional ceria overlayer to the Cu(110)-O surface leads to a nanoscopic stripe pattern, which creates defect regions of quasi-periodic lattice distortions. The symmetry and lattice mismatch at the interface is clarified to be responsible for the topographic stripe geometry and the related anisotropic strain defect regions at the ceria surface. This ceria monolayer is in a fully oxidized and thermodynamically stable state. PMID:26988695

  7. Antibody-based donor-acceptor spatial reconfiguration in decorated lanthanide-doped nanoparticle colloids for the quantification of okadaic acid biotoxin.

    PubMed

    Stipić, Filip; Burić, Petra; Jakšić, Željko; Pletikapić, Galja; Dutour Sikirić, Maja; Zgrablić, Goran; Frkanec, Leo; Lyons, Daniel M

    2015-11-01

    With the increasing movement away from the mouse bioassay for the detection of toxins in commercially harvested shellfish, there is a growing demand for the development of new and potentially field-deployable tests in its place. In this direction we report the development of a simple and sensitive nanoparticle-based luminescence technique for the detection of the marine biotoxin okadaic acid. Photoluminescent lanthanide nanoparticles were conjugated with fluorophore-labelled anti-okadaic acid antibodies which, upon binding to okadaic acid, gave rise to luminescence resonance energy transfer from the nanoparticle to the organic fluorophore dye deriving from a reduction in distance between the two. The intensity ratio of the fluorophore: nanoparticle emission peaks was found to correlate with okadaic acid concentration, and the sensor showed a linear response in the 0.37-3.97 μM okadaic acid range with a limit of detection of 0.25 μM. This work may have important implications for the development of new, cheap, and versatile biosensors for a range of biomolecules and that are sufficiently simple to be applied in the field or at point-of-care. PMID:26283497

  8. Antibody-based donor-acceptor spatial reconfiguration in decorated lanthanide-doped nanoparticle colloids for the quantification of okadaic acid biotoxin.

    PubMed

    Stipić, Filip; Burić, Petra; Jakšić, Željko; Pletikapić, Galja; Dutour Sikirić, Maja; Zgrablić, Goran; Frkanec, Leo; Lyons, Daniel M

    2015-11-01

    With the increasing movement away from the mouse bioassay for the detection of toxins in commercially harvested shellfish, there is a growing demand for the development of new and potentially field-deployable tests in its place. In this direction we report the development of a simple and sensitive nanoparticle-based luminescence technique for the detection of the marine biotoxin okadaic acid. Photoluminescent lanthanide nanoparticles were conjugated with fluorophore-labelled anti-okadaic acid antibodies which, upon binding to okadaic acid, gave rise to luminescence resonance energy transfer from the nanoparticle to the organic fluorophore dye deriving from a reduction in distance between the two. The intensity ratio of the fluorophore: nanoparticle emission peaks was found to correlate with okadaic acid concentration, and the sensor showed a linear response in the 0.37-3.97 μM okadaic acid range with a limit of detection of 0.25 μM. This work may have important implications for the development of new, cheap, and versatile biosensors for a range of biomolecules and that are sufficiently simple to be applied in the field or at point-of-care.

  9. Synthesis and atomic level in situ redox characterization in ceria and ceria zirconia

    NASA Astrophysics Data System (ADS)

    Wang, Ruigang

    2007-12-01

    Nanocrystalline ceria-based oxides are widely used in automotive three-way catalytic converters to reduce the emissions of carbon monoxide, nitrogen oxides, and unburned hydrocarbons. The primary function of ceria-based oxides in the catalytic process is to adjust the local oxygen partial pressure and maintain an air-to-fuel ratio near the stoichiometric value (˜14.5) required for the optimal catalyst performance for carbon monoxide, hydrocarbon oxidation, and nitrogen oxides reduction. In this dissertation, a study of the relationship between the nanoscale structure, chemistry, and the redox behavior on high surface area ceria and ceria zirconia is presented. Precipitation and spray freezing methods were used to synthesize nanocrystalline ceria and ceria zirconia solid solution powders respectively. The effect of thermal treatments in oxidizing and reducing atmospheres on the reducibility of the materials has been systematically investigated. X-ray diffraction and thermogravimetric analysis were used to characterize the average structure and reducibility. In situ environmental transmission electron microscope was exploited to visualize the dynamic changes during redox processes at the atomic level. This resulted in the identification of the nanoscale structure and chemistry for the most active nanoparticles in these oxides. The correlation between ex situ macroscopic redox properties and in situ redox behavior of individual nanoparticles is demonstrated. The addition of zirconia to ceria clearly enhances the reducibility and thermal stability of ceria. A fundamental difference between ceria and ceria zirconia during in situ redox processes is related to oxygen vacancy ordering. Ceria showed oxygen vacancy ordering during reduction, whereas ceria zirconia did not. It is suggested that the absence of oxygen vacancy ordering might be a fundamental factor for improved redox properties of ceria zirconia compared with pure ceria. The 50% ceria-50% zirconia solid

  10. Electrocaloric effect and luminescence properties of lanthanide doped (Na{sub 1/2}Bi{sub 1/2})TiO{sub 3} lead free materials

    SciTech Connect

    Zannen, M.; Lahmar, A. E-mail: zdravko.kutnjak@ijs.si; Asbani, B.; El Marssi, M.; Khemakhem, H.; Kutnjak, Z. E-mail: zdravko.kutnjak@ijs.si; Es Souni, M.

    2015-07-20

    Polycrystalline lead-free Sodium Bismuth Titanate (NBT) ferroelectric ceramics doped with rare earth (RE) element are prepared using solid state reaction method. Optical, ferroelectric, and electrocaloric properties were investigated. The introduction of RE{sup 3+} ions in the NBT host lattice shows different light emissions over the wavelength range from visible to near infrared region. The ferroelectric P-E hysteresis loops exhibit an antiferroelectric-like character near room temperature indicating possible existence of a morphotropic phase boundary. The enhanced electrocaloric response was observed in a broad temperature range due to nearly merged phase transitions. Coexistence of optical and electrocaloric properties is very promising for photonics or optoelectronic device applications.

  11. One-pot hydrothermal synthesis of lanthanide ions doped one-dimensional upconversion submicrocrystals and their potential application in vivo CT imaging.

    PubMed

    Gao, Guo; Zhang, Chunlei; Zhou, Zhijun; Zhang, Xin; Ma, Jiebing; Li, Chao; Jin, Weilin; Cui, Daxiang

    2013-01-01

    Multi-functional rare-earth Yb(3+) and Ln(3+) (Ln = Er, Tm and Ho) ions doped one-dimensional (1-D) upconversion submicrocrystals (NaYF(4) and NaGdF(4)) possessing upconversion luminescence, biocompatibility and magnetic properties have been synthesized by a one-pot hydrothermal method. Rare-earth Yb(3+) and Ln(3+) ions doped NaYF(4) microrods (~1 μm in diameter, 3-5 μm in length) exhibit porous properties, and the average pore sizes are ~28.2 nm. They show paramagnetism in the magnetic range of -60 to -2 kOe and 2 to 60 kOe at 300 K, and exhibit near superparamagnetic behaviour at the magnetic range of -2 to 2 kOe. Saturation magnetization was ~12.1 emu g(-1) at 2 K. The Yb(3+) and Ln(3+) ions doped NaGdF(4) submicrocrystals (~100 nm in diameter, 200-300 nm in length) show paramagnetism at 300 K, and exhibit superparamagnetic behaviour with a saturation magnetization of 129.2 emu g(-1) at 2 K. The magnetic properties of Yb(3+) and Ln(3+) ions doped 1-D upconversion submicrocrystals indicate they can be used for drug targeting under a magnetic field. Their unique upconversion emission (green for Yb(3+)/Er(3+) and blue for Yb(3+)/Tm(3+)) under 980 nm laser excitation indicate that they could be used for specific luminescent immunolabeling and imaging. MTT assays reveal that 1-D upconversion submicrocrystals have satisfactory bio-affinity, where the viability keeps in good state even at a concentration of 500 μg mL(-1), which is much higher than the concentration usually used in cell labelling. Luminescent microscopy images show that the morphologies of the cytoskeleton and cell nucleus are well maintained after incubating different concentrations of 1-D upconversion submicrocrystals. After injecting upconversion submicrocrystals into the mice (tumor sites or back normal tissue), a clearly distinguished CT signal was observed, indicating the synthesized 1-D submicrocrystals are effective for CT imaging in vivo.

  12. Luminescent macrocyclic lanthanide complexes

    DOEpatents

    Raymond, Kenneth N.; Corneillie, Todd M.; Xu, Jide

    2012-05-08

    The present invention provides a novel class of macrocyclic compounds as well as complexes formed between a metal (e.g., lanthanide) ion and the compounds of the invention. Preferred complexes exhibit high stability as well as high quantum yields of lanthanide ion luminescence in aqueous media without the need for secondary activating agents. Preferred compounds incorporate hydroxy-isophthalamide moieties within their macrocyclic structure and are characterized by surprisingly low, non-specific binding to a variety of polypeptides such as antibodies and proteins as well as high kinetic stability. These characteristics distinguish them from known, open-structured ligands.

  13. Luminescent macrocyclic lanthanide complexes

    DOEpatents

    Raymond, Kenneth N; Corneillie, Todd M; Xu, Jide

    2014-05-20

    The present invention provides a novel class of macrocyclic compounds as well as complexes formed between a metal (e.g., lanthanide) ion and the compounds of the invention. Preferred complexes exhibit high stability as well as high quantum yields of lanthanide ion luminescence in aqueous media without the need for secondary activating agents. Preferred compounds incorporate hydroxy-isophthalamide moieties within their macrocyclic structure and are characterized by surprisingly low, non-specific binding to a variety of polypeptides such as antibodies and proteins as well as high kinetic stability. These characteristics distinguish them from known, open-structured ligands.

  14. Sub-10 nm lanthanide doped BaLuF{sub 5} nanocrystals: Shape controllable synthesis, tunable multicolor emission and enhanced near-infrared upconversion luminescence

    SciTech Connect

    Rao, Ling; Lu, Wei; Wang, Haibo; Yi, Zhigao; Zeng, Songjun; Li, Zheng

    2015-04-15

    Highlights: • Sub-10 nm cubic phase BaLuF{sub 5} nanocrystals were synthesized by a hydrothermal method for the first time. • Tunable multicolor from yellow to yellow-green was achieved by controlling Gd{sup 3+} content in BaLuF{sub 5}:Yb/Er system. • Intense near-infrared upconversion luminescence in BaLuF{sub 5}:Gd/Yb/Tm nanocrystal. • The enhancement near-infrared luminescence can be realized by adjusting the content of Gd{sup 3+} in BaLuF{sub 5}:Gd/Yb/Tm system. - Abstract: In this study, sub-10 nm BaLuF{sub 5} nanocrystals with cubic phase structure were synthesized by a solvothermal method using oleic acid as the stabilizing agent. The as-prepared BaLuF{sub 5} nanocrystals were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), and analyzed by the upconversion (UC) spectra. The TEM results reveal that these samples present high uniformity. Compared with Gd-free samples, the size of BaLuF{sub 5}:Yb/Er doped with 10% Gd{sup 3+} decreased to 5.6 nm. In addition, BaLuF{sub 5}:Yb/Tm/Gd upconversion nanoparticles (UCNPs) presented efficient near-infrared (NIR)-NIR UC luminescence. Therefore, it is expected that these ultra-small BaLuF{sub 5} nanocrystals with well-controlled shape, size, and UC emission have potential applications in biomedical imaging fields.

  15. Design of lanthanide fingers: compact lanthanide-binding metalloproteins.

    PubMed

    am Ende, Christopher W; Meng, Hai Yun; Ye, Mao; Pandey, Anil K; Zondlo, Neal J

    2010-08-16

    Lanthanides have interesting chemical properties; these include luminescent, magnetic, and catalytic functions. Toward the development of proteins incorporating novel functions, we have designed a new lanthanide-binding motif, lanthanide fingers. These were designed based on the Zif268 zinc finger, which exhibits a beta beta alpha structural motif. Lanthanide fingers utilize an Asp(2)Glu(2) metal-coordination environment to bind lanthanides through a tetracarboxylate peptide ligand. The iterative design of a general lanthanide-binding peptide incorporated the following key elements: 1) residues with high alpha-helix and beta-sheet propensities in the respective secondary structures; 2) an optimized big box alpha-helix N-cap; 3) a Schellman alpha-helix C-cap motif; and 4) an optional D-Pro-Ser type II' beta-turn in the beta-hairpin. The peptides were characterized for lanthanide binding by circular dichroism (CD), NMR, and fluorescence spectroscopy. In all instances, stabilization of the peptide secondary structures resulted in an increase in metal affinity. The optimized protein design was a 25-residue peptide that was a general lanthanide-binding motif; this binds all lanthanides examined in a competitive aqueous environment, with a dissociation constant of 9.3 microM for binding Er(3+). CD spectra of the peptide-lanthanide complexes are similar to those of zinc fingers and other beta beta alpha proteins. Metal binding involves residues from the N-terminal beta-hairpin and the C terminal alpha-helical segments of the peptide. NMR data indicated that metal binding induced a global change in the peptide structure. The D-Pro-Ser type II' beta-turn motif could be replaced by Thr-Ile to generate genetically encodable lanthanide fingers. Replacement of the central Phe with Trp generated genetically encodable lanthanide fingers that exhibited terbium luminescence greater than that of an EF-hand peptide.

  16. Statistical thermodynamics of non-stoichiometric ceria and ceria zirconia solid solutions.

    PubMed

    Bulfin, B; Hoffmann, L; de Oliveira, L; Knoblauch, N; Call, F; Roeb, M; Sattler, C; Schmücker, M

    2016-08-17

    The thermodynamic redox properties of ceria and ceria zirconia solid solutions are analysed with a new methodology for modelling such systems based on the statistical mechanics of lattice configurations. Experimental thermogravimetric equilibrium data obtained for small non-stoichiometry measurements are combined with literature data to cover a large range of non-stoichiometry (CeO2-δ, δ = 0.001-0.32), temperature (1073-1773 K) and oxygen partial pressure (1-10(-13) bar). A dilute species model of defect clusters , obeying the law of mass action, was sufficient to describe the system over the whole range of conditions, leading to a simple analytical equation of state for the system. This offers new physical insight into the redox properties of ceria based materials, and the theoretical methods developed should also be of great interest for other materials which exhibit continuous oxygen non-stoichiometry similar to ceria, such as perovskite oxides. PMID:27494765

  17. Tailoring lanthanide nanocrystals for nanomedicine

    NASA Astrophysics Data System (ADS)

    Zhang, Yan; Tan, Timothy T. Y.

    2013-02-01

    Lanthanide nanocrystals have demonstrated strong potentials in nanomedicine due to its up-conversion and strong magnetic properties, and low toxicity. This talk will focus on strategies in lanthanide nanostructure tailoring to achieve up-conversion color emission tuning, MRI T1 and T2 contrast tuning, and the use of up-conversion fluorescence in drug delivery and cancer cells ablation.

  18. Aromatic triamide-lanthanide complexes

    DOEpatents

    Raymond, Kenneth N; Petoud, Stephane; Xu, Jide

    2013-10-08

    The present invention provides luminescent lanthanide metal chelates comprising a metal ion of the lanthanide series and a complexing agent comprising at least one phthalamidyl moiety. Also provided are probes incorporating the phthalamidyl ligands of the invention and methods utilizing the ligands of the invention and probes comprising the ligands of the invention.

  19. Impacts of a Nanosized Ceria Additive on Diesel Engine Emissions of Particulate and Gaseous Pollutants

    PubMed Central

    Zhang, Junfeng; Nazarenko, Yevgen; Zhang, Lin; Calderon, Leonardo; Lee, Ki-Bum; Garfunkel, Eric; Schwander, Stephan; Tetley, Teresa D.; Chung, Kian Fan; Porter, Alexandra E.; Ryan, Mary; Kipen, Howard; Lioy, Paul J.; Mainelis, Gediminas

    2014-01-01

    Fuel additives incorporating nanosized ceria have been increasingly used in diesel engines as combustion promoters. However, few studies have assessed the impact of these nanotechnology-based additives on pollutant emissions. Here, we systematically compare emission rates of particulate and gaseous pollutants from a single-cylinder, four-cycle diesel engine using fuel mixes containing nanoceria of varying concentrations. The test fuels were made by adding different amounts of a commercial fuel additive Envirox into an ultralow-sulfur diesel fuel at 0 (base fuel), 0.1-, 1-, and 10-fold the manufacturer-recommended concentration of 0.5 mL Envirox per liter of fuel. The addition of Envirox resulted in ceria-concentration-dependent emission reductions of CO2, CO, total particulate mass, formaldehyde, acetaldehyde, acrolein, and several polycyclic aromatic hydrocarbons. These reductions at the manufacturer-recommended doping concentration, however, were accompanied by a substantial increase of certain other air pollutants, specifically the number of ultrafine particles (+32%), NOx (+9.3%), and the particle-phase benzo[a]pyrene toxic equivalence quotient (+35%). Increasing fuel ceria concentrations also led to decreases in the size of emitted particles. Given health concerns related to ultrafine particles and NOx, our findings call for additional studies to further evaluate health risks associated with the use of nanoceria additives in various engines under various operating conditions. PMID:24144266

  20. Impacts of a nanosized ceria additive on diesel engine emissions of particulate and gaseous pollutants.

    PubMed

    Zhang, Junfeng; Nazarenko, Yevgen; Zhang, Lin; Calderon, Leonardo; Lee, Ki-Bum; Garfunkel, Eric; Schwander, Stephan; Tetley, Teresa D; Chung, Kian Fan; Porter, Alexandra E; Ryan, Mary; Kipen, Howard; Lioy, Paul J; Mainelis, Gediminas

    2013-11-19

    Fuel additives incorporating nanosized ceria have been increasingly used in diesel engines as combustion promoters. However, few studies have assessed the impact of these nanotechnology-based additives on pollutant emissions. Here, we systematically compare emission rates of particulate and gaseous pollutants from a single-cylinder, four-cycle diesel engine using fuel mixes containing nanoceria of varying concentrations. The test fuels were made by adding different amounts of a commercial fuel additive Envirox into an ultralow-sulfur diesel fuel at 0 (base fuel), 0.1-, 1-, and 10-fold the manufacturer-recommended concentration of 0.5 mL Envirox per liter of fuel. The addition of Envirox resulted in ceria-concentration-dependent emission reductions of CO2, CO, total particulate mass, formaldehyde, acetaldehyde, acrolein, and several polycyclic aromatic hydrocarbons. These reductions at the manufacturer-recommended doping concentration, however, were accompanied by a substantial increase of certain other air pollutants, specifically the number of ultrafine particles (+32%), NO(x) (+9.3%), and the particle-phase benzo[a]pyrene toxic equivalence quotient (+35%). Increasing fuel ceria concentrations also led to decreases in the size of emitted particles. Given health concerns related to ultrafine particles and NO(x), our findings call for additional studies to further evaluate health risks associated with the use of nanoceria additives in various engines under various operating conditions.

  1. Template engaged synthesis of hollow ceria-based composites.

    PubMed

    Chen, Guozhu; Rosei, Federico; Ma, Dongling

    2015-03-19

    Hollow ceria-based composites, which consist of noble metal nanoparticles or metal oxides as a secondary component, are being studied extensively for potential applications in heterogeneous catalysis. This is due to their unique features, which exhibit the advantages of a hollow structure (e.g. high surface area and low weight), and also integrate the properties of ceria and noble metals/metal oxides. More importantly, the synergistic effect between constituents in hollow ceria-based composites has been demonstrated in various catalytic reactions. In this feature article, we summarize the state-of-the-art in the synthesis of hollow ceria-based composites, including traditional hard-templates and more recently, sacrificial-template engaged strategies, highlighting the key role of selected templates in the formation of hollow composites. In addition, the catalytic applications of hollow ceria-based composites are briefly surveyed. Finally, challenges and perspectives on future advances of hollow ceria-based composites are outlined.

  2. Study on the CO Oxidation over Ceria-Based Nanocatalysts

    NASA Astrophysics Data System (ADS)

    Piumetti, Marco; Andana, Tahrizi; Bensaid, Samir; Russo, Nunzio; Fino, Debora; Pirone, Raffaele

    2016-03-01

    A series of ceria nanocatalysts have been prepared to study the structure dependency of the CO oxidation reaction. The ceria samples with well-defined nanostructures (nanocubes/Ce-NC and nanorods/Ce-NR) have been prepared using the hydrothermal method. Mesoporous ceria (Ce-MES) and ceria synthesized with solution combustion technique (Ce-SCS) have also been prepared for comparison. The lowest CO oxidation temperature has been reached by using ceria nanocubes (Ce-NC). This high activity draws immense contributions from the highly reactive (100) and (110) surfaces of the truncated nanocubes. The Ce-MES and Ce-SCS samples, despite their high surface areas, are unable to outdo the activity of Ce-NC and Ce-NR due to the abundant presence of (111) crystalline planes. This finding confirms the structure sensitivity of CO oxidation reaction catalyzed with ceria.

  3. Plasma sprayed ceria-containing interlayer

    DOEpatents

    Schmidt, Douglas S.; Folser, George R.

    2006-01-10

    A plasma sprayed ceria-containing interlayer is provided. The interlayer has particular application in connection with a solid oxide fuel cell used within a power generation system. The fuel cell advantageously comprises an air electrode, a plasma sprayed interlayer disposed on at least a portion of the air electrode, a plasma sprayed electrolyte disposed on at least a portion of the interlayer, and a fuel electrode applied on at least a portion of the electrolyte.

  4. Tuning the surface oxygen concentration of {111} surrounded ceria nanocrystals for enhanced photocatalytic activities

    NASA Astrophysics Data System (ADS)

    Younis, Adnan; Chu, Dewei; Kaneti, Yusuf Valentino; Li, Sean

    2015-12-01

    For oxide semiconductors, the morphology, particle size and oxygen vacancies are usually considered as key influential parameters for photocatalytic degradation of organic pollutants/dyes. It is widely accepted that cation doping not only modifies their phase and microstructures but also introduces variations in oxygen vacancy concentration. Herein, we report the fabrication of sub-10 nm sized pure and indium doped CeO2 nanocrystals (NCs) via a facile, green hydrothermal method for the investigation of photocatalytic activities. X-ray diffraction and transmission electron microscopy were employed to examine the crystal phase and morphology of the as-prepared nanocrystals. Raman and X-ray photoelectron spectroscopy techniques were implemented to investigate the presence and variations in oxygen vacancy concentration in un-doped and indium doped CeO2 nanocrystals. The photocatalytic activity results revealed that 10 at% doping is the optimal indium doping level to demonstrate superior dye removal efficiency (~40%) over un-doped and doped CeO2 NCs. Moreover, the 10% In-doped CeO2 nanocrystals expressed excellent cycling stability and superior photocatalytic performance toward other dye pollutants. Finally, on the basis of our findings, a possible photocatalytic mechanism in which indium doping can generate more surface oxygen vacancies in the ceria lattice which delay the electron-hole recombination rates, thus increasing the lifetime of electron-hole separation for enhanced photocatalytic performances was proposed.For oxide semiconductors, the morphology, particle size and oxygen vacancies are usually considered as key influential parameters for photocatalytic degradation of organic pollutants/dyes. It is widely accepted that cation doping not only modifies their phase and microstructures but also introduces variations in oxygen vacancy concentration. Herein, we report the fabrication of sub-10 nm sized pure and indium doped CeO2 nanocrystals (NCs) via a facile

  5. Nanoparticles of lanthanide oxysulfate/oxysulfide for improved oxygen storage/release.

    PubMed

    Zhang, Wuyuan; Arends, Isabel W C E; Djanashvili, Kristina

    2016-09-28

    Lanthanide oxysulfates have the ability to store and release large volumes of oxygen under oxidizing/reducing conditions, rendering them interesting as automotive catalysts. Herein we demonstrate a remarkable improvement of both processes by utilization of nanoparticles compared to the bulk materials. A further improvement of the catalytic activity was achieved by cost-effective doping with 1.9 wt% of Ni.

  6. Electrical properties of ceria-carbonate composite electrolytes

    SciTech Connect

    Zhu Wei; Xia Changrong . E-mail: xiacr@ustc.edu.cn; Ding Dong; Shi Xiaoya; Meng Guangyao

    2006-11-09

    Electrical conductivity and transport properties for composites consisting of samaria-doped ceria (SDC) and lithium-potassium carbonate were investigated at temperature of 450-550 deg. C. The conductivity at temperature above 500 deg. C as measured with ac impedance spectrum is 0.06-0.07 S cm{sup -1}, which is about one magnitude higher than that of SDC. The conductivity increases with carbonate content and is boosted to several times when the volume fraction of carbonate reaches 30%. An abrupt change in the electrical conductivity at 500 deg. C infers that superionic phase transition possibly occurs in the interface between SDC and carbonate. Negligible electronic conduction, {approx}10{sup -4} S cm{sup -1} at 500-550 deg. C, is observed with an ion-blocking cell. The dc transport numbers of carbonate ion and proton are determined by carbon dioxide and vapor concentration cells, respectively. Carbonate ionic transport number is about 0.67 above 500 deg. C whereas the protonic transport number is below 0.1. The oxygen ion transport number is calculated to be 0.23 at 550 deg. C and 0.31 at 500 deg. C.

  7. Copper-ceria interaction: A combined photoemission and DFT study

    NASA Astrophysics Data System (ADS)

    Szabová, Lucie; Skála, Tomáš; Matolínová, Iva; Fabris, Stefano; Farnesi Camellone, Matteo; Matolín, Vladimír

    2013-02-01

    Stoichiometric and partially reduced ceria films were deposited on preoxidized Ru(0 0 0 1) crystal by Ce evaporation in oxygen atmosphere of different pressures at 700 K. Copper-ceria interaction was investigated by deposition of metalic copper on both types of substrate. The samples were characterized by low energy electron diffraction (LEED), X-ray photoelectron spectroscopy (XPS) of core states and resonant photoelectron spectroscopy (RPES) of the valence bands. Copper adsorption on stoichiometric ceria caused reduction of CeO2, while on the oxygen-defficient ceria it partially reoxidized the substrate. This is in agreement with DFT+U calculations of copper adsorption on stoichiometric and defective ceria surfaces.

  8. Calibration beads containing luminescent lanthanide ion complexes

    EPA Science Inventory

    The reliability of lanthanide luminescence measurements, by both flow cytometry and digital microscopy, will be enhanced by the availability of narrow-band emitting lanthanide calibration beads. These beads can also be used to characterize spectrographic instruments, including mi...

  9. Electrical and microstructural characterization of two-step sintered ceria-based electrolytes

    NASA Astrophysics Data System (ADS)

    Lapa, C. M.; Souza, D. P. Ferreira de; Figueiredo, F. M. L.; Marques, F. M. B.

    Gadolinium-doped ceria-based materials with and without Ga-additions were prepared following several firing schedules including one peak sintering temperature (up to 1300 °C) with or without subsequent dwell at lower temperature (at 1150 °C). Sintered disks with submicrometric grain size and densifications in the order of 92% or higher, were obtained in this manner, with the final result depending slightly on the sintering profile and presence of Ga as dopant. All materials were characterized by scanning electron microscopy, X-ray diffraction and impedance spectroscopy in air, in the temperature range 200-800 °C. The grain boundary arcs were found slightly dependent on grain size and porosity but significantly on Ga-doping, due to the likely presence of large concentrations of Ga along the grain boundary region.

  10. Silica Supported Ceria Nanoparticles: A Hybrid Nanostructure To Increase Stability And Surface Reactivity Of Nano-crystalline Ceria

    SciTech Connect

    Munusamy, Prabhakaran; Sanghavi, Shail P.; Varga, Tamas; Thevuthasan, Suntharampillai

    2014-01-21

    The mixed oxidation state (3+/4+) of ceria nanoparticles of smaller sizes make them attractive materials for their catalytic antioxidant biological properties. However the unmodified smaller ceria nanoparticles are limited in their use due to particles agglomeration and reduced surface chemical reactivity in the solutions used to disperse the nanoparticles. This work describes an effort to stabilize small ceria nanoparticles, retaining their desired activity, on a larger stable silica support. The ceria nanoparticles attached to silica was synthesized by a solution synthesis technique in which the surface functional groups of silica nanoparticles were found to be essential for the formation of smaller ceria nanoparticles. The surface chemical and vibrational spectroscopy analysis revealed cerium–silicate (Ce-O-Si) covalent bond linkage between silica and cerium oxide nanoparticles. The colloidal properties (agglomerate particle size and suspension stability) of ceria attached to silica was significantly improved due to inherent physico-chemical characteristics of silica against random collision and gravitation settling as opposed to unmodified ceria nanoparticles in solution. The bio-catalytic activity of ceria nanoparticles in the 3+ oxidation state was not found to be limited by attachment to the silica support as measured by free radical scavenging activity in different biological media conditions.

  11. Biocompatibility evaluation of porous ceria foams for orthopedic tissue engineering.

    PubMed

    Ball, Jordan P; Mound, Brittnee A; Monsalve, Adam G; Nino, Juan C; Allen, Josephine B

    2015-01-01

    Ceria ceramics have the unique ability to protect cells from free radical-induced damage, making them materials of interest for biomedical applications. To expand upon the understanding of the potential of ceria as a biomaterial, porous ceria, fabricated via direct foaming, was investigated to assess its biocompatibility and its ability to scavenge free radicals. A mouse osteoblast (7F2) cell line was cultured with the ceria foams to determine the extent of the foams' toxicity. Toxicity assessments indicate that mouse osteoblasts cultured directly on the ceria scaffold for 72 h did not show a significant (p > 0.05) increase in toxicity, but rather show comparable toxicity to cells cultured on porous 45S5 Bioglass. The in vitro inflammatory response elicited from porous ceria foams was measured as a function of tumor necrosis factor alpha (TNF-α) secreted from a human monocytic leukemia cell line. Results indicate that the ceria foams do not cause a significant inflammatory response, eliciting a response of 27.1 ± 7.1 pg mL(-1) of TNF-α compared to 36.3 ± 5.8 pg mL(-1) from cells on Bioglass, and 20.1 ± 2.9 pg mL(-1) from untreated cells. Finally, we report cellular toxicity in response to free radicals from tert-butyl hydroperoxide with and without foamed ceria. Our preliminary results show that the foamed ceria is able to decrease the toxic effect of induced oxidative stress. Collectively, this study demonstrates that foamed ceria scaffolds do not activate an inflammatory response, and show potential free radical scavenging ability, thus they have promise as an orthopedic biomaterial.

  12. The Lanthanide Contraction beyond Coordination Chemistry.

    PubMed

    Ferru, Geoffroy; Reinhart, Benjamin; Bera, Mrinal K; Olvera de la Cruz, Monica; Qiao, Baofu; Ellis, Ross J

    2016-05-10

    The lanthanide contraction is conceptualized traditionally through coordination chemistry. Here we break this mold in a structural study of lanthanide ions dissolved in an amphiphilic liquid. The lanthanide contraction perturbs the weak interactions between molecular aggregates that drive mesoscale assembly and emergent behavior. The weak interactions correlate with lanthanide ion transport properties, suggesting new strategies for rare-earth separation that exploit forces outside of the coordination sphere.

  13. Composite ceria-coated aerogels and methods of making the same

    DOEpatents

    Eyring, Edward M; Ernst, Richard D; Turpin, Gregory C; Dunn, Brian C

    2013-05-07

    Ceria-coated aerogels can include an aerogel support material having a stabilized ceria coating thereon. The ceria coating can be formed by solution or vapor deposition of alcogels or aerogels. Additional catalytic metal species can also be incorporated into the coating to form multi-metallic compounds having improved catalytic activity. Further, the ceria coated aerogels retain high surface areas at elevated temperatures. Thus, improvements in catalytic activity and thermal stability can be achieved using these ceria-coated composite aerogels.

  14. Lanthanides: New life metals?

    PubMed

    Chistoserdova, Ludmila

    2016-08-01

    Lanthanides (Ln(3+)) that are Rare Earth Elements, until recently thought to be biologically inert, have recently emerged as essential metals for activity and expression of a special type of methanol dehydrogenase, XoxF. As XoxF enzyme homologs are encoded in a wide variety of microbes, including microbes active in important environmental processes such as methane and methanol metabolism, Ln(3+) may represent some of the key biogeochemical drivers in cycling of carbon and other elements. However, significant gaps in understanding the role of Ln(3+) in biological systems remain as the functions of most of the proteins potentially dependent of Ln(3+) and their roles in specific metabolic networks/respective biogeochemical cycles remain unknown. Moreover, enzymes dependent on Ln(3+) but not related to XoxF enzymes may exist, and these so far have not been recognized. Through connecting the recently uncovered genetic divergence and phylogenetic distribution of XoxF-like enzymes and through elucidation of their activities, metal and substrate specificities, along with the biological contexts of respective biochemical pathways, most parsimonious scenarios for their evolution could be uncovered. Generation of such data will firmly establish the role of Ln(3+) in the biochemistry of Life inhabiting this planet. PMID:27357406

  15. Oxygen transport in ceria: a first-principles study

    NASA Astrophysics Data System (ADS)

    Sergei, Simak

    2012-02-01

    Ceria (CeO2) is an important material for environmentally benign applications, ranging from solid-oxide fuel cells (SOFC) to oxygen storage [1-2]. The key characteristic needed to be improved is the mobility of oxygen ions. Optimization of ionic transport in ceria has been the topic of many studies. In particular, it has been discovered how the ionic conductivity in ceria might be improved by choosing the proper kind and concentration of dopants [3]. In this presentation we will approach the problem from a different direction by adjusting structural parameters of ceria via the change of external conditions. A systematic first-principles study of the energy landscape and kinetics of reduced ceria as a function of external parameters reveals a physically transparent way to improve oxygen transport in ceria. [4pt] [1] N. Skorodumova, S. Simak, B. Lundqvist, I. Abrikosov, and B. Johansson, Physical Review Letters 89, 14 (2002). [0pt] [2] A. Trovarelli, in Catalysis by Ceria and related materials (Imperial College Press, London, 2002). [0pt] [3] D. A. Andersson, S. I. Simak, N. V. Skorodumova, I. A.Abrikosov, and B. Johansson, Proceedings of the National Academy of Sciences of the United States of America 103, 3518 (2006).

  16. Probing adsorption sites for CO on ceria.

    PubMed

    Mudiyanselage, Kumudu; Kim, Hyun You; Senanayake, Sanjaya D; Baber, Ashleigh E; Liu, Ping; Stacchiola, Dario

    2013-10-14

    Ceria based catalysts show remarkable activity for CO conversion reactions such as CO oxidation and the water-gas shift reaction. The identification of adsorption sites on the catalyst surfaces is essential to understand the reaction mechanisms of these reactions, but the complexity of heterogeneous powder catalysts and the propensity of ceria to easily change oxidation states in the presence of small concentrations of either oxidizing or reducing agents make the process difficult. In this study, the adsorption of CO on CuOx/Cu(111) and CeOx/Cu(111) systems has been studied using infrared reflection absorption spectroscopy (IRRAS), X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) calculations. IR peaks for the adsorbed CO on O/Cu(111) with only chemisorbed oxygen, well-ordered Cu2O/Cu(111) and disordered copper oxide [CuOx/Cu(111)] were observed at 2070-2072, 2097-2098 and 2101-2111 cm(-1), respectively. On CeOx/Cu(111) systems CO chemisorbs at 90 K only on Cu sites under ultra-high vacuum (UHV) conditions, whereas at elevated CO pressures and low temperatures adsorption of CO on Ce(3+) is observed, with a corresponding IR peak at 2162 cm(-1). These experimental results are further supported by DFT calculations, and help to unequivocally distinguish the presence of Ce(3+) cations on catalyst samples by using CO as a probe molecule. PMID:23942870

  17. Establishing the Structural Integrity of Core-Shell Nanoparticles against Elemental Migration using Luminescent Lanthanide Probes.

    PubMed

    Chen, Bing; Peng, Dengfeng; Chen, Xian; Qiao, Xvsheng; Fan, Xianping; Wang, Feng

    2015-10-19

    Core-shell structured nanoparticles are increasingly used to host luminescent lanthanide ions but the structural integrity of these nanoparticles still lacks sufficient understanding. Herein, we present a new approach to detect the diffusion of dopant ions in core-shell nanostructures using luminescent lanthanide probes whose emission profile and luminescence lifetime are sensitive to the chemical environment. We show that dopant ions in solution-synthesized core-shell nanoparticles are firmly confined in the designed locations. However, annealing at certain temperatures (greater than circa 350 °C) promotes diffusion of the dopant ions and leads to degradation of the integrity of the nanoparticles. These insights into core-shell nanostructures should enhance our ability to understand and use lanthanide-doped luminescent nanoparticles.

  18. Ozonation of bezafibrate over ceria and ceria supported on carbon materials.

    PubMed

    Gonçalves, Alexandra G; Órfão, José J M; Pereira, Manuel Fernando R

    2015-01-01

    Two catalysts containing ceria dispersed on the surface of multi-walled carbon nanotubes and activated carbon were investigated as ozonation catalysts for the mineralization of bezafibrate (BZF). The results were compared with those obtained in the absence of the catalyst and in the presence of the parent carbon materials, as well as in the presence of ceria (CeO2). Carbon materials containing ceria showed an interesting catalytic effect. Both materials enhanced the mineralization of BZF relatively to single ozonation and ozonation catalysed by the corresponding carbon materials. In the catalytic ozonation with these materials, both surface and bulk reactions are supposed to occur. The BZF ozonation catalysed by CeO2 leaded to the highest mineralization degrees, indicating that the reaction mechanism followed in the presence of CeO2 (free radical oxidation in solution) leads to the formation of intermediates more easily degradable, mainly after 120 min of reaction. Some primary products and refractory final oxidation compounds in single and catalytic ozonation of BZF were followed. The original chlorine present on the BZF molecule is completely converted to chloride anion and part of the nitrogen is mainly converted to NO3- along with smaller amounts of NO2- and NH4+. Microtox tests revealed that simultaneous use of ozone and CeO2 originated lower acute toxicity. PMID:25189707

  19. Biological toxicity of lanthanide elements on algae.

    PubMed

    Tai, Peidong; Zhao, Qing; Su, Dan; Li, Peijun; Stagnitti, Frank

    2010-08-01

    The biological toxicity of lanthanides on marine monocellular algae was investigated. The specific objective of this research was to establish the relationship between the abundance in the seawater of lanthanides and their biological toxicities on marine monocellular algae. The results showed that all single lanthanides had similar toxic effects on Skeletonema costatum. High concentrations of lanthanides (29.04+/-0.61 micromol L(-1)) resulted in 50% reduction in growth of algae compared to the controls (0 micromol L(-1)) after 96 h (96 h-EC50). The biological toxicity of 13 lanthanides on marine monocellular algae was unrelated with the abundance of different lanthanide elements in nature, and the "Harkins rule" was not appropriate for the lanthanides. A mixed solution that contained equivalent concentrations of each lanthanide element had the same inhibition effect on algae cells as each individual lanthanide element at the same total concentration. This phenomenon is unique compared to the groups of other elements in the periodic table. Hence, we speculate that the monocellular organisms might not be able to sufficiently differentiate between the almost chemically identical lanthanide elements.

  20. Biological toxicity of lanthanide elements on algae.

    PubMed

    Tai, Peidong; Zhao, Qing; Su, Dan; Li, Peijun; Stagnitti, Frank

    2010-08-01

    The biological toxicity of lanthanides on marine monocellular algae was investigated. The specific objective of this research was to establish the relationship between the abundance in the seawater of lanthanides and their biological toxicities on marine monocellular algae. The results showed that all single lanthanides had similar toxic effects on Skeletonema costatum. High concentrations of lanthanides (29.04+/-0.61 micromol L(-1)) resulted in 50% reduction in growth of algae compared to the controls (0 micromol L(-1)) after 96 h (96 h-EC50). The biological toxicity of 13 lanthanides on marine monocellular algae was unrelated with the abundance of different lanthanide elements in nature, and the "Harkins rule" was not appropriate for the lanthanides. A mixed solution that contained equivalent concentrations of each lanthanide element had the same inhibition effect on algae cells as each individual lanthanide element at the same total concentration. This phenomenon is unique compared to the groups of other elements in the periodic table. Hence, we speculate that the monocellular organisms might not be able to sufficiently differentiate between the almost chemically identical lanthanide elements. PMID:20547408

  1. Ceria-based solid catalysts for organic chemistry.

    PubMed

    Vivier, Laurence; Duprez, Daniel

    2010-06-21

    Ceria has been the subject of thorough investigations, mainly because of its use as an active component of catalytic converters for the treatment of exhaust gases. However, ceria-based catalysts have also been developed for different applications in organic chemistry. The redox and acid-base properties of ceria, either alone or in the presence of transition metals, are important parameters that allow to activate complex organic molecules and to selectively orient their transformation. Pure ceria is used in several organic reactions, such as the dehydration of alcohols, the alkylation of aromatic compounds, ketone formation, and aldolization, and in redox reactions. Ceria-supported metal catalysts allow the hydrogenation of many unsaturated compounds. They can also be used for coupling or ring-opening reactions. Cerium atoms can be added as dopants to catalytic system or impregnated onto zeolites and mesoporous catalyst materials to improve their performances. This Review demonstrates that the exceptional surface (and sometimes bulk) properties of ceria make cerium-based catalysts very effective for a broad range of organic reactions.

  2. Dissolved oxygen sensing based on fluorescence quenching of ceria nanoparticles

    NASA Astrophysics Data System (ADS)

    Shehata, Nader; Meehan, Kathleen; Leber, Donald

    2012-10-01

    The development of oxygen sensors has positively impacted the fields of medical science, bioengineering, environmental monitoring, solar cells, industrial process control, and a number of military applications. Fluorescent quenching sensors have an inherent high sensitivity, chemical selectivity, and stability when compared to other types of sensors. While cerium oxide thin films have been used to monitor oxygen in the gas phase, the potential of cerium oxide (ceria) nanoparticles as the active material in sensor for oxygen gas has only recently been investigated. Ceria nanoparticles are one of the most unique nanomaterials that are being studied today due to the diffusion and reactivity of its oxygen vacancies, which contributes to its high oxygen storage capability. The reactivity of the oxygen vacancies, which is also related to conversion of cerium ion from the Ce+4 to Ce+3 state, affects the fluorescence properties of the ceria nanoparticles. Our research demonstrates that the ceria nanoparticles (~7 nm in diameter) have application as a fluorescence quenching sensor to measure dissolved oxygen in water. We have found a strong inverse correlation between the amplitude of the fluorescence emission (λexcitation = 430 nm and λpeak = 520 nm) and the dissolved oxygen concentration between 5 - 13 mg/L. The Stern-Volmer constant, which is an indication of the sensitivity of gas sensing is 184 M-1 for the ceria nanoparticles. The results show that ceria nanoparticles can be used in an improved, robust fluorescence sensor for dissolved oxygen in a liquid medium.

  3. Adhesion and Atomic Structures of Gold on Ceria Nanostructures: The Role of Surface Structure and Oxidation State of Ceria Supports.

    PubMed

    Lin, Yuyuan; Wu, Zili; Wen, Jianguo; Ding, Kunlun; Yang, Xiaoyun; Poeppelmeier, Kenneth R; Marks, Laurence D

    2015-08-12

    We report an aberration-corrected electron microscopy analysis of the adhesion and atomic structures of gold nanoparticle catalysts supported on ceria nanocubes and nanorods. Under oxidative conditions, the as-prepared gold nanoparticles on the ceria nanocubes have extended atom layers at the metal-support interface. In contrast, regular gold nanoparticles and rafts are present on the ceria nanorod supports. Under the reducing conditions of water-gas shift reaction, the extended gold atom layers and rafts vanish. In addition, the gold particles on the nanocubes change in morphology and increase in size while those on the nanorods are almost unchanged. The size, morphology, and atomic interface structures of gold strongly depend on the surface structures of ceria supports ((100) surface versus (111) surface) and the reaction environment (reductive versus oxidative). These findings provide insights into the deactivation mechanisms and the shape-dependent catalysis of oxide supported metal catalysts.

  4. Thermal Conductivity in Nanocrystalline Ceria Thin Films

    SciTech Connect

    Marat Khafizov; In-Wook Park; Aleksandr Chernatynskiy; Lingfeng He; Jianliang Lin; John J. Moore; David Swank; Thomas Lillo; Simon R. Phillpot; Anter El-Azab; David H. Hurley

    2014-02-01

    The thermal conductivity of nanocrystalline ceria films grown by unbalanced magnetron sputtering is determined as a function of temperature using laser-based modulated thermoreflectance. The films exhibit significantly reduced conductivity compared with stoichiometric bulk CeO2. A variety of microstructure imaging techniques including X-ray diffraction, scanning and transmission electron microscopy, X-ray photoelectron analysis, and electron energy loss spectroscopy indicate that the thermal conductivity is influenced by grain boundaries, dislocations, and oxygen vacancies. The temperature dependence of the thermal conductivity is analyzed using an analytical solution of the Boltzmann transport equation. The conclusion of this study is that oxygen vacancies pose a smaller impediment to thermal transport when they segregate along grain boundaries.

  5. Investigation of Gravity Lanthanide Separation Chemistry

    SciTech Connect

    Payne, Rosara F.; Schulte, Shannon M.; Douglas, Matthew; Friese, Judah I.; Farmer, Orville T.; Finn, Erin C.

    2011-03-01

    Lanthanides are common fission products and the ability to separate and quantify these elements is critical to rapid radiochemistry applications. Published lanthanide separations using Eichrom Ln Spec resin utilize an HCl gradient. Here it is shown that the efficacy and resolution of the separation is improved when a nitric acid gradient is used instead. The described method allows parallel processing of many samples in 1.5 hours followed by 60 minute counting for quantification of 9 isotopes of 7 lanthanide elements.

  6. Fracture-resistant lanthanide scintillators

    DOEpatents

    Doty, F. Patrick

    2011-01-04

    Lanthanide halide alloys have recently enabled scintillating gamma ray spectrometers comparable to room temperature semiconductors (<3% FWHM energy resolutions at 662 keV). However brittle fracture of these materials upon cooling hinders the growth of large volume crystals. Efforts to improve the strength through non-lanthanide alloy substitution, while preserving scintillation, have been demonstrated. Isovalent alloys having nominal compositions of comprising Al, Ga, Sc, Y, and In dopants as well as aliovalent alloys comprising Ca, Sr, Zr, Hf, Zn, and Pb dopants were prepared. All of these alloys exhibit bright fluorescence under UV excitation, with varying shifts in the spectral peaks and intensities relative to pure CeBr.sub.3. Further, these alloys scintillate when coupled to a photomultiplier tube (PMT) and exposed to .sup.137Cs gamma rays.

  7. Nanoparticles of lanthanide oxysulfate/oxysulfide for improved oxygen storage/release.

    PubMed

    Zhang, Wuyuan; Arends, Isabel W C E; Djanashvili, Kristina

    2016-09-28

    Lanthanide oxysulfates have the ability to store and release large volumes of oxygen under oxidizing/reducing conditions, rendering them interesting as automotive catalysts. Herein we demonstrate a remarkable improvement of both processes by utilization of nanoparticles compared to the bulk materials. A further improvement of the catalytic activity was achieved by cost-effective doping with 1.9 wt% of Ni. PMID:27515224

  8. Growth and characterization of Sc-doped EuO thin films

    SciTech Connect

    Altendorf, S. G.; Reisner, A.; Chang, C. F.; Hollmann, N.; Rata, A. D.; Tjeng, L. H.

    2014-02-03

    The preparation of 3d-transition metal-doped EuO thin films by molecular beam epitaxy is investigated using the example of Sc doping. The Sc-doped EuO samples display a good crystalline structure, despite the relatively small ionic radius of the dopant. The Sc doping leads to an enhancement of the Curie temperature to up to 125 K, remarkably similar to previous observations on lanthanide-doped EuO.

  9. Surface morphology, optical and electrochemical properties of undoped and Ni-doped CeO2 thin films prepared by polymeric precursor method

    NASA Astrophysics Data System (ADS)

    Khosousi Sani, Zara; Esmaeli Ghodsi, Farhad; Mazloom, Jamal

    2016-04-01

    In this study, undoped and Ni-doped CeO2 thin films were deposited onto glass and ITO substrates by polymeric precursor (Pechini) method. Grazing incidence X-ray diffraction analysis revealed that the ceria thin film has a cerianite structure with the average crystallite size of 14 nm while the doped samples are amorphous. X-ray photoelectron spectroscopy (XPS) confirmed the presence of predominant Ce4+ oxidation state of ceria and Ni2+ in the films. Scanning electron microscopy (SEM) micrographs showed that the surface texture is crack free and the CeO2 grains regularly distributed on the surface. Optical constant (refractive index and extinction coefficient) and thickness of films were calculated using pointwise unconstraint minimization approach. The optical transmittance increases and the absorption edge has a blue shift by Ni incorporation. The highest band gap value (i.e., 3.43 eV) was obtained for 2.5 mol.% Ni doping sample. The refractive index and extinction coefficient of ceria films were decreased by Ni doping. The evaluated thicknesses are in the range of 150-170 nm. The strength of interband transition was appraised as a function of nickel content by using dielectric function. Luminescent emission intensity of the ceria film was enhanced by Ni doping. Cyclic voltammetry (CV) measurement revealed that the total charge density and ion storage capacitance of ceria thin film were increased by Ni doping.

  10. Enantioselective catalysis using lanthanide Schiff base complexes

    SciTech Connect

    Watkin, J.G.

    1996-10-01

    The use of lanthanide-based catalysts to facilitate organic transformations is currently an area of rapid growth, in particular the application of lanthanide alkoxide and triflate derivatives as effective Lewis-acidic catalysts for Michael additions and aldol reactions, and bis-pentamethylcyclopentadienyl derivatives as extremely active catalysts for hydrogenation and enantioselective hydroamination reactions. We have begun an investigation into the use of lanthanide complexes containing chiral alkoxide ligands as Lewis-acidic catalysts for enantioselective organic reactions. Since the large ionic radii of the lanthanide +III metal centers can often lead to oligomerization of simple alkoxide species, we have also examined the use of multidentate, chelating Schiff base ligands to provide an asymmetric environment about a lanthanide metal center. Structural investigations of the catalysts will be described, together with the use of these catalysts in enantioselective Meerwein-Ponndorf-Verley reduction of ketones and nitroaldol reactions.

  11. Radiation-Induced Reduction of Ceria in Single and Polycrystalline Thin Films

    SciTech Connect

    Kumar, Amit; Devanathan, Ramaswami; Shutthanandan, V.; Kuchibhatla, Satyanarayana V N T; Karakoti, Ajay S.; Yang, Yong; Thevuthasan, Suntharampillai; Seal, Sudipta

    2012-01-12

    Ceria (CeO{sub 2}) is a technologically important ceramic material with a wide range of neoteric applications in catalysis, solid oxide fuel cells, oxygen gas sensors, hydrogen production, and ultraviolet shielding. Recent research has revealed promising biomedical applications of ceria. Nanoparticles of ceria have been shown to protect healthy cells from radiation-induced cellular damage. The mechanisms governing the radioprotection characteristics of ceria nanoparticles are not well understood and it has been hypothesized that reversible switching between Ce{sup 4+} and Ce{sup 3+} states may enable ceria nanoparticles to mop up free radicals.

  12. Effect of Ceria on the Sulfation and Desulfation Characteristics of a Model Lean NOx Trap Catalyst

    SciTech Connect

    Ji, Yaying; Toops, Todd J; Crocker, Mark

    2009-01-01

    The effect of ceria addition on the sulfation and desulfation characteristics of a model Ba-based lean NO{sub x} trap (LNT) catalyst was studied. According to DRIFTS and NO{sub x} storage capacity measurements, ceria is able to store sulfur during catalyst exposure to SO{sub 2}, thereby helping to limit sulfation of the main (Ba) NO{sub x} storage phase and maintain NO{sub x} storage capacity. Temperature programmed desulfation experiments revealed that desulfation of a model ceria-containing catalyst occurred in two stages, corresponding to sulfur elimination from the ceria phase at {approx}450 C, followed by sulfur loss from the Ba phase at {approx}650 C. Significantly, the ceria-containing catalyst displayed relatively lower sulfur evolution from the Ba phase than its non-ceria analog, confirming that the presence of ceria lessened the degree of sulfur accumulation on the Ba phase.

  13. Separation of actinides from lanthanides

    DOEpatents

    Smith, Barbara F.; Jarvinen, Gordon D.; Ryan, Robert R.

    1989-01-01

    An organic extracting solution and an extraction method useful for separating elements of the actinide series of the periodic table from elements of the lanthanide series, where both are in trivalent form. The extracting solution consists of a primary ligand and a secondary ligand, preferably in an organic solvent. The primary ligand is a substituted monothio-1,3-dicarbonyl, which includes a substituted 4-acyl-2-pyrazolin-5-thione, such as 4-benzoyl-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-thione (BMPPT). The secondary ligand is a substituted phosphine oxide, such as trioctylphosphine oxide (TOPO).

  14. Structural Modification of Nanocrystalline Ceria using Ion Beams

    SciTech Connect

    Zhang, Yanwen; Edmondson, Philip D; Varga, Tamas; Moll, Sandra; Namavar, Fereydoon; Weber, William J

    2011-01-01

    Exceptional size-dependent electronic-ionic conductivity of nanostructured ceria can significantly alter materials properties in chemical, physical, electronic and optical applications. Using energetic ions, we have demonstrated effective modification of interface volume and grain size in nanocrystalline ceria from a few nm up to ~ 25 nm, which is the critical region for controlling size-dependent material property. The unique self-healing response of radiation damage at grain boundaries is applied to control the grain size at nanoscale as a function of ion dose and irradiation temperature. Structural modification by energetic ions is proposed to achieve disirable electronic-ionic conductivity.

  15. Pt/Ceria-based Catalysts for Small Alcohol Electrooxidation

    NASA Astrophysics Data System (ADS)

    Menendez-Mora, Christian L.

    High emissions of fossil-based energy sources have led to scientists around the world to develop new alternatives for the future. In this sense, fuel cells are a remarkable and promising energy option with less environmental impact. The most used fuels for this technology are hydrogen and small chain alcohols, which can be oxidized to transform their chemical energy into electrical power. To do this, fuel cells need catalysts that will act as an active surface where the oxidation can take place. The problem with platinum catalysts is its possible CO poisoning with intermediates that are produced before the complete oxidation of alcohol to CO2. Different approaches have been taken to try to resolve this issue. In this case, cerium oxide (ceria) was selected as a co-catalyst to mitigate the effect of CO poisoning of platinum. Ceria is a compound that has the ability to work as an "oxygen tank" and can donate oxygen to carbon monoxide that is strongly adsorbed at platinum surface to produce CO2 (carbon dioxide), regenerating the Pt surface for further alcohol oxidation. Therefore, enhancing the current density as well as the power output of a fuel cell. First, an occlusion deposition technique was used to prepare platinum/ceria composite electrodes and tested them towards small chain alcohol oxidation such as methanol oxidation reaction in acidic and alkaline media. The preliminary results demonstrated that the Pt/ceria electrodes were more efficient towards methanol electrooxidation when compared to Pt electrodes. This enhancement was attributed to the presence of ceria. A second preparation method was selected for the synthesis of ceria/Pt catalysts. In this case, a hydrothermal method was used and the catalysis were studied for the effect of MeOH, EtOH and n-BuOH oxidation. The observed effect was that electrodes made of Pt/Pt:CeO2-x showed better catalytic effect than Pt/ceria and platinum electrodes. Moreover, a comparison between ceria nanorods versus

  16. Analysis of multinuclear lanthanide-induced shifts. 4. Some consequences of the lanthanide contraction

    NASA Astrophysics Data System (ADS)

    Peters, Joop A.

    The effects of the lanthanide contraction on lanthanide-induced shifts are estimated using simulated structures for a set of lanthanide chelates. The variations of the Ln-donor distances cause small conformational changes in the coordination polyhedron of the Ln(III) cation, and the induced pseudocontact shifts for a series of Ln complexes vary gradually going from La(III) to Lu(III). As a result of data manipulation these gradual variations may sometimes show up as an abrupt break in the middle of the lanthanide series.

  17. Adsorption and desorption characteristics of arsenic onto ceria nanoparticles

    PubMed Central

    2012-01-01

    The rapid increase in the use of engineered nanoparticles [ENPs] has resulted in an increasing concern over the potential impacts of ENPs on the environmental and human health. ENPs tend to adsorb a large variety of toxic chemicals when they are emitted into the environment, which may enhance the toxicity of ENPs and/or adsorbed chemicals. The study was aimed to investigate the adsorption and desorption behaviors of arsenic on ceria NPs in aqueous solution using batch technique. Results show that the adsorption behavior of arsenic on ceria NPs was strongly dependent on pH and independent of ionic strength, indicating that the electrostatic effect on the adsorption of these elements was relatively not important compared to surface chemical reactions. The adsorption isotherms fitted very well to both the Langmuir and Freundlich models. The thermodynamic parameters (ΔH0, ΔS0, and ΔG0) for the adsorption of arsenic were determined at three different temperatures of 283, 303, and 323 K. The adsorption reaction was endothermic, and the process of adsorption was favored at high temperature. The desorption data showed that desorption hysteresis occurred at the initial concentration studied. High adsorption capacity of arsenic on ceria NPs suggests that the synergistic effects of ceria NPs and arsenic on the environmental systems may exist when they are released into the environment. PMID:22269298

  18. Paper bioassay based on ceria nanoparticles as colorimetric probes.

    PubMed

    Ornatska, Maryna; Sharpe, Erica; Andreescu, Daniel; Andreescu, Silvana

    2011-06-01

    We report the first use of redox nanoparticles of cerium oxide as colorimetric probes in bioanalysis. The method is based on changes in the physicochemical properties of ceria nanoparticles, used here as chromogenic indicators, in response to the analyte. We show that these particles can be fully integrated in a paper-based bioassay. To construct the sensor, ceria nanoparticles and glucose oxidase were coimmobilized onto filter paper using a silanization procedure. In the presence of glucose, the enzymatically generated hydrogen peroxide induces a visual color change of the ceria nanoparticles immobilized onto the bioactive sensing paper, from white-yellowish to dark orange, in a concentration-dependent manner. A detection limit of 0.5 mM glucose with a linear range up to 100 mM and a reproducibility of 4.3% for n = 11 ceria paper strips were obtained. The assay is fully reversible and can be reused for at least 10 consecutive measurement cycles, without significant loss of activity. Another unique feature is that it does not require external reagents, as all the sensing components are fixed onto the paper platform. The bioassay can be stored for at least 79 days at room temperature while maintaining the same analytical performance. An example of analytical application was demonstrated for the detection of glucose in human serum. The results demonstrate the potential of this type of nanoparticles as novel components in the development of robust colorimetric bioassays. PMID:21524141

  19. Nitride tuning of lanthanide chromites.

    PubMed

    Black, Ashley P; Johnston, Hannah E; Oró-Solé, Judith; Bozzo, Bernat; Ritter, Clemens; Frontera, Carlos; Attfield, J Paul; Fuertes, Amparo

    2016-03-21

    LnCrO(3-x)N(x) perovskites with Ln = La, Pr and Nd and nitrogen contents up to x = 0.59 have been synthesised through ammonolysis of LnCrO4 precursors. These new materials represent one of the few examples of chromium oxynitrides. Hole-doping through O(2-)/N(3-) anion substitution suppresses the magnetic transition far less drastically than Ln(3+)/M(2+) (M = Ca, Sr) cation substitutions because of the greater covalency of metal-nitride bonds. Hence, nitride-doping is a more benign method for doping metal oxides without suppressing electronic transitions. PMID:26916315

  20. Catalytic Partial Oxidation of Methane Over Rh-Ceria Based Catalysts. Effect of Catalyst Reducibility

    SciTech Connect

    Salazar, M.D.; Berry, D.A.; Gardner, T.H.

    2007-09-01

    High catalytic activities are required during syn-gas generation via the partial oxidation of methane (POM). In order to study the role of catalyst reducibility, catalytic performance of Rh/Ce0.56Zr0.44O2-x and Rh/CeO2 was studied. Cerium oxide based support materials were prepared by co-precipitation followed by hydrothermal crystallization. Rhodium was incorporated by a modified incipient wetness technique. The catalytic activity, selectivity and stability of these materials as a function of time on stream were investigated. Results showed that Rh/Ce0.56Zr0.44O2 had a higher methane conversion than Rh/CeO2. The selectivity for the generation of H2 and CO was also higher over the former catalyst than over Rh/CeO2. These results may be directly correlated to the promotion in the reducibility of the Rh-ceria interface by doping CeO2 with Zr as evidenced by Temperature Programmed Reduction (TPR) experiments. These tests were performed from 40ºC to 1100ºC and results showed that the H2 uptake by the zirconium doped catalyst was higher than by the Rh/CeO2 catalyst. Further catalyst characterization also included composition, surface area and crystal phase. The addition of Zr to CeO2 caused the formation of small amount of tetragonal phase.

  1. Luminescent lanthanide chelates and methods of use

    DOEpatents

    Selvin, Paul R.; Hearst, John

    1997-01-01

    The invention provides lanthanide chelates capable of intense luminescence. The celates comprise a lanthanide chelator covalently joined to a coumarin-like or quinolone-like sensitizer. Exemplary sensitzers include 2- or 4-quinolones, 2- or 4-coumarins, or derivatives thereof e.g. carbostyril 124 (7-amino-4-methyl-2-quinolone), coumarin 120 (7-amino-4-methyl-2-coumarin), coumarin 124 (7-amino-4-(trifluoromethyl)-2-coumarin), aminomethyltrimethylpsoralen, etc. The chelates form high affinity complexes with lanthanides, such as terbium or europium, through chelator groups, such as DTPA. The chelates may be coupled to a wide variety of compounds to create specific labels, probes, diagnostic and/or therapeutic reagents, etc. The chelates find particular use in resonance energy transfer between chelate-lanthanide complexes and another luminescent agent, often a fluorescent non-metal based resonance energy acceptor. The methods provide useful information about the structure, conformation, relative location and/or interactions of macromolecules.

  2. The role of lanthanides in optical materials

    SciTech Connect

    Weber, M.J.

    1995-05-01

    A survey is presented of the use of the lanthanides as chemical components in transmitting optical materials and as activators in materials for luminescent, electro-optic, magneto-optic, and various photosensitive applications.

  3. Ce K edge XAS of ceria-based redox materials under realistic conditions for the two-step solar thermochemical dissociation of water and/or CO2.

    PubMed

    Rothensteiner, Matthäus; Sala, Simone; Bonk, Alexander; Vogt, Ulrich; Emerich, Hermann; van Bokhoven, Jeroen A

    2015-10-28

    X-ray absorption spectroscopy was used to characterise ceria-based materials under realistic conditions present in a reactor for solar thermochemical two-step water and carbon dioxide splitting. A setup suitable for in situ measurements in transmission mode at the cerium K edge from room temperature up to 1773 K is presented. Time-resolved X-ray absorption near-edge structure (XANES) data, collected for a 10 mol% hafnium-doped ceria sample (Ce0.9Hf0.1O2-δ) during reduction at 1773 K in a flow of inert gas and during re-oxidation by CO2 at 1073 K, enables the quantitative determination of the non-stoichiometry δ of the fluorite-type structure. XANES analysis suggests the formation of the hexagonal Ce2O3 phase upon reduction in 2% hydrogen/helium at 1773 K. We discuss the experimental limitations and possibilities of high-temperature in situ XAS at edges of lower energy as well as the importance of the technique for understanding and improving the properties of ceria-based oxygen storage materials for thermochemical solar energy conversion.

  4. The role of strain and structure on oxygen ion conduction in nanoscale zirconia and ceria thin films

    NASA Astrophysics Data System (ADS)

    Jiang, Jun

    Solid oxide fuel cells (SOFCs), an all solid-state energy conversion device, are promising for their high efficiency and materials stability. The solid oxide electrolytes are a key component that must provide high ionic conductivity, which is especially challenging for intermediate temperature SOFCs operating between 500 °C - 700 °C. Doped zirconia and ceria are the most common solid electrolyte materials. Recent reports have suggested that nanoscale ytrria stabilized zirconia (YSZ) thin films may provide better performance in this regard. However, the mechanism behind the increased conductivity of nanoscale thin films is still unclear and the reported experimental results are controversial. In the thesis presented here, the effects of mechanical strain and microstructure on the ionic conductivity have been investigated in ultrathin zirconia- and ceria-based thin films. Reactive RF co-sputtering with metal targets was used to prepare zirconia and ceria based thin films for high purity, modulated composition and thickness. The films were as thin as 10-20 atomic layers thick. X-ray photoelectron spectroscopy, X-ray diffraction and transmission electron microscopy were the main tools to investigate the composition, crystal orientation and microstructure of these sputtered thin films. Microscale interdigitated Pt electrodes were prepared through a lift-off process using photolithography. The electrochemical properties of these sputtered doped zirconia and ceria thin films were investigated using impedance spectroscopy. YSZ thin films deposited on MgO (111) and, especially, MgO (100) showed highly variable crystal orientations, while MgO (110) offered much more stable growth. Regardless of whether the growth was epitaxial or highly disordered polycrystalline, 50 nm thick YSZ thin films on MgO (100), (110), and (111) substrates exhibited similar conductivity with YSZ single crystal. While decreasing the thickness further to 12 nm, the conductivities of YSZ thin films

  5. Core–shell Ag@SiO{sub 2} nanoparticles of different silica shell thicknesses: Preparation and their effects on photoluminescence of lanthanide complexes

    SciTech Connect

    Kang, Jie; Li, Yuan; Chen, Yingnan; Wang, Ailing; Yue, Bin; Qu, Yanrong; Zhao, Yongliang; Chu, Haibin

    2015-11-15

    Highlights: • Ag@SiO{sub 2} nanoparticles of different silica shell thicknesses were prepared via the Stöber process. • Sm and Dy complexes with benzoate, 1,10-phenanthroline and 2,2′-bipyridine were synthesized. • The complex-doped Ag@SiO{sub 2} composites show stronger luminescent intensities than pure complexes. • The luminescent intensities of the composites strongly depend on the SiO{sub 2} shell thickness. - Abstract: Three kinds of almost spherical core–shell Ag@SiO{sub 2} nanoparticles of different silica shell thicknesses (10, 25 and 80 nm) were prepared via the Stöber process. The Ag core nanoparticles were prepared by reducing silver nitrate with sodium citrate. The size, morphology and structure of core–shell Ag@SiO{sub 2} nanoparticles were characterized by transmission electron microscopy. Subsequently, eight kinds of lanthanide complexes with benzoate, 1,10-phenanthroline and 2,2′-bipyridine were synthesized. The composition of the lanthanide complexes was characterized by elemental analysis, IR and UV spectra. Finally, lanthanide complexes were attached to the surface of Ag@SiO{sub 2} nanoparticles to form lanthanide-complex-doped Ag@SiO{sub 2} nanocomposites. The results show that the complex-doped Ag@SiO{sub 2} nanocomposites display much stronger luminescence intensities than the lanthanide complexes. Furthermore, the luminescence intensities of the lanthanide-complex-doped Ag@SiO{sub 2} nanocomposites with SiO{sub 2} shell thickness of 25 nm are stronger than those of the nanocomposites with SiO{sub 2} shell thickness of 10 and 80 nm.

  6. The effect of Nd on the properties of ceria-zirconia solid solution and the catalytic performance of its supported Pd-only three-way catalyst for gasoline engine exhaust reduction.

    PubMed

    Wang, Qiuyan; Li, Guangfeng; Zhao, Bo; Zhou, Renxian

    2011-05-15

    A series of ceria-zirconia-neodymia mixed oxides with different contents of neodymia and the supported Pd-only three-way catalysts before and after aging have been prepared and characterized. The influence of Nd doping on the structural/textural properties of ceria-zirconia (CZ) and the effect on the three-way catalytic performance are also investigated. The results demonstrate that the addition of neodymia results in the formation of ceria-zirconia-neodymia ternary solid solution (CZN) with better textural and structural properties as well as improved reducibility and redox behavior, leading to the promoted three-way catalytic activity and enlarged air/fuel operation window. The modified solid solution with 5 wt.% neodymia shows the preferable textural/structural properties considering that the capacity of foreign cation is limited in the crystal lattice of ceria-zirconia solid solution, and Pd/CZN5 shows the optimum three-way catalytic performance and wider air/fuel operation window, especially for the corresponding aged one.

  7. LANTHANIDE ENHANCE LUMINESCENCE (LEL) WITH ONE AND TWO PHOTON EXCITATION OF QUANTUM DYES LANTHANIDE (III) - MACROCYCLES

    EPA Science Inventory

    Title: Lanthanide Enhance Luminescence (LEL) with one and two photon excitation of Quantum Dyes? Lanthanide(III)-Macrocycles
    Principal Author:
    Robert C. Leif, Newport Instruments
    Secondary Authors:
    Margie C. Becker, Phoenix Flow Systems
    Al Bromm, Virginia Commonw...

  8. Synthesis, Structure, and Basic Magnetic and Thermoelectric Properties of the Light Lanthanide Aurobismuthides.

    PubMed

    Seibel, Elizabeth M; Xie, Weiwei; Gibson, Quinn D; Cava, Robert J

    2016-04-01

    We report the crystal structures and elementary properties of the new aurobismuthides La3Au3Bi4, Ce3Au3Bi4, Pr3Au3Bi4, Nd3Au3Bi4, Sm3Au3Bi4, and Gd3Au3Bi4. These ternary compounds are found only for the large lanthanides and crystallize in the cubic Y3Au3Sb4 structure type, which is a stuffed Th3P4-type derivative. The compounds are electron-precise, leading to semiconducting behavior, and display magnetic properties arising from localized lanthanide f states. Resistivity data, Seebeck coefficient measurements, and electronic structure calculations suggest that these phases are heavily doped, p-type semiconductors. Nd3Au3Bi4 and Sm3Au3Bi4 have Seebeck coefficients of 105 and 190 μV/K at 350 K, respectively, making them worthy of further thermoelectric studies.

  9. Nonaqueous method for dissolving lanthanide and actinide metals

    DOEpatents

    Crisler, L.R.

    1975-11-11

    Lanthanide and actinide beta-diketonate complex molecular compounds are produced by reacting a beta-diketone compound with a lanthanide or actinide element in the elemental metallic state in a mixture of carbon tetrachloride and methanol.

  10. Electrochemical reactivity and proton transport mechanisms in nanostructured ceria

    NASA Astrophysics Data System (ADS)

    Ding, J.; Strelcov, E.; Kalinin, S. V.; Bassiri-Gharb, N.

    2016-08-01

    Electrochemical reactivity and ionic transport at the nanoscale are essential in many energy applications. In this study, time-resolved Kelvin probe force microscopy (tr-KPFM) is utilized for surface potential mapping of nanostructured ceria, in both space and time domains. The fundamental mechanisms of proton injection and transport are studied as a function of environmental conditions and the presence or absence of triple phase boundaries. Finite element modeling is used to extract physical parameters from the experimental data, allowing not only quantification of the observed processes, but also decoupling of their contributions to the measured signal. The constructed phase diagrams of the parameters demonstrate a thermally activated proton injection reaction at the triple phase boundary, and two transport processes that are responsible for the low-temperature proton conductivity of nanostructured ceria.

  11. Structural modification of nanocrystalline ceria by ion beams

    SciTech Connect

    Zhang, Yanwen; Edmondson, Philip D.; Varga, Tamas; Moll, Sandra; Namavar, Fereydoon; Lan, Chune; Weber, William J.

    2011-01-01

    Exceptional size-dependent electronic–ionic conductivity of nanostructured ceria can significantly alter materials properties in chemical, physical, electronic and optical applications. Using energetic ions, we have demonstrated effective modification of interface volume and grain size in nanocrystalline ceria from a few nm up to ~25 nm, which is the critical region for controlling size-dependent material property. The grain size increases and follows an exponential law as a function of ion fluence that increases with temperature, while the cubic phase is stable under the irradiation. The unique self-healing response of radiation damage at grain boundaries is utilized to control the grain size at the nanoscale. Structural modification by energetic ions is proposed to achieve desirable electronic–ionic conductivity.

  12. Structural Modification of Nanocrystalline Ceria by Ion Beams

    SciTech Connect

    Zhang, Yanwen; Edmondson, Philip D.; Varga, Tamas; Moll, Sandra J.; Namavar, Fereydoon; Lan, Chune; Weber, William J.

    2011-05-25

    Using energetic ions, we have demonstrated effective modification of grain size in nanocrystalline ceria in the critical region for controlling exceptional size-dependent electronicionic conductivity. The grain size increases and follows an exponential law as a function of ion fluence that increases with temperature, while the cubic phase is stable under the irradiation. The unique self-healing response of radiation damage at grain boundaries is utilized to control the grain size at the nanoscale.

  13. In vitro selection of a new lanthanide-dependent DNAzyme for ratiometric sensing lanthanides.

    PubMed

    Huang, Po-Jung Jimmy; Vazin, Mahsa; Liu, Juewen

    2014-10-01

    Developing biosensors for lanthanides is an important but challenging analytical task. To address this problem, in vitro selection of RNA-cleaving DNAzymes was carried out using a library containing a region of 35 random nucleotides in the presence of Lu(3+), since Lu(3+) was reported to be the most efficient lanthanide for RNA cleavage. The resulting DNA sequences can be aligned to a single family with two conserved stretches of nucleotides. One of the representative DNAzymes (named Lu12) was further studied. Lu12 is more active with smaller lanthanides and has the lowest activity in the presence of the largest lanthanide (lutetium). Its cleavage rate is 0.12 min(-1) in the presence of 10 μM Nd(3+) at pH 6.0. This is a new DNAzyme, and a catalytic beacon sensor is designed by attaching a fluorophore/quencher pair, detecting Nd(3+) down to 0.4 nM (72 parts-per-trillion). This DNAzyme is highly selective for lanthanides as well, showing cleavage only with two nonlanthanide ions: Y(3+) and Pb(2+). We previously reported a DNAzyme named Ce13d, which has similar responses to all the trivalent lanthanides. Combining these two allows for a ratiometric assay that identifies a few large lanthanides.

  14. Soot Combustion over Nanostructured Ceria with Different Morphologies

    PubMed Central

    Zhang, Wen; Niu, Xiaoyu; Chen, Liqiang; Yuan, Fulong; Zhu, Yujun

    2016-01-01

    In this study, nano-structure ceria with three different morphologies (nanorod, nanoparticle and flake) have been prepared by hydrothermal and solvothermal methods. The ceria samples were deeply characterized by XRD, SEM, TEM, H2-TPR, XPS and in-situ DRIFTS, and tested for soot combustion in absence/presence NO atmospheres under loose and tight contact conditions. The prepared ceria samples exhibit excellent catalytic activities, especially, the CeO2 with nanorod (Ce-R) shows the best catalytic activity, for which the peak temperature of soot combustion (Tm) is about 500 and 368 °C in loose and tight contact conditions, respectively. The catalytic activity for Ce-R is higher than that of the reported CeO2 catalysts and reaches a level that of precious metals. The characterization results reveal that the maximal amounts of adsorbed oxygen species on the surface of the nanostructure Ce-R catalyst should be the crucial role to decide the catalytic soot performance. High BET surface area may also be a positive effect on soot oxidation activity under loose contact conditions. PMID:27353143

  15. Soot Combustion over Nanostructured Ceria with Different Morphologies

    NASA Astrophysics Data System (ADS)

    Zhang, Wen; Niu, Xiaoyu; Chen, Liqiang; Yuan, Fulong; Zhu, Yujun

    2016-06-01

    In this study, nano-structure ceria with three different morphologies (nanorod, nanoparticle and flake) have been prepared by hydrothermal and solvothermal methods. The ceria samples were deeply characterized by XRD, SEM, TEM, H2-TPR, XPS and in-situ DRIFTS, and tested for soot combustion in absence/presence NO atmospheres under loose and tight contact conditions. The prepared ceria samples exhibit excellent catalytic activities, especially, the CeO2 with nanorod (Ce-R) shows the best catalytic activity, for which the peak temperature of soot combustion (Tm) is about 500 and 368 °C in loose and tight contact conditions, respectively. The catalytic activity for Ce-R is higher than that of the reported CeO2 catalysts and reaches a level that of precious metals. The characterization results reveal that the maximal amounts of adsorbed oxygen species on the surface of the nanostructure Ce-R catalyst should be the crucial role to decide the catalytic soot performance. High BET surface area may also be a positive effect on soot oxidation activity under loose contact conditions.

  16. Soot Combustion over Nanostructured Ceria with Different Morphologies.

    PubMed

    Zhang, Wen; Niu, Xiaoyu; Chen, Liqiang; Yuan, Fulong; Zhu, Yujun

    2016-01-01

    In this study, nano-structure ceria with three different morphologies (nanorod, nanoparticle and flake) have been prepared by hydrothermal and solvothermal methods. The ceria samples were deeply characterized by XRD, SEM, TEM, H2-TPR, XPS and in-situ DRIFTS, and tested for soot combustion in absence/presence NO atmospheres under loose and tight contact conditions. The prepared ceria samples exhibit excellent catalytic activities, especially, the CeO2 with nanorod (Ce-R) shows the best catalytic activity, for which the peak temperature of soot combustion (Tm) is about 500 and 368 °C in loose and tight contact conditions, respectively. The catalytic activity for Ce-R is higher than that of the reported CeO2 catalysts and reaches a level that of precious metals. The characterization results reveal that the maximal amounts of adsorbed oxygen species on the surface of the nanostructure Ce-R catalyst should be the crucial role to decide the catalytic soot performance. High BET surface area may also be a positive effect on soot oxidation activity under loose contact conditions. PMID:27353143

  17. Stable high conductivity ceria/bismuth oxide bilayered electrolytes

    SciTech Connect

    Wachsman, E.D.; Jayaweera, P.; Jiang, N.; Lowe, D.M.; Pound, B.G.

    1997-01-01

    The authors have developed a high conductivity bilayered ceria/bismuth oxide anolyte/electrolyte that uses the Po{sub 2} gradient to obtain stability at the anolyte-electrolyte interface and reduced electronic conduction due to the electrolyte region. Results in terms of solid oxide fuel cell (SOFC) performance and stability are presented. These results include a 90 to 160 mV increase in open-circuit potential, depending on temperature, with the bilayered structure as compared to SOFCs fabricated from a single ceria layer. An open-circuit potential of >1.0 V was obtained at 500 C with the bilayered structure. This increase in open-circuit potential is obtained without any measurable increase in cell resistance and is stable for over 1,400 h of testing, under both open-circuit and maximum power conditions. Moreover, SOFCs fabricated from the bilayered structure result in a 33% greater power density as compared to cells with a single ceria electrolyte layer.

  18. Electronic Structure of Small Lanthanide Containing Molecules

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

    Lanthanide-based materials have unusual electronic properties because of the high number of electronic degrees of freedom arising from partial occupation of 4f orbitals, which make these materials optimal for their utilization in many applications including electronics and catalysis. Electronic spectroscopy of small lanthanide molecules helps us understand the role of these 4f electrons, which are generally considered core-like because of orbital contraction, but are energetically similar to valence electrons. The spectroscopy of small lanthanide-containing molecules is relatively unexplored and to broaden this understanding we have completed the characterization of small cerium, praseodymium, and europium molecules using photoelectron spectroscopy coupled with DFT calculations. The characterization of PrO, EuH, EuO/EuOH, and CexOy molecules have allowed for the determination of their electron affinity, the assignment of numerous anion to neutral state transitions, modeling of anion/neutral structures and electron orbital occupation.

  19. Separations of actinides, lanthanides and other metals

    DOEpatents

    Smith, Barbara F.; Jarvinen, Gordon D.; Ensor, Dale D.

    1995-01-01

    An organic extracting solution comprised of a bis(acylpyrazolone or a substituted bis(acylpyrazolone) and an extraction method useful for separating certain elements of the actinide series of the periodic table having a valence of four from one other, and also from one or more of the substances in a group consisting of hexavalent actinides, trivalent actinides, trivalent lanthanides, trivalent iron, trivalent aluminum, divalent metals, and monovalent metals and also from one or more of the substances in a group consisting of hexavalent actinides, trivalent actinides, trivalent lanthanides, trivalent iron, trivalent aluminum, divalent metals, and monovalent metals and also useful for separating hexavalent actinides from one or more of the substances in a group consisting of trivalent actinides, trivalent lanthanides, trivalent iron, trivalent aluminum, divalent metals, and monovalent metals.

  20. Curvature of the Lanthanide Contraction: An Explanation

    SciTech Connect

    Raymond, Kenneth; Wellman, Daniel; Sgarlata, Carmelo; Hill, Aru

    2009-12-21

    A number of studies have shown that for isostructural series of the lanthanides (elements La through Lu), a plot of equivalent metal-ligand bond lengths versus atomic number differs significantly from linearity and can be better fit as a quadratic equation. However, for hydrogen type wave functions, it is the inverse of the average distance of the electron from the nucleus (an estimate of size) that varies linearly with effective nuclear charge. This generates an apparent quadratic dependence of radius with atomic number. Plotting the inverse of lanthanide ion radii (the observed distance minus the ligand size) as a function of effective nuclear charge gives very good linear fits for a variety of lanthanide complexes and materials. Parameters obtained from this fit are in excellent agreement with the calculated Slater shielding constant, k.

  1. Actinide Lanthanide Separation Process – ALSEP

    SciTech Connect

    Gelis, Artem V.; Lumetta, Gregg J.

    2014-01-29

    Separation of the minor actinides (Am, Cm) from the lanthanides at an industrial scale remains a significant technical challenge for closing the nuclear fuel cycle. To increase the safety of used nuclear fuel (UNF) reprocessing, as well as reduce associated costs, a novel solvent extraction process has been developed. The process allows for partitioning minor actinides, lanthanides and fission products following uranium/plutonium/neptunium removal; minimizing the number of separation steps, flowsheets, chemical consumption, and waste. This new process, Actinide Lanthanide SEParation (ALSEP), uses an organic solvent consisting of a neutral diglycolamide extractant, either N,N,N',N'-tetra(2 ethylhexyl)diglycolamide (T2EHDGA) or N,N,N',N'-tetraoctyldiglycolamide (TODGA), and an acidic extractant 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]), dissolved in an aliphatic diluent (e.g. n-dodecane). The An/Ln co-extraction is conducted from moderate-to-strong nitric acid, while the selective stripping of the minor actinides from the lanthanides is carried out using a polyaminocarboxylic acid/citrate buffered solution at pH anywhere between 3 and 4.5. The extraction and separation of the actinides from the fission products is very effective in a wide range of HNO3 concentrations and the minimum separation factors for lanthanide/Am exceed 30 for Nd/Am, reaching > 60 for Eu/Am under some conditions. The experimental results presented here demonstrate the great potential for a combined system, consisting of a neutral extractant such as T2EHDGA or TODGA, and an acidic extractant such as HEH[EHP], for separating the minor actinides from the lanthanides.

  2. Eco-friendly Synthesis of Ceria Foam via Carboxymethylcellulose Gelation: Application for the Epoxidation of Chalcone

    EPA Science Inventory

    A simple and innovative process is described for the eco-friendly preparation of ceria foams via the carboxymethylcellulose gelation by Ce4+ cations; heat treatment of the ensuing xerogels produces ceria foams. The influence of the concentration of cerium and of the calcination t...

  3. Understanding the Formation and Evolution of Ceria Nanoparticles Under Hydrothermal Conditions

    SciTech Connect

    Tyrsted, Christoffer; Ørnsbjerg; #8197; Jensen, Kirsten Marie; Bøjesen, Espen Drath; Lock, Nina; Christensen, Mogens; Billinge, Simon J.L.; Brummerstedt; #8197; Iversen, Bo

    2012-10-23

    The formation and evolution of ceria nanoparticles during hydrothermal synthesis was investigated by in-situ total scattering and powder diffraction. The nucleation of pristine crystalline ceria nanoparticles originated from previously unknown cerium dimer complexes. The nanoparticle growth was highly accelerated under supercritical conditions.

  4. Shear viscosity coefficient of liquid lanthanides

    SciTech Connect

    Patel, H. P. Thakor, P. B. Prajapati, A. V.; Sonvane, Y. A.

    2015-05-15

    Present paper deals with the computation of shear viscosity coefficient (η) of liquid lanthanides. The effective pair potential v(r) is calculated through our newly constructed model potential. The Pair distribution function g(r) is calculated from PYHS reference system. To see the influence of local field correction function, Hartree (H), Tailor (T) and Sarkar et al (S) local field correction function are used. Present results are compared with available experimental as well as theoretical data. Lastly, we found that our newly constructed model potential successfully explains the shear viscosity coefficient (η) of liquid lanthanides.

  5. Lanthanides in silicate glasses: A vibrational spectroscopic study

    NASA Astrophysics Data System (ADS)

    Ellison, Adam J. G.; Hess, Paul C.

    1990-09-01

    Parallel- and perpendicular-polarized Raman and KBr pellet transmission IR spectra of quenched 10K2O-50SiO2-nR2O3 (R = La, Gd, Yb; n = 0, 1, 5, 10 mol) glasses are presented. Increasing lanthanide oxide concentration produces partially-polarized high-frequency bands at 1030, 940, and 860 cm-1, assigned to the symmetric stretching modes of SiO4 tetrahedra containing 1, 2, and 4 nonbridging oxygen, respectively, in which the nonbridging oxygen coordinate primarily with lanthanides. Lanthanides therefore form silicate anions that are depolymerized relative to the bulk liquid and which have no counterparts in R2O3-SiO2 binary systems. The spectra indicate that there is little sharing of nonbridging oxygen by K and lanthanides. The spectra of glasses containing different lanthanides at the same concentration are qualitatively and quantitatively very similar. Lanthanides have energetically unfavorable interactions with the network structure of polymerized liquids compared to cations of lower valence. If lanthanides coordinate nonbridging oxygen without the aid of K, then lanthanide saturation concentrations will show modest increases with increasing (Na,K)/Al in peralkaline liquids, except in liquids in which P2O5 concentration is comparable to the total lanthanide concentration. Since differences in lanthanide ionic radii have small effects upon the spectra, lanthanide solution mechanisms in silicate glasses (and by inference silicate liquids) are probably very similar.

  6. Study of ceria-carbonate nanocomposite electrolytes for low-temperature solid oxide fuel cells.

    PubMed

    Fan, L; Wang, C; Di, J; Chen, M; Zheng, J; Zhu, B

    2012-06-01

    Composite and nanocomposite samarium doped ceria-carbonates powders were prepared by solid-state reaction, citric acid-nitrate combustion and modified nanocomposite approaches and used as electrolytes for low temperature solid oxide fuel cells. X-ray Diffraction, Scanning Electron Microscope, low-temperature Nitrogen Adsorption/desorption Experiments, Electrochemical Impedance Spectroscopy and fuel cell performance test were employed in characterization of these materials. All powders are nano-size particles with slight aggregation and carbonates are amorphous in composites. Nanocomposite electrolyte exhibits much lower impedance resistance and higher ionic conductivity than those of the other electrolytes at lower temperature. Fuel cell using the electrolyte prepared by modified nanocomposite approach exhibits the best performance in the whole operation temperature range and achieves a maximum power density of 839 mW cm(-2) at 600 degrees C with H2 as fuel. The excellent physical and electrochemical performances of nanocomposite electrolyte make it a promising candidate for low-temperature solid oxide fuel cells.

  7. Method bacterial endospore quantification using lanthanide dipicolinate luminescence

    NASA Technical Reports Server (NTRS)

    Ponce, Adrian (Inventor); Venkateswaran, Kasthuri J. (Inventor); Kirby, James Patrick (Inventor)

    2007-01-01

    A lanthanide is combined with a medium to be tested for endospores. The dipicolinic acid released from the endospores binds the lanthanides, which have distinctive emission (i.e., luminescence) spectra, and are detected using photoluminescence. The concentration of spores is determined by preparing a calibration curve generated from photoluminescence spectra of lanthanide complex mixed with spores of a known concentration. A lanthanide complex is used as the analysis reagent, and is comprised of lanthanide ions bound to multidentate ligands that increase the dipicolinic acid binding constant through a cooperative binding effect with respect to lanthanide chloride. The resulting combined effect of increasing the binding constant and eliminating coordinated water and multiple equilibria increase the sensitivity of the endospore assay by an estimated three to four orders of magnitude over prior art of endospore detection based on lanthanide luminescence.

  8. Effect of Ceria on the Storage and Regeneration Behavior of a Model Lean NOx Trap Catalyst

    SciTech Connect

    Ji, Yaying; Toops, Todd J; Crocker, Dr. Mark

    2007-01-01

    In this study the effect of ceria addition on the performance of a model Ba-based lean NO{sub x} trap (LNT) catalyst was examined. The presence of ceria improved NO{sub x} storage capacity in the temperature range 200-400 C under both continuous lean and lean-rich cycling conditions. Temperature-programmed experiments showed that NO{sub x} stored in the ceria-containing catalyst was thermally less stable and more reactive to reduction with both H{sub 2} and CO as reductants, albeit at the expense of additional reductant consumed by reduction of the ceria. These findings demonstrate that the incorporation of ceria in LNTs not only improves NO{sub x} storage efficiency but also positively impacts LNT regeneration behavior.

  9. Microarray immunoassay for phenoxybenzoic acid using polymer-functionalized lanthanide oxide nanoparticles as fluorescent labels

    NASA Astrophysics Data System (ADS)

    Nichkova, Mikaela; Dosev, Dosi; Gee, Shirley J.; Hammock, Bruce D.; Kennedy, Ian M.

    2005-11-01

    Fluorescent properties and low production cost makes lanthanide oxide nanoparticles attractive labels in biochemistry. Nanoparticles with different fluorescent spectra were produced by doping of oxides such as Y IIO 3 and Gd IIO 3 with different lanthanide ions (Eu, Tb, Sm) giving the possibility for multicolor labeling. Protein microarrays have the potential to play a fundamental role in the miniaturization of biosensors, clinical immunological assays, and protein-protein interaction studies. Here we present the application of fluorescent lanthanide oxide nanoparticles as labels in microarray-based immunoassay for phenoxybenzoic acid (PBA), a generic biomarker of human exposure to the highly potent insecticides pyrethroids. A novel polymer-based protocol was developed for biochemical functionalization of the nanoparticles. Microarrays of antibodies were fabricated by microcontact printing in line patterns onto glass substrates and immunoassays were successfully performed using the corresponding functionalized nanoparticles. The applicability of the fluorophore nanoparticles as reporters for detection of antibody-antigen interactions has been demonstrated for phenoxybenzoic acid (PBA)/anti-PBA IgG. The sensitivity of the competitive fluorescent immunoassay for PBA was similar to that of the corresponding ELISA.

  10. Study of Lanthanide Complexes with BTFA in Silica Gels by Photoacoustic Spectroscopy

    NASA Astrophysics Data System (ADS)

    Liu, R. Y.; Zhang, H. X.; Yang, Y. T.; Zhang, S. Y.; Liu, X. J.

    2016-06-01

    In this work, lanthanide β -diketonate complexes Ln(btfa){}3 \\cdot 2H2O (Ln^{3+}: Eu^{3+}, Sm^{3+ }, and Tb^{3+}; btfa: 4,4,4-trifluoro-l-phenyl-1,3-butanedione) were incorporated into silica gels by a sol-gel method. Photoacoustic (PA) spectra of these complex-doped silica samples were measured and studied. The PA intensity of the β -diketonate ligand is nearly the same for lanthanide complexes in wet gels. After heat treatment at 150°C, however, the PA intensity of the ligand increases for Eu^{3+}, Sm^{3+}, and Tb^{3+} complexes in silica gels, respectively. Different PA intensities of the samples are interpreted by comparison with their luminescence spectra. The luminescence result is consistent with the PA spectra. The result indicates that lanthanide β -diketonate complexes cannot be formed in silica gels without a suitable heat treatment. Moreover, the relaxation process model is proposed based on the PA and luminescence results.

  11. Effect of Lanthanide Ions on Dynamic Nuclear Polarization Enhancement and Liquid State T1 Relaxation

    PubMed Central

    Gordon, Jeremy; Fain, Sean B.; Rowland, Ian J

    2012-01-01

    In the dynamic nuclear polarization process, microwave irradiation facilitates exchange of polarization from a radical’s unpaired electron to nuclear spins at cryogenic temperatures, increasing polarization by >10000. Doping samples with Gd3+ ions further increases the achievable solid-state polarization. However, upon dissolution, paramagnetic lanthanide metals can be potent relaxation agents, decreasing liquid-state polarization. Here, the effects of lanthanide metals on the solid and liquid-state magnetic properties of [1-13C]pyruvate are studied. The results show that in addition to gadolinium, holmium not only increases the achievable polarization but also the rate of polarization. Liquid-state relaxation studies found that unlike gadolinium, holmium minimally affects T1. Additionally, results reveal that linear contrast agents dissociate in pyruvic acid, greatly reducing liquid-state T1. While macrocyclic agents do not readily dissociate, they yield lower solid-state polarization. Results indicate that polarization with free lanthanides and subsequent chelation during dissolution produces the highest polarization enhancement while minimizing liquid-state relaxation. PMID:22367680

  12. Spectroscopic Investigation of Surface-Dependent Acid–Base Property of Ceria Nanoshapes

    SciTech Connect

    Wu, Zili; Mann, Amanda K. P.; Li, Meijun; Overbury, Steven H.

    2015-03-12

    In addition to their well-known redox character, the acid-base property is another interesting aspect of ceria-based catalysts. Thus, the effect of surface structure on the acid-base property of ceria was studied in detail by utilizing ceria nanocrystals with different morphologies (cubes, octahedra and rods) that exhibit crystallographically well-defined surface facets. The nature, type, strength and amount of acid and base sites on these ceria nanoshapes were investigated via in situ IR spectroscopy combined with various probe molecules. Pyridine adsorption shows the presence of Lewis acid sites (Ce cations) on the ceria nanoshapes. These Lewis acid sites are relatively weak and similar in strength among the three nanoshapes according to the probing by both pyridine and acetonitrile. Both Br nsted (hydroxyl group) and Lewis (surface lattice oxygen) base sites are present on the ceria nanoshapes as probed by CO2 adsorption. CO2 and chloroform adsorption indicate that the strength and amount of the Lewis base sites are shape dependent: rods > cubes > octahedra. Moreover, the weak and strong surface dependence of the acid and base sites, respectively, are a result of interplay between the surface structure dependent coordination unsaturation status of the Ce cations and O anions and the amount of defect sites on the three ceria nanoshapes. Furthermore, it was found that the nature of the acid-base sites of ceria can be impacted by impurities, such as Na and P residues that result from their use as structure-directing reagent in the hydrothermal synthesis of the ceria nanocrystals. Finally, our observation calls for precaution in interpreting the catalytic behavior of nanoshaped ceria where trace impurities may be present.

  13. Spectroscopic Investigation of Surface-Dependent Acid–Base Property of Ceria Nanoshapes

    DOE PAGES

    Wu, Zili; Mann, Amanda K. P.; Li, Meijun; Overbury, Steven H.

    2015-03-12

    In addition to their well-known redox character, the acid-base property is another interesting aspect of ceria-based catalysts. Thus, the effect of surface structure on the acid-base property of ceria was studied in detail by utilizing ceria nanocrystals with different morphologies (cubes, octahedra and rods) that exhibit crystallographically well-defined surface facets. The nature, type, strength and amount of acid and base sites on these ceria nanoshapes were investigated via in situ IR spectroscopy combined with various probe molecules. Pyridine adsorption shows the presence of Lewis acid sites (Ce cations) on the ceria nanoshapes. These Lewis acid sites are relatively weak andmore » similar in strength among the three nanoshapes according to the probing by both pyridine and acetonitrile. Both Br nsted (hydroxyl group) and Lewis (surface lattice oxygen) base sites are present on the ceria nanoshapes as probed by CO2 adsorption. CO2 and chloroform adsorption indicate that the strength and amount of the Lewis base sites are shape dependent: rods > cubes > octahedra. Moreover, the weak and strong surface dependence of the acid and base sites, respectively, are a result of interplay between the surface structure dependent coordination unsaturation status of the Ce cations and O anions and the amount of defect sites on the three ceria nanoshapes. Furthermore, it was found that the nature of the acid-base sites of ceria can be impacted by impurities, such as Na and P residues that result from their use as structure-directing reagent in the hydrothermal synthesis of the ceria nanocrystals. Finally, our observation calls for precaution in interpreting the catalytic behavior of nanoshaped ceria where trace impurities may be present.« less

  14. Lung deposition and extrapulmonary translocation of nano-ceria after intratracheal instillation

    NASA Astrophysics Data System (ADS)

    He, Xiao; Zhang, Haifeng; Ma, Yuhui; Bai, Wei; Zhang, Zhiyong; Lu, Kai; Ding, Yayun; Zhao, Yuliang; Chai, Zhifang

    2010-07-01

    The broad potential applications of manufactured nanomaterials call for urgent assessment of their environmental and biological safety. However, most of the previous work focused on the cell level performance; little was known about the consequences of nanomaterial exposure at the whole-body and organ levels. In the present paper, the radiotracer technique was employed to study the pulmonary deposition and the translocation to secondary target organs after ceria nanoparticles (nano-ceria) were intratracheally instilled into Wistar rats. It was found that 63.9 ± 8.2% of the instilled nano-ceria remained in the lung by 28 d postexposure and the elimination half-life was 103 d. At the end of the test period, only 1/8-1/3 of the daily elimination of nano-ceria from the lung was cleared via the gastrointestinal tract, suggesting that phagocytosis by alveolar macrophages (AMs) with subsequent removal towards the larynx was no longer the predominant route for the elimination of nano-ceria from the lung. The whole-body redistribution of nano-ceria demonstrated that the deposited nano-ceria could penetrate through the alveolar wall into the systemic circulation and accumulate in the extrapulmonary organs. In vitro study suggested that nano-ceria would agglomerate and form sediments in the bronchoalveolar aqueous surrounding while binding to protein would be conducive to the redispersion of nano-ceria. The decrease in the size of agglomerates might enhance the penetration of nano-ceria into the systemic circulation. Our findings suggested that the effect of nanomaterial exposure, even at low concentration, should be assessed because of the potential lung and systemic cumulative toxicity of the nanomaterials.

  15. Biological and Clinical Aspects of Lanthanide Coordination Compounds

    PubMed Central

    Misra, Sudhindra N.; M., Indira Devi; Shukla, Ram S.

    2004-01-01

    The coordinating chemistry of lanthanides, relevant to the biological, biochemical and medical aspects, makes a significant contribution to understanding the basis of application of lanthanides, particularly in biological and medical systems. The importance of the applications of lanthanides, as an excellent diagnostic and prognostic probe in clinical diagnostics, and an anticancer material, is remarkably increasing. Lanthanide complexes based X-ray contrast imaging and lanthanide chelates based contrast enhancing agents for magnetic resonance imaging (MRI) are being excessively used in radiological analysis in our body systems. The most important property of the chelating agents, in lanthanide chelate complex, is its ability to alter the behaviour of lanthanide ion with which it binds in biological systems, and the chelation markedly modifies the biodistribution and excretion profile of the lanthanide ions. The chelating agents, especially aminopoly carboxylic acids, being hydrophilic, increase the proportion of their complex excreted from complexed lanthanide ion form biological systems. Lanthanide polyamino carboxylate-chelate complexes are used as contrast enhancing agents for Magnetic Resonance Imaging. Conjugation of antibodies and other tissue specific molecules to lanthanide chelates has led to a new type of specific MRI contrast agents and their conjugated MRI contrast agents with improved relaxivity, functioning in the body similar to drugs. Many specific features of contrast agent assisted MRI make it particularly effective for musculoskeletal and cerebrospinal imaging. Lanthanide-chelate contrast agents are effectively used in clinical diagnostic investigations involving cerebrospinal diseases and in evaluation of central nervous system. Chelated lanthanide complexes shift reagent aided 23Na NMR spectroscopic analysis is used in cellular, tissue and whole organ systems. PMID:18365075

  16. Energetics of Rare Earth Doped Uranium Oxide Solid Solutions

    NASA Astrophysics Data System (ADS)

    Zhang, Lei

    The physical and chemical properties of UO2 nuclear fuels are affected as fission products accumulate during irradiation. The lanthanides, a main group of fission products, form extensive solid solutions with uranium oxide in the fluorite structure. Thermodynamic studies of such solid solutions had been performed to obtain partial molar free energies of oxygen as a function of dopant concentration and temperature; however, direct measurement of formation enthalpies was hampered by the refractory nature of these oxides. In this work, high temperature oxide melt solution calorimetry was utilized to study the thermochemistry of various rare earth doped uranium oxide LnxU 1-xO2-0.5x+y (Ln = La, Y, Nd) over a wide range of dopant concentrations and oxygen contents. The sintered solid solutions were carefully characterized to determine their phase purity, chemical composition, and uranium oxidation state, with most of the materials in the oxygen excess regime. The enthalpies of formation of LnxU1-xO2-0.5x+y were calculated from the calorimetric data. The oxidation enthalpies of these solid solutions are similar to that of UO2. The formation enthalpies from constituent oxides (LnO1.5, UO2, and UO3) become increasingly negative with addition of dopant cations and appear relatively independent of the uranium oxidation state (oxygen content) when the type and concentration of the dopants are the same. This is valid in the oxygen excess regime; thus an estimation of formation enthalpies of LnxU1-xO2 materials can be made. The formation enthalpies from elements of hyperstoichiometric LnxU1-xO 2-0.5x+y materials obtained from calorimetric measurements are in good agreement with those calculated from free energy data. A direct comparison between the formation enthalpies from calorimetric study and computational research using density functional theory was also performed. The experimental and computational energies of LnxU 1-xO2 (Ln = La, Y, Nd) generally agree within 10 k

  17. Synthesis and In Situ Environmental Transmission Electron Microscopy Investigations of Ceria-Based Oxides for Solid Oxide Fuel Cell Anodes

    NASA Astrophysics Data System (ADS)

    Sharma, Vaneet

    The behavior of a solid oxide fuel cell (SOFC) cermet (ceramic-metal composite) anode under reaction conditions depends significantly on the structure, morphology and atomic scale interactions between the metal and the ceramic components. In situ environmental transmission electron microscope (ETEM) is an important tool which not only allows us to perform the basic nanoscale characterization of the anode materials, but also to observe in real-time, the dynamic changes in the anode material under near-reaction conditions. The earlier part of this dissertation is focused on the synthesis and characterization of Pr- and Gd-doped cerium oxide anode materials. A novel spray drying set-up was designed and constructed for preparing nanoparticles of these mixed-oxides and nickel oxide for anode fabrication. X-ray powder diffraction was used to investigate the crystal structure and lattice parameters of the synthesized materials. Particle size distribution, morphology and chemical composition were investigated using transmission electron microscope (TEM). The nanoparticles were found to possess pit-like defects of average size 2 nm after subjecting the spray-dried material to heat treatment at 700 °C for 2 h in air. A novel electron energy-loss spectroscopy (EELS) quantification technique for determining the Pr and Gd concentrations in the mixed oxides was developed. Nano-scale compositional heterogeneity was observed in these materials. The later part of the dissertation focuses mainly on in situ investigations of the anode materials under a H2 environment in the ETEM. Nano-scale changes in the stand-alone ceramic components of the cermet anode were first investigated. Particle size and composition of the individual nanoparticles of Pr-doped ceria (PDC) were found to affect their reducibility in H2 gas. Upon reduction, amorphization of the nanoparticles was observed and was linked to the presence of pit-like defects in the spray-dried material. Investigation of metal

  18. Characterization of swift heavy ion irradiation damage in ceria

    SciTech Connect

    Yablinsky, Clarissa A.; Devanathan, Ram; Pakarinen, Janne; Gan, Jian; Severin, Daniel; Trautmann, Christina; Allen, Todd R.

    2015-03-04

    Swift heavy ion induced radiation damage is investigated for ceria (CeO2), which serves as a UO2 fuel surrogate. Microstructural changes resulting from an irradiation with 940 MeV gold ions of 42 keV/nm electronic energy loss are investigated by means of electron microscopy accompanied by electron energy loss spectroscopy showing that there exists a small density reduction in the ion track core. While chemical changes in the ion track are not precluded, evidence of them was not observed. Classical molecular dynamics simulations of thermal spikes in CeO2 with an energy deposition of 12 and 36 keV/nm show damage consisting of isolated point defects at 12 keV/nm, and defect clusters at 36 keV/nm, with no amorphization at either energy. Inferences are drawn from modeling about density changes in the ion track and the formation of interstitial loops that shed light on features observed by electron microscopy of swift heavy ion irradiated ceria.

  19. Characterization of swift heavy ion irradiation damage in ceria

    SciTech Connect

    Yablinsky, Clarissa; Devanathan, Ram; Pakarinen, Janne; Gan, Jian; Severin, Daniel; Trautmann, Christina; Allen, T. R.

    2015-05-14

    We have examined microstructural evolution in irradiated ceria (CeO2) using swift heavy ion irradiation, electron microscopy, and atomistic simulation. CeO2, a UO2 fuel surrogate, was irradiated with gold ions at an energy of 1 GeV to fluences up to 1x1014 ions/cm2. Transmission electron microscopy accompanied by electron energy loss spectroscopy showed that the ion tracks were of similar size at all fluences, and that there was no chemical change in the ion track core. Classical molecular dynamics simulations of thermal spikes in CeO2 with energy deposition of 12 and 36 keV/nm show damage consisting of isolated point defects at the lower energy and defect clusters at 36 keV/nm, with no amorphization at either energy. Inferences are drawn from modeling about density changes in the ion track and the formation of interstitial loops that shed light on features observed by electron microscopy of swift heavy ion irradiated ceria.

  20. Characterization of swift heavy ion irradiation damage in ceria

    DOE PAGES

    Yablinsky, Clarissa A.; Devanathan, Ram; Pakarinen, Janne; Gan, Jian; Severin, Daniel; Trautmann, Christina; Allen, Todd R.

    2015-03-04

    Swift heavy ion induced radiation damage is investigated for ceria (CeO2), which serves as a UO2 fuel surrogate. Microstructural changes resulting from an irradiation with 940 MeV gold ions of 42 keV/nm electronic energy loss are investigated by means of electron microscopy accompanied by electron energy loss spectroscopy showing that there exists a small density reduction in the ion track core. While chemical changes in the ion track are not precluded, evidence of them was not observed. Classical molecular dynamics simulations of thermal spikes in CeO2 with an energy deposition of 12 and 36 keV/nm show damage consisting of isolatedmore » point defects at 12 keV/nm, and defect clusters at 36 keV/nm, with no amorphization at either energy. Furthermore, inferences are drawn from modeling about density changes in the ion track and the formation of interstitial loops that shed light on features observed by electron microscopy of swift heavy ion irradiated ceria.« less

  1. Characterization of swift heavy ion irradiation damage in ceria

    SciTech Connect

    Yablinsky, Clarissa A.; Devanathan, Ram; Pakarinen, Janne; Gan, Jian; Severin, Daniel; Trautmann, Christina; Allen, Todd R.

    2015-03-04

    Swift heavy ion induced radiation damage is investigated for ceria (CeO2), which serves as a UO2 fuel surrogate. Microstructural changes resulting from an irradiation with 940 MeV gold ions of 42 keV/nm electronic energy loss are investigated by means of electron microscopy accompanied by electron energy loss spectroscopy showing that there exists a small density reduction in the ion track core. While chemical changes in the ion track are not precluded, evidence of them was not observed. Classical molecular dynamics simulations of thermal spikes in CeO2 with an energy deposition of 12 and 36 keV/nm show damage consisting of isolated point defects at 12 keV/nm, and defect clusters at 36 keV/nm, with no amorphization at either energy. Furthermore, inferences are drawn from modeling about density changes in the ion track and the formation of interstitial loops that shed light on features observed by electron microscopy of swift heavy ion irradiated ceria.

  2. De Novo Designed Imaging Agents Based on Lanthanide Peptides Complexes.

    PubMed

    Peacock, A F A

    2016-01-01

    Herein are discussed a selection of lanthanide peptide/protein complexes in view of their potential applications as imaging agents, both in terms of luminescence detection and magnetic resonance imaging. Though this chapter covers a range of different peptides and protein, if focuses specifically on the opportunities afforded by the de novo design of coiled coils, miniature protein scaffolds, and the development on lanthanide-binding sites into these architectures. The requirements for lanthanide coordination and the challenges that need to be addressed when preparing lanthanide peptides with a view to their potential adoption as clinical imaging applications, will be highlighted. PMID:27586349

  3. The Actinide-Lanthanide Separation Process

    SciTech Connect

    Lumetta, Gregg J.; Gelis, Artem V.; Carter, Jennifer C.; Niver, Cynthia M.; Smoot, Margaret R.

    2014-02-21

    The Actinide-Lanthanide SEParation (ALSEP) process is described. The process uses an extractant phase consisting of either N,N,N',N'-tetraoctyldiglycolamide (TODGA) or N,N,N',N'-tetra(2 ethylhexyl)diglycolamide (T2EHDGA) combined with 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]). The neutral TODGA or T2EHDGA serves to co-extract the trivalent actinide and lanthanide ions from nitric acid media. Switching the aqueous phase chemistry to a citrate buffered diethylenetriaminepentaacetic acid (DTPA) solution at pH 2.5 to 4 results in selective transfer of the actinides to the aqueous phase, thus resulting in separation of these two groups of elements.

  4. Giant exchange interaction in mixed lanthanides

    PubMed Central

    Vieru, Veacheslav; Iwahara, Naoya; Ungur, Liviu; Chibotaru, Liviu F.

    2016-01-01

    Combining strong magnetic anisotropy with strong exchange interaction is a long standing goal in the design of quantum magnets. The lanthanide complexes, while exhibiting a very strong ionic anisotropy, usually display a weak exchange coupling, amounting to only a few wavenumbers. Recently, an isostructural series of mixed (Ln = Gd, Tb, Dy, Ho, Er) have been reported, in which the exchange splitting is estimated to reach hundreds wavenumbers. The microscopic mechanism governing the unusual exchange interaction in these compounds is revealed here by combining detailed modeling with density-functional theory and ab initio calculations. We find it to be basically kinetic and highly complex, involving non-negligible contributions up to seventh power of total angular momentum of each lanthanide site. The performed analysis also elucidates the origin of magnetization blocking in these compounds. Contrary to general expectations the latter is not always favored by strong exchange interaction. PMID:27087470

  5. Lanthanide-halide based humidity indicators

    DOEpatents

    Beitz, James V.; Williams, Clayton W.

    2008-01-01

    The present invention discloses a lanthanide-halide based humidity indicator and method of producing such indicator. The color of the present invention indicates the humidity of an atmosphere to which it is exposed. For example, impregnating an adsorbent support such as silica gel with an aqueous solution of the europium-containing reagent solution described herein, and dehydrating the support to dryness forms a substance with a yellow color. When this substance is exposed to a humid atmosphere the water vapor from the air is adsorbed into the coating on the pore surface of the silica gel. As the water content of the coating increases, the visual color of the coated silica gel changes from yellow to white. The color change is due to the water combining with the lanthanide-halide complex on the pores of the gel.

  6. Giant exchange interaction in mixed lanthanides

    NASA Astrophysics Data System (ADS)

    Vieru, Veacheslav; Iwahara, Naoya; Ungur, Liviu; Chibotaru, Liviu F.

    2016-04-01

    Combining strong magnetic anisotropy with strong exchange interaction is a long standing goal in the design of quantum magnets. The lanthanide complexes, while exhibiting a very strong ionic anisotropy, usually display a weak exchange coupling, amounting to only a few wavenumbers. Recently, an isostructural series of mixed (Ln = Gd, Tb, Dy, Ho, Er) have been reported, in which the exchange splitting is estimated to reach hundreds wavenumbers. The microscopic mechanism governing the unusual exchange interaction in these compounds is revealed here by combining detailed modeling with density-functional theory and ab initio calculations. We find it to be basically kinetic and highly complex, involving non-negligible contributions up to seventh power of total angular momentum of each lanthanide site. The performed analysis also elucidates the origin of magnetization blocking in these compounds. Contrary to general expectations the latter is not always favored by strong exchange interaction.

  7. Nanometrization of Lanthanide-Based Coordination Polymers.

    PubMed

    Neaime, Chrystelle; Daiguebonne, Carole; Calvez, Guillaume; Freslon, Stéphane; Bernot, Kevin; Grasset, Fabien; Cordier, Stéphane; Guillou, Olivier

    2015-11-23

    Heteronuclear lanthanide-based coordination polymers are microcrystalline powders, the luminescence properties of which can be precisely tuned by judicious choice of the rare-earth ions. In this study, we demonstrate that such materials can also be obtained as stable solutions of nanoparticles in non-toxic polyols. Bulk powders of the formula [Ln2-2x Ln'2x (bdc)3 ⋅4 H2 O]∞ (where H2 bdc denotes 1,4-benzene-dicarboxylic acid, 0≤x≤1, and Ln and Ln' denote lanthanide ions of the series La to Tm plus Y) afford nanoparticles that have been characterized by dynamic light-scattering (DLS) and transmission electron microscopy (TEM) measurements. Their luminescence properties are similar to those of the bulk materials. Stabilities versus time and versus dilution with another solvent have been studied. This study has revealed that it is possible to tune the size of the nanoparticles. This process offers a reliable means of synthesizing suspensions of nanoparticles with tunable luminescence properties and tunable size distributions in a green solvent (glycerol). The process is also extendable to other coordination polymers and other solvents (ethylene glycol, for example). It constitutes a new route for the facile solubilization of lanthanide-based coordination polymers. PMID:26471940

  8. Switchable sensitizers stepwise lighting up lanthanide emissions

    PubMed Central

    Zhang, Yan; Jiao, Peng-Chong; Xu, Hai-Bing; Tang, Ming-Jing; Yang, Xiao-Ping; Huang, Shaoming; Deng, Jian-Guo

    2015-01-01

    Analagous to a long-ranged rocket equipped with multi-stage engines, a luminescent compound with consistent emission signals across a large range of concentrations from two stages of sensitizers can be designed. In this approach, ACQ, aggregation-caused quenching effect of sensitizers, would stimulate lanthanide emission below 10−4 M, and then at concentrations higher than 10−3 M, the “aggregation-induced emission” (AIE) effect of luminophores would be activated with the next set of sensitizers for lanthanide emission. Simultaneously, the concentration of the molecules could be monitored digitally by the maximal excitation wavelengths, due to the good linear relationship between the maximal excitation wavelengths and the concentrations {lg(M)}. This model, wherein molecules are assembled with two stages (both AIE and ACQ effect) of sensitizers, may provide a practicable strategy for design and construction of smart lanthanide bioprobes, which are suitable in complicated bioassay systems in which concentration is variable. PMID:25791467

  9. Actinide and lanthanide separation process (ALSEP)

    SciTech Connect

    Guelis, Artem V.

    2013-01-15

    The process of the invention is the separation of minor actinides from lanthanides in a fluid mixture comprising, fission products, lanthanides, minor actinides, rare earth elements, nitric acid and water by addition of an organic chelating aid to the fluid; extracting the fluid with a solvent comprising a first extractant, a second extractant and an organic diluent to form an organic extractant stream and an aqueous raffinate. Scrubbing the organic stream with a dicarboxylic acid and a chelating agent to form a scrubber discharge. The scrubber discharge is stripped with a simple buffering agent and a second chelating agent in the pH range of 2.5 to 6.1 to produce actinide and lanthanide streams and spent organic diluents. The first extractant is selected from bis(2-ethylhexyl)hydrogen phosphate (HDEHP) and mono(2-ethylhexyl)2-ethylhexyl phosphonate (HEH(EHP)) and the second extractant is selected from N,N,N,N-tetra-2-ethylhexyl diglycol amide (TEHDGA) and N,N,N',N'-tetraoctyl-3-oxapentanediamide (TODGA).

  10. Nanometrization of Lanthanide-Based Coordination Polymers.

    PubMed

    Neaime, Chrystelle; Daiguebonne, Carole; Calvez, Guillaume; Freslon, Stéphane; Bernot, Kevin; Grasset, Fabien; Cordier, Stéphane; Guillou, Olivier

    2015-11-23

    Heteronuclear lanthanide-based coordination polymers are microcrystalline powders, the luminescence properties of which can be precisely tuned by judicious choice of the rare-earth ions. In this study, we demonstrate that such materials can also be obtained as stable solutions of nanoparticles in non-toxic polyols. Bulk powders of the formula [Ln2-2x Ln'2x (bdc)3 ⋅4 H2 O]∞ (where H2 bdc denotes 1,4-benzene-dicarboxylic acid, 0≤x≤1, and Ln and Ln' denote lanthanide ions of the series La to Tm plus Y) afford nanoparticles that have been characterized by dynamic light-scattering (DLS) and transmission electron microscopy (TEM) measurements. Their luminescence properties are similar to those of the bulk materials. Stabilities versus time and versus dilution with another solvent have been studied. This study has revealed that it is possible to tune the size of the nanoparticles. This process offers a reliable means of synthesizing suspensions of nanoparticles with tunable luminescence properties and tunable size distributions in a green solvent (glycerol). The process is also extendable to other coordination polymers and other solvents (ethylene glycol, for example). It constitutes a new route for the facile solubilization of lanthanide-based coordination polymers.

  11. Thermally stable single-atom platinum-on-ceria catalysts via atom trapping.

    PubMed

    Jones, John; Xiong, Haifeng; DeLaRiva, Andrew T; Peterson, Eric J; Pham, Hien; Challa, Sivakumar R; Qi, Gongshin; Oh, Se; Wiebenga, Michelle H; Pereira Hernández, Xavier Isidro; Wang, Yong; Datye, Abhaya K

    2016-07-01

    Catalysts based on single atoms of scarce precious metals can lead to more efficient use through enhanced reactivity and selectivity. However, single atoms on catalyst supports can be mobile and aggregate into nanoparticles when heated at elevated temperatures. High temperatures are detrimental to catalyst performance unless these mobile atoms can be trapped. We used ceria powders having similar surface areas but different exposed surface facets. When mixed with a platinum/aluminum oxide catalyst and aged in air at 800°C, the platinum transferred to the ceria and was trapped. Polyhedral ceria and nanorods were more effective than ceria cubes at anchoring the platinum. Performing synthesis at high temperatures ensures that only the most stable binding sites are occupied, yielding a sinter-resistant, atomically dispersed catalyst. PMID:27387946

  12. Control of Metal Nanocrystal Size Reveals Metal-Support Interface Role for Ceria Catalysts

    SciTech Connect

    Cargnello, M; Doan-Nguyen, VVT; Gordon, TR; Diaz, RE; Stach, EA; Gorte, RJ; Fornasiero, P; Murray, CB

    2013-08-15

    Interactions between ceria (CeO2) and supported metals greatly enhance rates for a number of important reactions. However, direct relationships between structure and function in these catalysts have been difficult to extract because the samples studied either were heterogeneous or were model systems dissimilar to working catalysts. We report rate measurements on samples in which the length of the ceria-metal interface was tailored by the use of monodisperse nickel, palladium, and platinum nanocrystals. We found that carbon monoxide oxidation in ceria-based catalysts is greatly enhanced at the ceria-metal interface sites for a range of group VIII metal catalysts, clarifying the pivotal role played by the support.

  13. Nanostructured ceria based thin films ({<=}1 {mu}m) As cathode/electrolyte interfaces

    SciTech Connect

    Hierso, J.; Boy, P.; Valle, K.; Vulliet, J.; Blein, F.; Laberty-Robert, Ch.; Sanchez, C.

    2013-01-15

    Gadolinium doped cerium oxide (CGO: Ce{sub 0,9}Gd{sub 0,1}O{sub 2-{delta}}) films were used as an oxygen anion diffusion layer at the cathode/electrolyte interface of Solid Oxide Fuel Cells (SOFCs), between LSCF (lanthanum strontium cobalt ferrite) and YSZ (yttria-stabilized zirconia). Thin ({approx}100 nm) and thick ({approx}700 nm) mesoporous CGO layers were synthesized through a sol-gel process including organic template coupled with the dip-coating method. Structural and microstructural characterizations were performed, highlighting a well-bonded crystalline CGO nanoparticles network which delineates a 3-D inter-connected mesoporous network. Their electrical behaviors were investigated by impedance spectroscopy analysis of YSZ/mesoporous-CGO/LSCF half-cell. Anode-supported SOFCs, operating at 800 Degree-Sign C, with either dense or mesoporous CGO dip-coated interlayers were also fabricated [NiO-YSZ anode/YSZ/CGO/LSCF cathode]. The impact of the mesoporous CGO interlayers on SOFCs performances was investigated by galvanostatic analysis and compared to the behavior of a dense CGO interlayer. The polarization curves revealed an enhancement in the electrical performance of the cell, which is assigned to a decrease of the polarization resistance at the cathode/electrolyte interface. The integrity and connectivity of the CGO nanoparticles bonded network facilitates O{sup 2-} transport across the interface. - Graphical abstract: Thin and thick CGO films have been prepared through a sol-gel process and their potential application as SOFC cathode/electrolyte interlayer in SOFC has been investigated. Highlights: Black-Right-Pointing-Pointer Mesoporous ceria based thin films exhibit interesting performances for Solid Oxide Fuel Cell. Black-Right-Pointing-Pointer Mesoporous films were synthesized through the sol-gel process combined with the dip-coating. Black-Right-Pointing-Pointer Integrity and connectivity of the nanoparticles facilitates O{sup 2-} transport across the

  14. Modifying ceria (111) with a TiO2 nanocluster for enhanced reactivity.

    PubMed

    Nolan, Michael

    2013-11-14

    Modification of ceria catalysts is of great interest for oxidation reactions such as oxidative dehydrogenation of alcohols. Improving the reactivity of ceria based catalysts for these reactions means that they can be run at lower temperatures and density functional theory (DFT) simulations of new structures and compositions are proving valuable in the development of these catalysts. In this paper, we have used DFT+U (DFT corrected for on-site Coulomb interactions) to examine the reactivity of a novel modification of ceria, namely, modifying with TiO2, using the example of a Ti2O4 species adsorbed on the ceria (111) surface. The oxygen vacancy formation energy in the Ti2O4-CeO2 system is significantly reduced over the bare ceria surfaces, which together with previous work on ceria-titania indicates that the presence of the interface favours oxygen vacancy formation. The energy gain upon hydrogenation of the catalyst, which is the rate determining step in oxidative dehydrogenation, further points to the improved oxidation power of this catalyst structure. PMID:24320294

  15. A Thermodynamic Investigation of the Redox Properties of Ceria-Titania Mixed Oxides

    SciTech Connect

    Zhou,G.; Hanson, J.; Gorte, R.

    2008-01-01

    Ceria-titania solutions with compositions of Ce0.9Ti0.1O2 and Ce0.8Ti0.2O2 were prepared by the citric-acid (Pechini) method and characterized using X-ray diffraction (XRD) for structure, coulometric titration for redox thermodynamics, and water-gas-shift (WGS) reaction rates. Following calcination at 973 K, XRD suggests that the mixed oxides exist as single phase, fluorite structures, although there was no significant change in the lattice parameter compared to pure ceria. The mixed oxides are shown to be significantly more reducible than bulk ceria, with enthalpies for re-oxidation being approximately -500 kJ/mol O2, compared to -760 kJ/mol O2 for bulk ceria. However, WGS rates over 1 wt% Pd supported on ceria, Ce0.8Ti0.2O2, and Ce0.8Zr0.2O2 were nearly the same. For calcination at 1323 K, the mixed oxides separated into ceria and titania phases, as indicated by both the XRD and thermodynamic results.

  16. Adhesion and Atomic Structures of Gold on Ceria Nanostructures:The Role of Surface Structure and Oxidation State of Ceria Supports

    SciTech Connect

    Lin, Yuyuan; Wu, Zili; Wen, Jianguo; Poeppelmeier, Kenneth R; Marks, Laurence D

    2015-01-01

    Recent advances in heterogeneous catalysis have demonstrated that oxides supports with the same material but different shapes can result in metal catalysts with distinct catalytic properties. The shape-dependent catalysis was not well-understood owing to the lack of direct visualization of the atomic structures at metal-oxide interface. Herein, we utilized aberration-corrected electron microscopy and revealed the atomic structures of gold particles deposited on ceria nanocubes and nanorods with {100} or {111} facets exposed. For the ceria nanocube support, gold nanoparticles have extended atom layers at the metal-support interface. In contrast, regular gold nanoparticles and rafts are present on the ceria nanorod support. After hours of water gas shift reaction, the extended gold atom layers and rafts vanish, which is associated with the decrease of the catalytic activities. By understanding the atomic structures of the support surfaces, metal-support interfaces, and morphologies of the gold particles, a direct structure-property relationship is established.

  17. 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

  18. Salicylamide-lanthanide complexes for use as luminescent markers

    SciTech Connect

    Raymond, Kenneth N.; Petoud, Stephane; Cohen, Seth; Xu, Jide

    2008-07-29

    The present invention provides luminescent lanthanide metal chelates comprising a metal ion of the lanthanide series and a complexing agent comprising at least one salicylamidyl moiety. Also provided are probes incorporating the salicylamidyl ligands of the invention and methods utilizing the ligands of the invention and probes comprising the ligands of the invention.

  19. Improved method for extracting lanthanides and actinides from acid solutions

    DOEpatents

    Horwitz, E.P.; Kalina, D.G.; Kaplan, L.; Mason, G.W.

    1983-07-26

    A process for the recovery of actinide and lanthanide values from aqueous acidic solutions uses a new series of neutral bi-functional extractants, the alkyl(phenyl)-N,N-dialkylcarbamoylmethylphosphine oxides. The process is suitable for the separation of actinide and lanthanide values from fission product values found together in high-level nuclear reprocessing waste solutions.

  20. Salicylamide-lanthanide complexes for use as luminescent markers

    DOEpatents

    Raymond, Kenneth N.; Petoud, Stephane; Cohen, Seth; Xu, Jide

    2002-01-01

    The present invention provides luminescent lanthanide metal chelates comprising a metal ion of the lanthanide series and a complexing agent comprising at least one salicylamidyl moiety. Also provided are probes incorporating the salicylamidyl ligands of the invention and methods utilizing the ligands of the invention and probes comprising the ligands of the invention.

  1. Phthalamide lanthanide complexes for use as luminescent markers

    DOEpatents

    Raymond, Kenneth N.; Petoud, Stephane; Cohen, Seth M.; Xu, Jide

    2003-01-01

    The present invention provides luminescent lanthanide metal chelates comprising a metal ion of the lanthanide series and a complexing agent comprising at least one phthalamidyl moiety. Also provided are probes incorporating the phthalamidyl ligands of the invention and methods utilizing the ligands of the invention and probes comprising the ligands of the invention.

  2. Salicylamide-lanthanide complexes for use as luminescent markers

    DOEpatents

    Raymond, Kenneth N.; Petoud, Stephane; Cohen, Seth; Xu, Jide

    2006-03-28

    The present invention provides luminescent lanthanide metal chelates comprising a metal ion of the lanthanide series and a complexing agent comprising at least one salicylamidyl moiety. Also provided are probes incorporating the salicylamidyl ligands of the invention and methods utilizing the ligands of the invention and probes comprising the ligands of the invention.

  3. Phthalamide-lanthanide complexes for use as luminescent markers

    DOEpatents

    Raymond, Kenneth N.; Petoud, Stephane; Cohen, Seth M.; Xu, Jide

    2005-03-08

    The present invention provides luminescent lanthanide metal chelates comprising a metal ion of the lanthanide series and a complexing agent comprising at least one phthalamidyl moiety. Also provided are probes incorporating the phthalamidyl ligands of the invention and methods utilizing the ligands of the invention and probes comprising the ligands of the invention.

  4. Phthalamide-lanthanide complexes for use as luminescent markers

    DOEpatents

    Raymond, Kenneth N.; Petoud, Stephane; Cohen, Seth; Xu, Jide

    2008-10-28

    The present invention provides luminescent lanthanide metal chelates comprising a metal ion of the lanthanide series and a complexing agent comprising at least one phthalamidyl moiety. Also provided are probes incorporating the phthalamidyl ligands of the invention and methods utilizing the ligands of the invention and probes comprising the ligands of the invention.

  5. Highly sensitive and robust peroxidase-like activity of porous nanorods of ceria and their application for breast cancer detection.

    PubMed

    Tian, Zhimin; Li, Jing; Zhang, Zhiyun; Gao, Wei; Zhou, Xuemei; Qu, Yongquan

    2015-08-01

    Porous nanorods of ceria (PN-Ceria), a novel ceria nanostructure with a large surface area and a high surface Ce(3+) fraction, exhibited strong intrinsic peroxidase activity toward a classical peroxidase substrate in the presence of H2O2. Peroxidase-like activity of ceria originated from surface Ce(3+) species as the catalytic center, thereby explaining the high performance of PN-Ceria as an artificial enzyme mimicking peroxidase. Compared with the natural enzyme horseradish peroxidase (HRP), PN-Ceria showed several advantages such as low cost, easy storage, high sensitivity, and, prominently, chemical and catalytic stability under harsh conditions. Importantly, the enzymatic activity of PN-Ceria remained nearly constant and stable over a wide range of temperature and pH values, ensuring the accuracy and reliability of measurements of its peroxidase-like activity. A PN-Ceria based novel diagnostic system was developed for breast cancer detection with a higher sensitivity than the standard HRP detection system. Our work has laid a solid foundation for the development of PN-Ceria as a novel diagnostic tool for clinical use.

  6. Chemistry - Oxygen Vacancies and Catalysis on Ceria Surfaces

    SciTech Connect

    Campbell, Charles T.; Peden, Charles HF.

    2005-07-29

    Chemistry occurring at the surface of metal oxides is critical in a variety of industrial applications including catalysis and photocatalysis, optical display technology, solar energy devices and corrosion prevention. Defects have long been recognized to be the most reactive sites on the surfaces of many oxide materials. The most common types of defects present on the surfaces of metal oxides are oxygen vacancies and step edges. The nature of surface oxygen vacancies, and their number, distribution and diffusion across the surface of oxides, are thus issues of major scientific importance. One of the most interesting oxides in this respect is CeO2, since oxygen vacancies play the key role in giving this material it's industrially important ''oxygen-storage capacity''. This capacity makes modern automotive exhaust treatment catalysts containing CeO2 much more effective than their predecessors without CeO2. Ceria is also well known as a support which enhances the performance of transition metal catalysts, relative to other oxide supports, in a variety of other reactions including water-gas shift, steam reforming of oxygenates and PROX 1-7, all of which hold promise for enabling a hydrogen economy 1. Related to ceria's facile redox capacity (ability to rapidly form and eliminate oxygen vacancy defects) is the poorly understood observation that some less reducible oxides, such as zirconia (ZrO2), are used as additives that actually enhance this ''oxygen storage'' property of CeO2. In this issue, Esch and coworkers in Trieste, Italy report an exciting study that for the first time clearly elucidates the structure, distribution and formation of oxygen vacancies on a cerium oxide surface 8. They have elegantly combined beautiful, atomic-resolution imaging using scanning-tunneling microscopy (STM) on a ceria surface with state-of-the-art quantum mechanical calculations using Density Functional Theory (DFT) to raise our understanding of CeO2 surfaces to a much higher level

  7. Continuous Precipitation of Ceria Nanoparticles from a Continuous Flow Micromixer

    SciTech Connect

    Tseng, Chih Heng; Paul, Brian; Chang, Chih-hung; Engelhard, Mark H.

    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.

  8. Formation of alumina-ceria mixed oxide in model systems

    NASA Astrophysics Data System (ADS)

    Skála, Tomáš; Tsud, Nataliya; Prince, Kevin C.; Matolín, Vladimír

    2011-02-01

    Interaction of aluminium with cerium oxide was studied by photoelectron spectroscopy of Al/CeO2(1 1 1) and CeO2/Al(1 1 1) model systems. It was found in both cases that metallic aluminium was immediately oxidized, CeO2 was partially reduced and a mixed oxide with cerium present as Ce3+ was formed. The compound is probably cerium aluminate CeAlO3 mixed with Al2O3 or Ce2O3. In both cases the intermixing was limited by the diffusion of aluminium into ceria. The excess of deposited material above this limit formed AlOx and CeO2 overlayers on the top of the mixed oxide + aluminate/CeO2 and mixed oxide + aluminate/Al films, respectively.

  9. Morphological Control and Characterization of Monodispersed Ceria Particles

    SciTech Connect

    Minamidate, Y.; Yin, S.; Devaraju, M. K.; Sato, T.

    2010-11-24

    The morphological control of cerium oxide particles was carried out by a homogeneous precipitation followed by calcination in air at 400 deg. C. The effects of pre-aging temperature, aging time and precipitation reagents on the morphologies of final products were investigated. When urea was used as a precipitation reagent, monodispersed spherical and flake-like cerium carbonate hydroxide precursor was precipitated in the solution at 90 deg. C for 2 h after pre-aging at 25 deg. C - 50 deg. C for 24-72 h. On the other hand, monodispersed nanosize rod-like cerium hydroxide particles were obtained using triethanolamine as precipitation reagent. Ceria particles with the same morphologies and slightly smaller particle size than those of as-prepared cerium precursor could be obtained after calcination in air at 400 deg. C. Physical-chemical characteristics of the monodispersed cerium oxide particles were evaluated.

  10. Ceria Nanotube Formed by Sacrificed Precursors Template through Oswald Ripening

    PubMed Central

    Pang, Laixue; Wang, Xiaoying; Tang, Xinde

    2015-01-01

    Controllable preparation of ceria nanotube was realized by hydrothermal treatment of Ce(OH)CO3 precursors. The gradually changing morphologies and microstructures of cerium oxide were characterized by X-ray powder diffraction, scanning electron microscopy and transmission electron microscopy. A top-down path is illuminated to have an insight to the morphological transformation from nanorod to nanotube by adjusting the reaction time. The growth process is investigated by preparing a series of intermediate morphologies during the shape evolution of CeO2nanostructure based on the scanning electron microscopy image observation. On the basis of the time-dependent experimental observation, the possible formation mechanism related to oriented attachment and Oswald ripening was proposed, which might afford some guidance for the synthesis of other inorganic nanotubes. PMID:26151866

  11. Effect of cobalt doping on structural, optical and redox properties cerium oxide nanoparticles

    NASA Astrophysics Data System (ADS)

    Ansari, Anees A.; Labis, J.; Alam, M.; Ramay, Shahid M.; Ahmad, N.; Mahmood, Asif

    2016-03-01

    Cobalt-doped ceria nanoparticles were synthesized using the polyol method under co-precipitation hydrolysis. The structural, morphological, optical and redox properties were observed to investigate the influence of different concentration of cobalt ion doping on the prepared CeO2 nanomaterials in terms of X-ray diffraction, field-emission transmission electron microscopy, thermogravimetric analysis, Fourier-transform infrared spectroscopy, UV/vis absorption spectroscopy and temperature program reduction techniques. The optical band gap energy was calculated from the optical absorption spectra for doped ceria nanoparticles, which have been found to be 2.68, 2.77, and 2.82 eV for the 2, 4, and 7 mol% Co ion-doped CeO2 nanoparticles, respectively. As observed, the band gap energies increases as the doping Co ion concentrations increased, which could be due to significant increased oxygen vacancies with Co doping. The synergistic interaction between Co and CeO2 was the main factor responsible for high catalytic activity of cobalt-doped CeO2 model catalysts.

  12. Ceria-Based Anodes for Next Generation Solid Oxide Fuel Cells

    NASA Astrophysics Data System (ADS)

    Mirfakhraei, Behzad

    Mixed ionic and electronic conducting materials (MIECs) have been suggested to represent the next generation of solid oxide fuel cell (SOFC) anodes, primarily due to their significantly enhanced active surface area and their tolerance to fuel components. In this thesis, the main focus has been on determining and tuning the physicochemical and electrochemical properties of ceria-based MIECs in the versatile perovskite or fluorite crystal structures. In one direction, BaZr0.1Ce0.7Y0.1 M0.1O3-delta (M = Fe, Ni, Co and Yb) (BZCY-M) perovskites were synthesized using solid-state or wet citric acid combustion methods and the effect of various transition metal dopants on the sintering behavior, crystal structure, chemical stability under CO2 and H 2S, and electrical conductivity, was investigated. BZCY-Ni, synthesized using the wet combustion method, was the best performing anode, giving a polarization resistance (RP) of 0.4 O.cm2 at 800 °C. Scanning electron microscopy and X-ray diffraction analysis showed that this was due to the exsolution of catalytic Ni nanoparticles onto the oxide surface. Evolving from this promising result, the effect of Mo-doped CeO 2 (nCMO) or Ni nanoparticle infiltration into a porous Gd-doped CeO 2 (GDC) anode (in the fluorite structure) was studied. While 3 wt. % Ni infiltration lowered RP by up to 90 %, giving 0.09 O.cm2 at 800 °C and exhibiting a ca. 5 times higher tolerance towards 10 ppm H2, nCMO infiltration enhanced the H2 stability by ca. 3 times, but had no influence on RP. In parallel work, a first-time study of the Ce3+ and Ce 4+ redox process (pseudocapacitance) within GDC anode materials was carried out using cyclic voltammetry (CV) in wet H2 at high temperatures. It was concluded that, at 500-600 °C, the Ce3+/Ce 4+ reaction is diffusion controlled, probably due to O2- transport limitations in the outer 5-10 layers of the GDC particles, giving a very high capacitance of ca. 70 F/g. Increasing the temperature ultimately

  13. High-performance electrode for medium-temperature solid oxide fuel cells. Control of microstructure of ceria-based anodes with highly dispersed ruthenium electrocatalysts

    SciTech Connect

    Uchida, Hiroyuki; Osuga, Takashi; Watanabe, Masahiro

    1999-05-01

    In order to enhance gas-diffusion rates in a mixed-conducting samaria-doped ceria (SDC) anode, micrometer-sized pores were prepared by sintering a SDC paste containing fine polymer beads (d = 1.2 {micro}m) coated on an yttria-stabilized zirconia electrolyte. SDC anodes prepared under different conditions were examined to determine their pore-size distribution, pore volume, ohmic resistance, polarization behavior, and morphological structure. Both the anodic overpotential and the ohmic resistance of SDC anodes were lowered appreciably by controlling their microstructures. The performance of a SDC anode with optimized microstructure was enhanced further with highly dispersed Ru catalysts at 3 wt % loading, especially at low operating temperatures at about 800 C. The current density on a Ru-SDC anode at an overpotential of 0.1 V was 0.5 A/cm{sup 2} at 800 C.

  14. Understanding stability trends along the lanthanide series.

    PubMed

    Regueiro-Figueroa, Martín; Esteban-Gómez, David; de Blas, Andrés; Rodríguez-Blas, Teresa; Platas-Iglesias, Carlos

    2014-04-01

    The stability trends across the lanthanide series of complexes with the polyaminocarboxylate ligands TETA(4-) (H4TETA=2,2',2'',2'''-(1,4,8,11-tetraazacyclotetradecane-1,4,8,11-tetrayl)tetraacetic acid), BCAED(4-) (H4BCAED=2,2',2'',2'''-{[(1,4-diazepane-1,4-diyl)bis(ethane-2,1-diyl)]bis(azanetriyl)}tetraacetic acid), and BP18C6(2-) (H2BP18C6=6,6'-[(1,4,10,13-tetraoxa-7,16-diazacyclooctadecane-7,16-diyl)bis(methylene)]dipicolinic acid) were investigated using DFT calculations. Geometry optimizations performed at the TPSSh/6-31G(d,p) level, and using a 46+4f(n) ECP for lanthanides, provide bond lengths of the metal coordination environments in good agreement with the experimental values observed in the X-ray structures. The contractions of the Ln(3+) coordination spheres follow quadratic trends, as observed previously for different isostructural series of complexes. We show here that the parameters obtained from the quantitative analysis of these data can be used to rationalize the observed stability trends across the 4f period. The stability trends along the lanthanide series were also evaluated by calculating the free energy for the reaction [La(L)](n+/-)(sol)+Ln(3+)(sol)→[Ln(L)](n+/-)(sol)+La(3+)(sol). A parameterization of the Ln(3+) radii was performed by minimizing the differences between experimental and calculated standard hydration free energies. The calculated stability trends are in good agreement with the experimental stability constants, which increase markedly across the series for BCAED(4-) complexes, increase smoothly for the TETA(4-) analogues, and decrease in the case of BP18C6(2-) complexes. The resulting stability trend is the result of a subtle balance between the increased binding energies of the ligand across the lanthanide series, which contribute to an increasing complex stability, and the increase in the absolute values of hydration energies along the 4f period.

  15. Multicoordinate ligands for actinide/lanthanide separations.

    PubMed

    Dam, Henk H; Reinhoudt, David N; Verboom, Willem

    2007-02-01

    In nuclear waste treatment processes there is a need for improved ligands for the separation of actinides (An(III)) and lanthanides (Ln(III)). Several research groups are involved in the design and synthesis of new An(III) ligands and in the confinement of these and existing An(III) ligands onto molecular platforms giving multicoordinate ligands. The preorganization of ligands considerably improves the An(III) extraction properties, which are largely dependent on the solubility and rigidity of the platform. This tutorial review summarizes the most important An(III) ligands with emphasis on the preorganization strategy using (macrocyclic) platforms.

  16. Complexes of Lapachol and Lawsone with Lanthanides.

    PubMed

    Genovese, Salvatore; Taddeo, Vito Alessandro; Epifano, Francesco; Fiorito, Serena

    2015-11-01

    Naturally occurring 2-hydroxy-1,4-naphthoquinones are well known to form readily stable complexes with transition metals. In this short communication we describe for the first time the synthesis and preliminary data about structural characterization of complexes between two naturally widespread 2-hydroxy-1,4-naphthoquinones, namely lapachol (1) and lawsone (2), with selected lanthanides like lanthanum, gadolinium, and ytterbium. When tested as cytotoxic compounds, such complexes exhibited an activity that was either higher or equal to that of the parent naphthoquinone. PMID:26749803

  17. Efficient Ceria-Platinum Inverse Catalyst for Partial Oxidation of Methanol.

    PubMed

    Ostroverkh, Anna; Johánek, Viktor; Kúš, Peter; Šedivá, Romana; Matolín, Vladimír

    2016-06-28

    Ceria-platinum-based bilayered thin films deposited by magnetron sputtering were developed and tested in regard to their catalytic activity for methanol oxidation by employing a temperature-programmed reaction (TPR) technique. The composition and structure of the samples were characterized by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Both conventional (oxide-supported metal nanoparticles [NPs]) and inverse configurations (metal with oxide overlayer) were analyzed to uncover the structural dependence of activity and selectivity of these catalysts with respect to different pathways of methanol oxidation. We clearly demonstrate that the amount of cerium oxide (ceria) loading has a profound influence on methanol oxidation reaction characteristics. Adding a noncontinuous adlayer of ceria greatly enhances the catalytic performance of platinum (Pt) in favor of partial oxidation of methanol (POM), gaining an order of magnitude in the absolute yield of hydrogen. Moreover, the undesired by-production of carbon monoxide (CO) is strongly suppressed, making the ceria-platinum inverse catalyst a great candidate for clean hydrogen production. It is suggested that the methanol oxidation process is facilitated by the synergistic effect between both components of the inverse catalyst (involving oxygen from ceria and providing a reaction site on the adjacent Pt surface) as well as by the fact that the ability of ceria to exchange oxygen (i.e., to alter the oxidation state of Ce between 3+ and 4+) during the reaction is inversely proportional to its thickness. The increased redox capability of the discontinuous ceria adlayer shifts the preferred reaction pathway from dehydrogenation of hydroxymethyl intermediate to CO in favor of its oxidation to formate. PMID:27254727

  18. Ceria in an oxygen environment: Surface phase equilibria and its descriptors

    NASA Astrophysics Data System (ADS)

    Botu, Venkatesh; Ramprasad, Rampi; Mhadeshwar, Ashish B.

    2014-01-01

    Ceria offers great promise in catalysis, due to its facile switchable oxidation state manifested from its oxygen buffering capability. This work presents the first equilibrium surface phase diagram of ceria exposed to various oxygen providing reservoirs (e.g., a pure O2 reservoir as well as NO/NO2, H2/H2O, or CO/CO2 redox environments) using first principles thermodynamics. For a pure O2 environment, the stoichiometric ceria (111) surface is favored at ambient conditions. Any appreciable surface reduction is observed only at ultra-low oxygen partial pressures (< 10- 30 atm) and room temperature or at temperatures > 2000 K and ambient pressures. On the other hand, a redox environment promotes surface reduction at temperatures as low as 300 K. Semi-local, Hubbard modified semi-local, and hybrid electronic exchange-correlation functionals are used to capture the energetics and phase transitions. We observe no difference between the three theories in the energetics governing ceria surface reduction in the dilute limit. The predicted phase transitions by all levels of theory are in agreement with each other and in excellent agreement with literature experimental data. Creation of oxygen vacancies in the sub-surface is energetically favored over surface vacancies, and is pivotal in determining the key features of the surface phase diagram. Consequently, we identify the oxygen vacancy formation energy as a descriptor for the surface reactivity of ceria in various oxygen environments. This single governing factor could be used in future studies to probe the surface reactivity of ceria and also to design improved ceria-based materials for redox reactions.

  19. Single Component Lanthanide Hybrids Based on Metal-Organic Framework for Near-Ultraviolet White Light LED.

    PubMed

    Zhao, Yan-Wu; Zhang, Fu-Qiang; Zhang, Xian-Ming

    2016-09-14

    Near-UV single-phase white-light phosphor (Eu0.045Tb0.955CPOMBA/La0.6Eu0.1Tb0.3CPOMBA) based on metal-organic framework was prepared by in situ doping isostructural lanthanide MOF with Eu(3+) and Tb(3+), and it is found that the energy can effectively transfer from organic ligand to lanthanides, which can overcome weak absorption under direct excitation of lanthanide ions due to the forbidden f-f transitions. The photoluminescence and thermostability of the new MOF phosphor are investigated, and effective white-light emission is achieved under 365 and 380 nm excitations. By employing Eu0.045Tb0.955CPOMBA as phosphor, we fabricated a near-ultraviolet white-light-emitting diode (n-UV WLED) (365 nm) with low CCT (5733 K), high CRI (Ra = 73.4), and CIE chromaticity coordinate (0.3264, 0.3427). This approach may open new perspectives for developing single-phase UV phosphors. PMID:27560457

  20. Single Component Lanthanide Hybrids Based on Metal-Organic Framework for Near-Ultraviolet White Light LED.

    PubMed

    Zhao, Yan-Wu; Zhang, Fu-Qiang; Zhang, Xian-Ming

    2016-09-14

    Near-UV single-phase white-light phosphor (Eu0.045Tb0.955CPOMBA/La0.6Eu0.1Tb0.3CPOMBA) based on metal-organic framework was prepared by in situ doping isostructural lanthanide MOF with Eu(3+) and Tb(3+), and it is found that the energy can effectively transfer from organic ligand to lanthanides, which can overcome weak absorption under direct excitation of lanthanide ions due to the forbidden f-f transitions. The photoluminescence and thermostability of the new MOF phosphor are investigated, and effective white-light emission is achieved under 365 and 380 nm excitations. By employing Eu0.045Tb0.955CPOMBA as phosphor, we fabricated a near-ultraviolet white-light-emitting diode (n-UV WLED) (365 nm) with low CCT (5733 K), high CRI (Ra = 73.4), and CIE chromaticity coordinate (0.3264, 0.3427). This approach may open new perspectives for developing single-phase UV phosphors.

  1. Lanthanide Complexes as a Test for Evidence of Life

    NASA Technical Reports Server (NTRS)

    Benavides, Jeannette

    1998-01-01

    The objective of this research is to advance the understanding of the interaction of lanthanide metals with biological organic molecules and to develop a technique to detect these compounds in the solid state and in situ in Mars and other planetary bodies. The detection of these complexes should provide evidence of life past or present. In addition, detection of the metals alone will provide important information about the geological history of a planetary body. Lanthanides were chosen as our focus of interest because they form very stable complexes with organic molecules in solution and they produce intense luminescence in the ultraviolet and visible spectra. The rare earth complexes available are mostly synthetic for diverse applications in medicine. There is not much work done on the complexes that form in nature. Lanthanides have many applications and they are mined aR over the world, however, since the interest has been only in the elements, the analytical techniques employed destroy any organic ligands that may be present. In order to determine if and which lanthanide complexes form in nature and their concentration, soil samples have been collected from areas rich in soluble lanthanide compounds like phosphates and also rich in vegetation. The soil samples will be analyzed and the lanthanide complexes if present will be isolated and characterized. A spectrometer to detect the lanthanide complexes in situ and in the solid state will be designed. In this workshop, the research approach and its implications will be discussed.

  2. Tailoring Bicelle Morphology and Thermal Stability with Lanthanide-Chelating Cholesterol Conjugates.

    PubMed

    Isabettini, Stéphane; Liebi, Marianne; Kohlbrecher, Joachim; Ishikawa, Takashi; Windhab, Erich J; Fischer, Peter; Walde, Peter; Kuster, Simon

    2016-09-01

    Bicelles composed of DMPC and phospholipids capable of chelating lanthanide ions, such as 1,2-dimyristoyl-sn-glycero-3-phospho-ethanolamine-diethylene triaminepentaacetate (DMPE-DTPA), are highly tunable magnetically responsive soft materials. Further doping of these systems with cholesterol-DTPA conjugates complexed to a lanthanide ion considerably enhances the bicelle's size and magnetic alignability. The high value of these cholesterol conjugates for bicelle design remains largely unexplored. Herein, we examine how molecular structural alterations within the cholesterol-DTPA conjugates lead to contrasting self-assembled polymolecular aggregate structures when incorporated into DMPC/DMPE-DTPA/Tm(3+) bilayers. The nature of the linker connecting the DTPA-chelating moiety to the sterol backbone is examined by synthesizing conjugates of various linker lengths and polarities. The incorporation of these compounds within the bilayer results in polymolecular aggregate geometries of higher curvature. The increasing degrees of freedom for conformational changes conveyed to the chelator headgroup with increasing linker atomic length reduce the cholesterol-DTPA conjugate's critical packing parameter. Consequently, an inverse correlation between the number of carbon atoms in the linker and the bicelle radius is established. The introduction of polarity into the carbon chain of the linker did not cause major changes in the polymolecular aggregate architecture. Under specific conditions, the additives permit the formation of remarkably temperature-resistant bicelles. The versatility of design offered by these amphiphiles gives rise to new and viable tools for the growing field of magnetically responsive soft materials. PMID:27529644

  3. Lanthanide coordination polymers: Synthesis, diverse structure and luminescence properties

    SciTech Connect

    Song, Xue-Qin Lei, Yao-Kun; Wang, Xiao-Run; Zhao, Meng-Meng; Peng, Yun-Qiao; Cheng, Guo-Quan

    2014-10-15

    The new semirigid exo-bidentate ligand incorporating furfurysalicylamide terminal groups, namely, 1,4-bis([(2′-furfurylaminoformyl)phenoxyl]methyl)-2,5-bismethylbenzene (L) was synthesized and used as building blocks for constructing lanthanide coordination polymers with luminescent properties. The series of lanthanide nitrate complexes have been characterized by elemental analysis, IR spectroscopy, and X-ray diffraction analysis. The semirigid ligand L, as a bridging ligand, reacts with lanthanide nitrates forming three distinct structure types: chiral noninterpenetrated two-dimensional (2D) honeycomblike (6,3) (hcb, Schläfli symbol 6{sup 3}, vertex symbol 6 6 6) topological network as type I, 1D zigzag chain as type II and 1D trapezoid ladder-like chain as type III. The structural diversities indicate that lanthanide contraction effect played significant roles in the structural self-assembled process. The luminescent properties of Eu{sup III}, Tb{sup III} and Dy{sup III} complexes are discussed in detail. Due to the good match between the lowest triplet state of the ligand and the resonant energy level of the lanthanide ion, the lanthanide ions in Eu{sup III}, Tb{sup III} and Dy{sup III} complexes can be efficiently sensitized by the ligand. - Graphical abstract: We present herein six lanthanide coordination polymers of a new semirigid exo-bidentate ligand which not only display diverse structures but also possess strong luminescence properties. - Highlights: • We present lanthanide coordination polymers of a new semirigid exo-bidentate ligand. • The lanthanide coordination polymers exhibit diverse structures. • The luminescent properties of Tb{sup III}, Eu{sup III} and Dy{sup III} complexes are discussed in detail.

  4. The Crystal Structure of Lanthanide Zirconates

    NASA Astrophysics Data System (ADS)

    Clements, Richard; Kennedy, Brendan; Ling, Christopher; Stampfl, Anton P. J.

    2010-03-01

    The lanthanide zirconates of composition Ln2Zr2O7 (Ln = La-Gd) are of interest for use in inert matrix fuels and nuclear wasteforms. The series undergoes a pyrochlore to fluorite phase transition as a function of the Ln atomic radii. The phase transition has been attributed to disordering of both the cation and the anion [1]. We have undertaken a synthesis of the lanthanide zirconate series Ln2Zr2O7 (Ln = La-Gd), Ln0.2Zr0.8O1.9 (Ln = Tb-Yb) and NdxHo2-xZr2O7 (0

  5. Ion exchange in hydroxyapatite with lanthanides.

    PubMed

    Cawthray, Jacqueline F; Creagh, A Louise; Haynes, Charles A; Orvig, Chris

    2015-02-16

    Naturally occurring hydroxyapatite, Ca5(PO4)3(OH) (HAP), is the main inorganic component of bone matrix, with synthetic analogues finding applications in bioceramics and catalysis. An interesting and valuable property of both natural and synthetic HAP is the ability to undergo cationic and anionic substitution. The lanthanides are well-suited for substitution for the Ca(2+) sites within HAP, because of their similarities in ionic radii, donor atom requirements, and coordination geometries. We have used isothermal titration calorimetry (ITC) to investigate the thermodynamics of ion exchange in HAP with a representative series of lanthanide ions, La(3+), Sm(3+), Gd(3+), Ho(3+), Yb(3+) and Lu(3+), reporting the association constant (Ka), ion-exchange thermodynamic parameters (ΔH, ΔS, ΔG), and binding stoichiometry (n). We also probe the nature of the La(3+):HAP interaction by solid-state nuclear magnetic resonance ((31)P NMR), X-ray diffraction (XRD), and inductively coupled plasma-optical emission spectroscopy (ICP-OES), in support of the ITC results. PMID:25594577

  6. Picosecond dynamics from lanthanide chloride melts

    NASA Astrophysics Data System (ADS)

    Kalampounias, Angelos G.

    2012-12-01

    The picosecond dynamics of molten lanthanide chlorides is studied by means of vibrational spectroscopy. Polarized Raman spectra of molten LaCl3, NdCl3, GdCl3, DyCl3, HoCl3 and YCl3 are fitted to a model enabling to obtain the times of vibrational dephasing, tν and vibrational frequency modulation tω. Our aim is to find possible sensitive indicators of short-time dynamics. It has been found that all lanthanide chlorides exhibit qualitative similarities in the vibrational relaxation and frequency modulation times in the molten state. It appears that the vibrational correlation functions of all melts comply with the Rothschild approach assuming that the environmental modulation is described by a stretched exponential decay. The evolution of the dispersion parameter α indicates the deviation of the melts from the model simple liquid and the similar local environment in which the oscillator is placed and with which it is coupled. The "packing" of the anions around central La3+ cation seems to be the key factor for the structure and the dynamics of the melts. The results are discussed in the framework of the current phenomenological status of the field.

  7. Effects of different precursors on size and optical properties of ceria nanoparticles prepared by microwave-assisted method

    SciTech Connect

    Samiee, Sara; Goharshadi, Elaheh K.

    2012-04-15

    Highlights: Black-Right-Pointing-Pointer A rapid and efficient microwave method was applied for synthesis of nano ceria. Black-Right-Pointing-Pointer Changing precursor has great effects on optical properties and size of nano ceria. Black-Right-Pointing-Pointer Fabrication of ceria nanoparticles using Ce{sup 4+} salts leads to better results. Black-Right-Pointing-Pointer Band gap energies of ceria nanoparticles were evaluated by UV-vis spectroscopy. -- Abstract: Cerium oxide, ceria (CeO{sub 2}), is one of the favourable nanoparticles (NPs) that possesses many remarkable properties so that it can be used in medicine, chemistry, environment, energy, information, industry, and so on. In this study, the crystalline ceria NPs were successfully prepared by an efficient microwave-assisted heating technique from an aqueous solution using different cerium salts (Ce(IV) and Ce(III) salts). The products were characterized by X-ray powder diffraction (XRD), transmission electron microscope (TEM), FTIR spectroscopy, Raman spectroscopy, and UV-vis absorption spectroscopy. The results revealed that changing the precursor led to great effects on size, band gap energy, and the reaction time of preparing the ceria NPs. The significant feature of this manuscript is that the effects of different precursors on the structural and optical properties of ceria NPs were investigated for the first time. The average particle size of different samples was below 8 nm.

  8. Support shape effect in metal oxide catalysis: ceria nanoshapes supported vanadia catalysts for oxidative dehydrogenation of iso-butane

    SciTech Connect

    Wu, Zili; Schwartz, Viviane; Li, Meijun; Rondinone, Adam Justin; Overbury, Steven {Steve} H

    2012-01-01

    The activation energy of VOx/CeO2 catalysts in oxidative dehydrogenation of iso-butane was found dependent on the shape of ceria support: rods < octahedra, closely related to the surface oxygen vacancy formation energy and defects amount of the two ceria supports with different crystallographic surface planes.

  9. Some aspects of the geochemistry of yttrium and the lanthanides

    USGS Publications Warehouse

    Fleischer, Michael

    1965-01-01

    Recent data on the relative abundances of the lanthanides and yttrium in meteorites, basaltic rocks, granitic rocks and sedimentary rocks are reviewed. It is shown that the data are inadequate to substantiate or to disprove Taylor's derivation from these data of a 1:1 abundance ratio of basaltic to granitic rocks in the continental crust. Graphs are given to illustrate the variation of lanthanides in minerals with paragenesis. Both the paragenesis and the crystal chemistry of minerals affect the composition of the lanthanides.

  10. Comparison of ceria nanoparticle concentrations in effluent from chemical mechanical polishing of silicon dioxide.

    PubMed

    Zazzera, Larry; Mader, Brian; Ellefson, Mark; Eldridge, Jess; Loper, Steve; Zabasajja, John; Qian, Julie

    2014-11-18

    This work measured and compared the effluent from the chemical mechanical polishing (CMP) of silicon dioxide using ceria slurry and ceria fixed abrasive. CMP waste streams were tested for total solids, cerium, silicon, and 6 nm to 20 μm diameter particles. The concentration of cerium and total solids in the effluent were very different for the two polishes studied. The fixed abrasive polish produced 94% less CeO2 emissions per SiO2 removed. The higher ceria levels in the slurry effluent are associated with 99-279 nm particles, and attributed to ceria abrasive. The lower concentration of ceria in the effluent from the fixed abrasive process is due to the lower wear rate of mineral from the fixed abrasive, compared to the more environmentally mobile mineral in the slurry. These results support the "bonded" nature of the abrasive particles in fixed abrasive polishing and are relevant to sustainability strategies that seek to reduce particle emissions in surface conditioning technology.

  11. Comparison of ceria nanoparticle concentrations in effluent from chemical mechanical polishing of silicon dioxide.

    PubMed

    Zazzera, Larry; Mader, Brian; Ellefson, Mark; Eldridge, Jess; Loper, Steve; Zabasajja, John; Qian, Julie

    2014-11-18

    This work measured and compared the effluent from the chemical mechanical polishing (CMP) of silicon dioxide using ceria slurry and ceria fixed abrasive. CMP waste streams were tested for total solids, cerium, silicon, and 6 nm to 20 μm diameter particles. The concentration of cerium and total solids in the effluent were very different for the two polishes studied. The fixed abrasive polish produced 94% less CeO2 emissions per SiO2 removed. The higher ceria levels in the slurry effluent are associated with 99-279 nm particles, and attributed to ceria abrasive. The lower concentration of ceria in the effluent from the fixed abrasive process is due to the lower wear rate of mineral from the fixed abrasive, compared to the more environmentally mobile mineral in the slurry. These results support the "bonded" nature of the abrasive particles in fixed abrasive polishing and are relevant to sustainability strategies that seek to reduce particle emissions in surface conditioning technology. PMID:25317965

  12. Enhanced hydrogen oxidation activity and H2S tolerance of Ni-infiltrated ceria solid oxide fuel cell anodes

    NASA Astrophysics Data System (ADS)

    Mirfakhraei, Behzad; Paulson, Scott; Thangadurai, Venkataraman; Birss, Viola

    2013-12-01

    The effect of Ni infiltration into porous Gd-doped ceria (GDC) anodes on their H2 oxidation performance, with and without added 10 ppm H2S, is reported here. Porous GDC anodes (ca. 10 μm thick) were deposited on yttria stabilized zirconia (YSZ) supports and then infiltrated with catalytic amounts of a Ni nitrate solution, followed by electrochemical testing in a 3-electrode half-cell setup at 500-800 °C. Infiltration of 3 wt.% Ni into the porous GDC anode lowered the polarization resistance by up to 85%, affecting mainly the low frequency impedance arc. When exposed to 10 ppm H2S, the Ni-infiltrated anodes exhibited a ca. 5 times higher tolerance toward sulfur poisoning compared to GDC anodes alone, also showing excellent long-term stability in 10 ppm H2S. In the presence of H2S, it is proposed that Ni, likely distributed as a nanophase, helps to maintain a clean GDC surface at the Ni/GDC interface at which the H2 oxidation reaction takes place. In turn, the GDC will readily supply oxygen anions to the adjacent Ni surfaces, thus helping to remove adsorbed sulfur.

  13. Thermal NF3 fluorination/oxidation of cobalt, yttrium, zirconium, and selected lanthanide oxides

    SciTech Connect

    Scheele, Randall D.; McNamara, Bruce K.; Casella, Andrew M.; Kozelisky, Anne E.; Neiner, Doinita

    2013-02-01

    This paper presents results of our continuing 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. This article focuses on fission products that do not have volatile fluorides or oxyfluorides at expected operations temperatures. Our thermodynamic calculations show that nitrogen trifluoride has the potential to completely fluorinate fission product oxides to their fluorides. Simultaneous thermogravimetric and differential thermal analyses show that the oxides of cobalt, zirconium, and the lanthanides are fluorinated but do not form volatile fluorides when treated with nitrogen trifluoride at temperatures up to 550°C. Our studies of gadolinium-doped commercial nuclear fuel indicate that nitrogen trifluoride can extract uranium from the non-volatile gadolinium.

  14. Experimental Findings On Minor Actinide And Lanthanide Separations Using Ion Exchange

    SciTech Connect

    Hobbs, D. T.; Shehee, T. C.; Clearfield, A.

    2013-09-17

    for lanthanide ions in dilute nitric acid. The K-TSP ion exchanger exhibited the highest affinity for lanthanides in dilute nitric acid solutions. The Ge-TSP ion exchanger shows promise as a material with high affinity, but additional tests are needed to confirm the preliminary results. On the other hand, carbon nanotubes and nitrogen-doped carbon nanotubes exhibited low, but measureable affinities for lanthanide ions in dilute nitric acid solutions (pH 3 and 6). The MWCNT exhibited much lower affinities than the K-TSP in dilute nitric acid solutions. However, the MWCNT are much more chemically stable in concentrated nitric acid solutions and, therefore, may be candidates for ion exchange in more concentrated nitric acid solutions.

  15. The synthesis of CeO2 nanospheres with different hollowness and size induced by copper doping

    NASA Astrophysics Data System (ADS)

    Liu, Wei; Liu, Xiufang; Feng, Lijun; Guo, Jinxin; Xie, Anran; Wang, Shuping; Zhang, Jingcai; Yang, Yanzhao

    2014-08-01

    In this paper, copper-doped ceria oxides with different hollowness and size are fabricated by changing the Cu2+ doping concentration in the mixed water-glycol system. Results show that the copper-doped CeO2 oxides undergo a morphology transformation from the solid nanospheres to core-shell, then to hollow nanospheres with the increase of the Cu2+ doping concentration. The corresponding size becomes smaller during this transfer process. The Cu2+ doping induced acceleration in the nucleation and growth process is further investigated. The resultant Cu2+-doped CeO2 oxides exhibit enhanced CO conversion performance and better reduction behaviors.In this paper, copper-doped ceria oxides with different hollowness and size are fabricated by changing the Cu2+ doping concentration in the mixed water-glycol system. Results show that the copper-doped CeO2 oxides undergo a morphology transformation from the solid nanospheres to core-shell, then to hollow nanospheres with the increase of the Cu2+ doping concentration. The corresponding size becomes smaller during this transfer process. The Cu2+ doping induced acceleration in the nucleation and growth process is further investigated. The resultant Cu2+-doped CeO2 oxides exhibit enhanced CO conversion performance and better reduction behaviors. Electronic supplementary information (ESI) available: Fig. S1 the TEM images of the Cu2+-doped CeO2 (a-c): P2, P5 and P6; Fig. S2 EDS spectrum of the Cu2+-doped ceria sample; Fig. S3 the HRTEM images about lattice fringes of the Cu2+-doped CeO2: (a and b) P3; (c and d) P4; Fig. S4 the corresponding XPS survey spectrum of nanospheres: P1 and P4; Fig. S5 XRD pattern of P3 obtained at different solvothermal time, illustrated as (a) 1 h, (b) 2 h, (c) 4 h and (d) 8 h; Fig. S6 the TEM images of (a) the P1 sample at 36 h and (b) the P4 sample at 2 h; Fig. S7 N2 adsorption-desorption isotherms of the pure and Cu2+ doped CeO2: (a) P1, (b) P2, (c) P3, (d) P4, (e) P5 and (f) P6. Insets are the

  16. Lanthanide complexes of azidophenacyl-DO3A as new synthons for click chemistry and the synthesis of heterometallic lanthanide arrays.

    PubMed

    Tropiano, Manuel; Kenwright, Alan M; Faulkner, Stephen

    2015-04-01

    Lanthanide complexes of azidophenacyl DO3A are effective substrates for click reactions with ethyne derivatives, giving rise to aryl triazole appended lanthanide complexes, in which the aryl triazole acts as an effective sensitising chromophore for lanthanide luminescence. They also undergo click chemistry with propargylDO3A derivatives, giving rise to heterometallic complexes.

  17. Toward tuning the surface functionalization of small ceria nanoparticles

    SciTech Connect

    Huang, Xing; Wang, Binghui; Grulke, Eric A.; Beck, Matthew J.

    2014-02-21

    Understanding and controlling the performance of ceria nanoparticle (CNP) catalysts requires knowledge of the detailed structure and property of CNP surfaces and any attached functional groups. Here we report thermogravimetric analysis results showing that hydrothermally synthesized ∼30 nm CNPs are decorated with 12.9 hydroxyl groups per nm{sup 2} of CNP surface. Quantum mechanical calculations of the density and distribution of bound surface groups imply a scaling relationship for surface group density that balances formal charges in the functionalized CNP system. Computational results for CNPs with only hydroxyl surface groups yield a predicted density of bound hydroxyl groups for ∼30 nm CNPs that is ∼33% higher than measured densities. Quantitative agreement between predicted and measured hydroxyl surface densities is achieved when calculations consider CNPs with both –OH and –O{sub x} surface groups. For this more general treatment of CNP surface functionalizations, quantum mechanical calculations predict a range of stable surface group configurations that depend on the chemical potentials of O and H, and demonstrate the potential to tune CNP surface functionalizations by varying temperature and/or partial pressures of O{sub 2} and H{sub 2}O.

  18. Chitosan as template for the synthesis of ceria nanoparticles

    SciTech Connect

    Sifontes, A.B.; Gonzalez, G.; Ochoa, J.L.; Tovar, L.M.; Zoltan, T.; Canizales, E.

    2011-11-15

    Graphical abstract: Cerium oxide nanoparticles with cubic fluorite structure were prepared using chitosan as template, cerium nitrate as a starting material and sodium hydroxide as a precipitating agent. Calcinated powders at 350 {sup o}C contain agglomerated particles with average particle size of {approx}4 nm, very high porosity and foam-like morphology formed by open and close pores. Highlights: {yields} Pure CeO{sub 2} nanoparticles can take place using chitosan as template. {yields} A porous material was obtained. {yields} Blueshifts in the ultraviolet absorption spectra have been observed in cerium oxide nanocrystallites. -- Abstract: Cerium oxide (CeO{sub 2}), nanoparticles were prepared using chitosan as template, cerium nitrate as a starting material and sodium hydroxide as a precipitating agent. The resultant ceria-chitosan spheres were calcined at 350 {sup o}C. The synthesized powders were characterized by, XRD, HRTEM, UV-vis, FTIR, and TG-DTA. The average size of the nanoparticles obtained was {approx}4 nm and BET specific surface area {approx}105 m{sup 2} g{sup -1}. Blueshifts in the ultraviolet absorption spectra have been observed in cerium oxide nanocrystallites. The band-gap was found to be 4.5 eV. The blueshifts are well explained for diameters down to less than a few nanometers by the change in the electronic band structure.

  19. Unique Electronic and Structural Effects in Vanadia/Ceria-Catalyzed Reactions.

    PubMed

    Wu, Xin-Ping; Gong, Xue-Qing

    2015-10-21

    Vanadia/ceria supported catalysts exhibit ultrahigh catalytic activities in oxidative dehydrogenation (ODH) reactions. Here, we performed systematic density functional theory calculations to illustrate the underlying mechanisms. It is found that unique electronic and structural effects are both crucial in the catalytic processes. Calculations of the catalytic performance of different oxygen species in oxidation of methanol to formaldehyde suggested that the oxygen of the interface V-O-Ce group is catalytically more active, especially when H adsorption energy is small, indicating the strong structural effect in the vanadia/ceria supported catalyst. In addition, new empty localized states of O 2p generated in a ceria-supported system through depositing VO3- and VO4-type monomeric vanadia species are determined to participate in the whole ODH reaction processes and help to reduce the barriers at various steps. PMID:26440141

  20. Electrochemical synthesis and properties of ceria films grown on stainless steel

    NASA Astrophysics Data System (ADS)

    Živković, Lj. S.; Lair, V.; Lupan, O.; Ringuedé, A.

    2011-12-01

    Electrochemical synthesis of ceria films was performed on a stainless steel substrate in view of Solid Oxide Fuel Cells (SOFC) applications. Films were obtained from aqueous nitrate solutions via cathodic deposition method at room temperature. A constant potential value of -0.8 V/(SCE) was applied to reduce the molecular oxygen as hydroxide precursor, leading to a formation of adherent, homogeneous and covering films in 20 min deposition time. Structure, morphology and composition of as-grown coatings were studied by X-ray diffraction, Raman and energy-dispersive X-ray spectroscopy, as well as scanning electron microscopy. Cubic fluorite-type nanostructured ceria of leaf-like particles was synthesized. Thermal annealing (600°C, 1 h) was found to enhance ceria crystallinity.

  1. Ceria nanoclusters on graphene/Ru(0001): A new model catalyst system

    NASA Astrophysics Data System (ADS)

    Novotny, Z.; Netzer, F. P.; Dohnálek, Z.

    2016-10-01

    The growth of ceria nanoclusters on single-layer graphene on Ru(0001) has been examined, with a view towards fabricating a stable system for model catalysis studies. The surface morphology and cluster distribution as a function of oxide coverage and substrate temperature has been monitored by scanning tunneling microscopy (STM), whereas the chemical composition of the cluster deposits has been determined by Auger electron spectroscopy (AES). The ceria nanoparticles are of the CeO2(111)-type and are anchored at the intrinsic defects of the graphene surface, resulting in a variation of the cluster densities across the macroscopic sample surface. The ceria clusters on graphene display a remarkable stability against reduction in ultrahigh vacuum up to 900 K, but some sintering of clusters is observed for temperatures > 450 K. The evolution of the cluster size distribution suggests that the sintering proceeds via a Smoluchowski ripening mechanism, i.e. diffusion and aggregation of entire clusters.

  2. Separation of Minor Actinides from Lanthanides by Dithiophosphinic Acid Extractants

    SciTech Connect

    D. R. Peterman; M. R. Greenhalgh; R. D. Tillotson; J. R. Klaehn; M. K. Harrup; T. A. Luther; J. D. Law; L. M. Daniels

    2008-09-01

    The selective extraction of the minor actinides (Am(III) and Cm(III)) from the lanthanides is an important part of advanced reprocessing of spent nuclear fuel. This separation would allow the Am/Cm to be fabricated into targets and recycled to a reactor and the lanthanides to be dispositioned. This separation is difficult to accomplish due to the similarities in the chemical properties of the trivalent actinides and lanthanides. Research efforts at the Idaho National Laboratory have identified an innovative synthetic pathway yielding new regiospecific dithiophosphinic acid (DPAH) extractants. The synthesis provides DPAH derivatives that can address the issues concerning minor actinide separation and extractant stability. For this work, two new symmetric DPAH extractants have been prepared. The use of these extractants for the separation of minor actinides from lanthanides will be discussed.

  3. Lanthanides migration and immobilization in U-Zr nuclear fuels

    NASA Astrophysics Data System (ADS)

    Bozzolo, G.; Hofman, G. L.; Yacout, A. M.; Mosca, H. O.

    2012-06-01

    Redistribution of lanthanides fission products during irradiation and migration to the surface of U-Zr based metallic fuels is a concern due to their interaction with the cladding. The existing remedy for preventing this effect is the introduction of diffusion barriers on the cladding inner surface or by adding thermodynamically stable compound-forming elements to the fuel. Exploring this second option, in this work atomistic modeling with the Bozzolo-Ferrante-Smith (BFS) method for alloys is used to study the formation of lanthanide-rich precipitates in U-Zr fuel and the segregation patterns of all constituents to the surface. Surface energies for all elements were computed and, together with the underlying concepts of the computational methodology and large scale simulations, the migration of lanthanides to the surface region in U-Zr fuels is explained. The role of additions to the fuel such as In, Ga, and Tl for immobilization of lanthanides is discussed.

  4. Separation of actinides from lanthanides utilizing molten salt electrorefining

    SciTech Connect

    Grimmett, D.L.; Fusselman, S.P.; Roy, J.J.; Gay, R.L.; Krueger, C.L.; Storvick, T.S.; Inoue, T.; Hijikata, T.; Takahashi, N.

    1996-10-01

    TRUMP-S (TRansUranic Management through Pyropartitioning Separation) is a pyrochemical process being developed to separate actinides form fission products in nuclear waste. A key process step involving molten salt electrorefining to separate actinides from lanthanides has been studied on a laboratory scale. Electrorefining of U, Np, Pu, Am, and lanthanide mixtures from molten cadmium at 450 C to a solid cathode utilizing a molten chloride electrolyte resulted in > 99% removal of actinides from the molten cadmium and salt phases. Removal of the last few percent of actinides is accompanied by lowered cathodic current efficiency and some lanthanide codeposition. Actinide/lanthanide separation ratios on the cathode are ordered U > Np > Pu > Am and are consistent with predictions based on equilibrium potentials.

  5. Lanthanide ions as required cofactors for DNA catalysts.

    PubMed

    Dokukin, Victor; Silverman, Scott K

    2012-01-01

    We report that micromolar concentrations of lanthanide ions can be required cofactors for DNA-hydrolyzing deoxyribozymes. Previous work identified deoxyribozymes that simultaneously require both Zn(2+) and Mn(2+) to achieve DNA-catalyzed DNA hydrolysis (10(12) rate enhancement); a mutant of one such DNA catalyst requires only Zn(2+). Here we show that in vitro selection in the presence of 10 µM lanthanide ion (Ce(3+), Eu(3+), or Yb(3+)) along with 1 mM Zn(2+) leads to numerous DNA-hydrolyzing deoxyribozymes that strictly require the lanthanide ion as well as Zn(2+) for catalytic activity. These DNA catalysts have a range of lanthanide dependences, including some deoxyribozymes that strongly favor one particular lanthanide ion (e.g., Ce(3+) > Eu(3+) > Yb(3+)) and others that function well with more than one lanthanide ion. Intriguingly, two of the Yb(3+)-dependent deoxyribozymes function well with Yb(3+) alone (K(d,app) ~10 µM, in the absence of Zn(2+)) and have little or no activity with Eu(3+) or Ce(3+). In contrast to these selection outcomes when lanthanide ions were present, new selections with Zn(2+) or Mn(2+) alone, or Zn(2+) with Mg(2+)/Ca(2+), led primarily to deoxyribozymes that cleave DNA by deglycosylation and β-elimination rather than by hydrolysis, including several instances of depyrimidination. We conclude that lanthanide ions warrant closer attention as cofactors when identifying new nucleic acid catalysts, especially for applications in which high concentrations of polyvalent metal ion cofactors are undesirable.

  6. Lighting up cells with lanthanide self-assembled helicates

    PubMed Central

    Bünzli, Jean-Claude G.

    2013-01-01

    Lanthanide bioprobes and bioconjugates are ideal luminescent stains in view of their low propensity to photobleaching, sharp emission lines and long excited state lifetimes permitting time-resolved detection for enhanced sensitivity. We show here how the interplay between physical, chemical and biochemical properties allied to microfluidics engineering leads to self-assembled dinuclear lanthanide luminescent probes illuminating live cells and selectively detecting biomarkers expressed by cancerous human breast cells. PMID:24511387

  7. Influence of Ceria on the NOx Storage/Reduction Behavior of Lean NOx Trap Catalysts

    SciTech Connect

    Ji, Yaying; Choi, Jae-Soon; Toops, Todd J; Crocker, Dr. Mark; Naseri, Mojghan

    2008-01-01

    The effect of La2O3-stabilized ceria incorporation on the functioning of fully formulated lean NOx trap catalysts was investigated. Monolithic catalysts were prepared, corresponding to loadings of 0, 50 and 100 g CeO2/L, together with a catalyst containing 100 g/L of ceria-zirconia (Ce0.7Zr0.3O2). Loadings of the other main components (Pt, Rh and BaO) were held constant. Catalyst evaluation was performed on a bench flow reactor under simulated diesel exhaust conditions, employing NOx storage/reduction cycles. NOx storage efficiency in the temperature range 150-350 C was observed to increase with ceria loading, resulting in higher NOx conversion levels. At 150 C, high rich phase NOx slip was observed for all of the catalysts, resulting from an imbalance in the rates of nitrate decomposition and NOx reduction. Optimal NOx conversion was obtained in the range 250-350 C for all the catalysts, while at 450 C high rich phase NOx slip from the most highly loaded ceria-containing catalyst resulted in lower NOx conversion than for the ceria-free formulation. N2O was the major NOx reduction product at 150 C over all of the catalysts, although low NOx conversion levels limited the N2O yield. At higher temperatures N2 was the main product of NOx reduction, although NH3 formation was also observed. Selectivity to NH3 decreased with increasing ceria loading, indicating that NH3 is consumed by reaction with stored oxygen in the rear of the catalyst.

  8. A model of oxygen transport in Pt/ceria catalysts from isotope exchange

    SciTech Connect

    Holmgren, A.; Andersson, B.; Duprez, D.

    1999-03-10

    From isotope oxygen exchange reactions and simulations of these experiments, the important steps in oxygen transport in Pt/ceria were distinguished and their rates were estimated. A Pt/alumina sample was also experimentally investigated for comparison. Oxygen surface diffusion as well as oxygen spillover from Pt to ceria was found to be fast in comparison with adsorption/desorption of oxygen on the metal and oxygen bulk diffusion. The exchange rate was found to be higher on a very-low-Pt-dispersion sample than on a high-dispersion sample, which in the model was explained by the different adsorption properties of oxygen.

  9. Growth of semiconducting single-walled carbon nanotubes by using ceria as catalyst supports.

    PubMed

    Qin, Xiaojun; Peng, Fei; Yang, Feng; He, Xiaohui; Huang, Huixin; Luo, Da; Yang, Juan; Wang, Sheng; Liu, Haichao; Peng, Lianmao; Li, Yan

    2014-02-12

    The growth of semiconducting single-walled carbon nanotubes (s-SWNTs) on flat substrates is essential for the application of SWNTs in electronic and optoelectronic devices. We developed a flexible strategy to selectively grow s-SWNTs on silicon substrates using a ceria-supported iron or cobalt catalysts. Ceria, which stores active oxygen, plays a crucial role in the selective growth process by inhibiting the formation of metallic SWNTs via oxidation. The so-produced ultralong s-SWNT arrays are immediately ready for building field effect transistors. PMID:24392872

  10. Calibration beads containing luminescent lanthanide ion complexes

    NASA Astrophysics Data System (ADS)

    Leif, Robert C.; Jin, Dayong; Piper, James; Vallarino, Lidia M.; Williams, John W.; Yang, Sean; Zucker, Robert M.

    2008-02-01

    The reliability of lanthanide luminescence measurements, by both flow cytometry and digital microscopy, will be enhanced by the availability of narrow-band emitting lanthanide calibration beads. These beads can also be used to characterize spectrographic instruments, including microscopes. Methods: 0.5, 3, and 5 micron (µm) beads containing a luminescent europium-complex were manufactured and the luminescence distribution of the 5 µm beads was measured with a time-delayed luminescence flow cytometer and a timedelayed digital microscope. The distribution of the luminescence intensity from the europium-complex in individual beads was determined on optical sections by confocal microscopy. The emission spectra of the beads under UV excitation were determined with a PARISS® spectrophotometer. The kinetics of the luminescence bleaching caused by UV irradiation were measured under LED excitation with a fluorescence microscope. Results: The kinetics of UV bleaching were very similar for the 0.5, 3, and 5 µm beads. Emission peaks were found at 592, 616, and 685 nanometers (nm). The width of the principal peak at half-maximum (616 nm) was 9.9 nm. The luminescence lifetimes in water and in air were 340 and 460 microseconds (µs), respectively. The distribution of the europium- complex in the beads was homogeneous. Conclusions: The 5 µm beads can be used for spectral calibration of microscopes equipped with a spectrograph, as test particles for time-delayed luminescence flow cytometers, and possibly as labels for macromolecules and cells.

  11. Mesoporous NiO-samaria doped ceria for low-temperature solid oxide fuel cells.

    PubMed

    Kim, Jin-Yeop; Kim, Ji Hyeon; Choi, Hyung Wook; Kim, Kyung Hwan; Park, Sang Joon

    2014-08-01

    In order to prepare anode material for low-temperature solid oxide fuel cells (SOFCs), the mesoporous NiO-SDC was synthesized using a cationic surfactant (cetyltrimethyl-ammonium bromide; CTAB) for obtaining wide triple-phase boundary (TPB). In addition, Ni-SDC anode-supported SOFC single cells with YSZ electrolyte and LSM cathode were fabricated and the performance of single cells was evaluated at 600 °C. The microstructure of NiO-SDC was characterized by XRD, EDX, SEM, and BET, and the results showed that the mesoporous NiO-SDC with 10 nm pores could be obtained. It was found that the surface area and the electrical performance were strongly influenced by the Ni content in Ni-SDC cermets. After calcined at 600 °C, the surface area of NiO-SDC was between 90-117 m2/g at 35-45 Ni wt%, which was sufficiently high for providing large TPB in SOFC anode. The optimum Ni content for cell performance was around 45 wt% and the corresponding MPD was 0.36 W/cm2. Indeed, the mesoporous NiO-SDC cermet may be of interest for use as an anode for low-temperature SOFCs.

  12. Oxygen vacancy ordering within anion-deficient Ceria

    SciTech Connect

    Hull, S.; Norberg, S.T.; Ahmed, I.; Eriksson, S.G.; Marrocchelli, D.; Madden, P.A.

    2009-10-15

    The structural properties of anion deficient ceria, CeO{sub 2-{delta}}, have been studied as a function of oxygen partial pressure, p(O{sub 2}), over the range 0>=log{sub 10p}(O{sub 2})>=-18.9 at 1273(2) K using the neutron powder diffraction technique. Rietveld refinement of the diffraction data collected on decreasing p(O{sub 2}) showed increases in the cubic lattice parameter, a, the oxygen nonstoichiometry, delta, and the isotropic thermal vibration parameters, u{sub Ce} and u{sub O}, starting at log{sub 10p}(O{sub 2}){approx}-11. The increases are continuous, but show a distinct kink at log{sub 10p}(O{sub 2}){approx}-14.5. Analysis of the total scattering (Bragg plus diffuse components) using reverse Monte Carlo (RMC) modelling indicates that the O{sup 2-} vacancies preferentially align as pairs in the <111> cubic directions as the degree of nonstoichiometry increases. This behaviour is discussed with reference to the chemical crystallography of the CeO{sub 2}-Ce{sub 2}O{sub 3} system at ambient temperature and, in particular, to the nature of the long-range ordering of O{sup 2-} vacancies within the crystal structure of Ce{sub 7}O{sub 12}. - Graphical abstract: Partial radial distribution function for oxygen vacancies within CeO{sub 1.710} at 1273 K (solid line) showing the increased tendency for local ordering in <111> directions compared to a random distribution (dashed line).

  13. Lanthanide accumulation in the periplasmic space of Escherichia coli B.

    PubMed

    Bayer, M E; Bayer, M H

    1991-01-01

    Treatment of growing Escherichia coli B with lanthanide ions [lanthanum(III), terbium(III), and europium(III)] and subsequent aldehyde-OsO4 fixation caused areas of high contrast to appear within the periplasm (the space between inner and outer membrane of the cell envelope). X-ray microanalysis of ultrathin sections of Epon-embedded or acrylic resin-embedded cells revealed the presence of the lanthanide and of phosphorus in the areas, whose contrast greatly exceeded that of other stained structures. Comparatively small amounts of the lanthanide were also present in the outer membrane and in the cytoplasm. The distribution of the periplasmic areas of high contrast was found to be random and not clustered at areas of current or future septum formation. Irregular cell shapes were observed after lanthanide treatment before onset of fixation. In contrast to glutaraldehyde-OsO4 fixation, glutaraldehyde used as the sole fixer caused a scattered distribution of the lanthanide. Cryofixation (slam-freezing) and freeze substitution revealed a lanthanum stain at both the periplasm and the outer part of the outer membrane. Deenergization of the cell membrane by either phage T4 or carbonyl cyanide m-chlorophenylhydrazone abolished the metal accumulation. Furthermore, addition of excess calcium, administered together with the lanthanide solution, diminished the quantity and size of areas of high contrast. Cells grown in media of high NaCl concentration revealed strongly stained areas of periplasmic precipitates, whereas cells grown under low-salt conditions showed very few high-contrast patches in the periplasm. Terbium treatment (during fixation) enhanced the visibility of the sites of inner-outer membrane contact (the membrane adhesion sites) in plasmolized cells, possibly as the result of an accumulation of the metal at the adhesion domains. The data suggest a rapid interaction of the lanthanides with components of the cell envelope, the periplasm, and the energized inner

  14. Embedded ceria nanoparticles in gel improve electrophoretic separation: a preliminary demonstration.

    PubMed

    Zarei, Mohammad; Ahmadzadeh, Hossein; Goharshadi, Elaheh K

    2015-07-01

    Slab gel electrophoresis is still the gold standard method for the separation of biomolecules such as proteins and DNA with advantages such as simplicity, affordability, and high throughput, but it suffers from inadequate separation speed and resolution. Single capillary gel electrophoresis, on the other hand, offers faster separation time and improved resolution at the expense of higher cost and loss of high throughput capability. The high surface to volume ratio of the capillary causes improved heat dissipation leading to a reduced Joule heating and a higher resolution. Here, for the first time, we show the use of dispersed ceria nanoparticles (NPs) to improve the resolution and speed of protein separation in slab gel electrophoresis. We measured the rheological parameters of separation medium in order to find a meaningful relationship between viscosity changes, Joule heating, and band broadening. The results showed that ceria NPs decrease the viscosity of polyacrylamide gel. By loading 0.03% (w/v) ceria NPs into polyacrylamide gel at 25 °C, the viscosity decreased 22% and the thermal conductivity increased to 81%, which resulted in 35% reduction in Joule heating and 47% increase in resolution. This work is a cross disciplinary of theoretical physical chemistry for thermal conductivity and rheological measurements of PA and ceria suspensions and application in slab gel electrophoresis. We report here, for the first time, that embedded NPs in PA gel could potentially interface high throughput capability of slab gel electrophoresis with high separation speed of single capillary electrophoresis. PMID:25948088

  15. 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.

  16. Release of ceria nanoparticles grafted on hybrid organic-inorganic films for biomedical application.

    PubMed

    Pinna, Alessandra; Figus, Cristiana; Lasio, Barbara; Piccinini, Massimo; Malfatti, Luca; Innocenzi, Plinio

    2012-08-01

    The controlled release of nanoparticles from a hybrid organic-inorganic surface allows for developing several applications based on a slow delivery of oxygen scavengers into specific environments. We have successfully grafted ceria nanoparticles on a hybrid film surface and tested their release in a buffer solution; the tests have shown that the particles are continuously delivered within a time scale of hours. The hybrid film has been synthesized using 3-glycidoxypropyltrimethoxysilane as precursor alkoxide; the synthesis has been performed in highly basic conditions to control the polycondensation reactions of both organic and inorganic networks via controlled aging of the solution. Only films prepared from aged solutions are able to graft ceria nanoparticles on their surface. The ceria nanoparticles have been characterized by X-ray diffraction, transmission electron microscopy and UV-vis spectroscopy, the hybrid films have been analyzed by Fourier transform infrared spectroscopy, atomic force microscopy and Raman spectroscopy. Raman imaging has been used for the release test. The hybrid film-ceria nanoparticles system fulfils the requirements of optical transparency and stability in buffer solutions which are necessary for biomedical applications.

  17. Formation of N3(-) during interaction of NO with reduced ceria.

    PubMed

    Mihaylov, Mihail Y; Ivanova, Elena Z; Aleksandrov, Hristiyan A; St Petkov, Petko; Vayssilov, Georgi N; Hadjiivanov, Konstantin I

    2015-04-01

    We show that the first stages of interaction between NO and reduced ceria comprise the formation of azides, N3(-), with simultaneous oxidation of Ce(3+) to Ce(4+). This finding imposes revision on some current views of catalytic NO conversion and may contribute to design of new deNOx materials and processes. PMID:25714684

  18. Interaction of Zr with oxidized and partially reduced ceria thin films

    NASA Astrophysics Data System (ADS)

    Wang, Weijia; Hu, Shanwei; Han, Yong; Pan, Xiao; Xu, Qian; Zhu, Junfa

    2016-11-01

    The growth and electronic properties of Zr on the ceria thin films were studied by X-ray photoelectron spectroscopy, low energy electron diffraction (LEED), scanning tunneling microscopy (STM) and work function measurements. Metallic zirconium was vapor-deposited on the well-ordered fully oxidized CeO2(111) and partially reduced CeO2-x(111) (0 < x < 0.5) thin films, which were epitaxially grown on a Ru(0001) substrate, under ultrahigh vacuum (UHV) conditions. The results show that the deposition of Zr on both ceria surfaces leads to electron transfer from Zr to ceria, accompanied by partial reduction of Ce from Ce4 + to Ce3 + states and oxidation of metallic Zr to Zr4 +. Moreover, with increasing the Zr coverage, the reduction degree of ceria films increases and eventually only Ce3 + is observed at a high coverage of Zr. The STM results suggest that Zr grows two-dimensionally (2D) on the CeO2(111) thin film at low coverages due to the strong interaction between Zr and CeO2(111).

  19. Greener iodination of arenes using sulphated ceria-zirconia catalysts in polyethylene glycol

    EPA Science Inventory

    An environmentally benign method for the selective monoiodination of diverse aromatic compounds has been developed using reusable sulphated ceria-zirconia under mild conditions. The protocol provides moderate to good yields of aryl iodides in PEG-200 as a greener solvent. The cat...

  20. Embedded Ceria Nanoparticles in Crosslinked PVA Electrospun Nanofibers as Optical Sensors for Radicals.

    PubMed

    Shehata, Nader; Samir, Effat; Gaballah, Soha; Hamed, Aya; Elrasheedy, Asmaa

    2016-01-01

    This work presents a new nanocomposite of cerium oxide (ceria) nanoparticles embedded in electrospun PVA nanofibers for optical sensing of radicals in solutions. Our ceria nanoparticles are synthesized to have O-vacancies which are the receptors for the radicals extracted from peroxide in water solution. Ceria nanoparticles are embedded insitu in PVA solution and then formed as nanofibers using an electrospinning technique. The formed nanocomposite emits visible fluorescent emissions under 430 nm excitation, due to the active ceria nanoparticles with fluorescent Ce(3+) ionization states. When the formed nanocomposite is in contact with peroxide solution, the fluorescence emission intensity peak has been found to be reduced with increasing concentration of peroxide or the corresponding radicals through a fluorescence quenching mechanism. The fluorescence intensity peak is found to be reduced to more than 30% of its original value at a peroxide weight concentration up to 27%. This work could be helpful in further applications of radicals sensing using a solid mat through biomedical and environmental monitoring applications. PMID:27571083

  1. Embedded Ceria Nanoparticles in Crosslinked PVA Electrospun Nanofibers as Optical Sensors for Radicals

    PubMed Central

    Shehata, Nader; Samir, Effat; Gaballah, Soha; Hamed, Aya; Elrasheedy, Asmaa

    2016-01-01

    This work presents a new nanocomposite of cerium oxide (ceria) nanoparticles embedded in electrospun PVA nanofibers for optical sensing of radicals in solutions. Our ceria nanoparticles are synthesized to have O-vacancies which are the receptors for the radicals extracted from peroxide in water solution. Ceria nanoparticles are embedded insitu in PVA solution and then formed as nanofibers using an electrospinning technique. The formed nanocomposite emits visible fluorescent emissions under 430 nm excitation, due to the active ceria nanoparticles with fluorescent Ce3+ ionization states. When the formed nanocomposite is in contact with peroxide solution, the fluorescence emission intensity peak has been found to be reduced with increasing concentration of peroxide or the corresponding radicals through a fluorescence quenching mechanism. The fluorescence intensity peak is found to be reduced to more than 30% of its original value at a peroxide weight concentration up to 27%. This work could be helpful in further applications of radicals sensing using a solid mat through biomedical and environmental monitoring applications. PMID:27571083

  2. Gold nanoparticles supported in zirconia-ceria mesoporous thin films: a highly active reusable heterogeneous nanocatalyst.

    PubMed

    Violi, Ianina L; Zelcer, Andrés; Bruno, Mariano M; Luca, Vittorio; Soler-Illia, Galo J A A

    2015-01-21

    Gold nanoparticles (NP) trapped in the mesopores of mixed zirconia-ceria thin films are prepared in a straightforward and reproducible way. The films exhibit enhanced stability and excellent catalytic activity in nitro-group reduction by borohydride and electrocatalytic activity in CO and ethanol oxidation and oxygen reduction.

  3. A Simple Empirical Analysis of the Enthalpies of Formation of Lanthanide Halides and Oxides.

    ERIC Educational Resources Information Center

    Smith, Derek W.

    1986-01-01

    Proposes a simple and general method whereby the lattice energies of lanthanide(II) and (IV) compounds are derived directly from those found experimentally for the corresponding lanthanide(III) compounds. The method is applicable to all lanthanide halides and oxides and involves calculations which can be easily and quickly performed by students.…

  4. Ceria catalyst for inert-substrate-supported tubular solid oxide fuel cells running on methane fuel

    NASA Astrophysics Data System (ADS)

    Zhao, Kai; Kim, Bok-Hee; Du, Yanhai; Xu, Qing; Ahn, Byung-Guk

    2016-05-01

    A ceria catalyst is applied to an inert-substrate supported tubular single cell for direct operation on methane fuel. The tubular single cell comprises a porous yttria-stabilized zirconia (YSZ) supporter, a Ni-Ce0.8Sm0.2O1.9 anode, a YSZ/Ce0.8Sm0.2O1.9 bi-layer electrolyte, and a La0.6Sr0.4Co0.2Fe0.8O3-δ cathode. The ceria catalyst is incorporated into the porous YSZ supporter layer by a cerium nitrate impregnation. The effects of ceria on the microstructure and electrochemical performance of the tubular single cell are investigated with respect to the number of impregnations. The optimum number of impregnations is determined to be four based on the maximum power density and polarization property of the tubular single cell in hydrogen and methane fuels. At 700 °C, the tubular single cell shows similar maximum power densities of ∼260 mW cm-2 in hydrogen and methane fuels, respectively. Moreover, the ceria catalyst significantly improves the performance stability of the cell running on methane fuel. At a current density of 350 mA cm-2, the single cell shows a low degradation rate of 2.5 mV h-1 during the 13 h test in methane fuel. These results suggest the feasibility of applying the ceria catalyst to the inert-substrate supported tubular single cell for direct operation on methane fuel.

  5. Ceria catalyst for inert-substrate-supported tubular solid oxide fuel cells running on methane fuel

    NASA Astrophysics Data System (ADS)

    Zhao, Kai; Kim, Bok-Hee; Du, Yanhai; Xu, Qing; Ahn, Byung-Guk

    2016-05-01

    A ceria catalyst is applied to an inert-substrate supported tubular single cell for direct operation on methane fuel. The tubular single cell comprises a porous yttria-stabilized zirconia (YSZ) supporter, a Ni-Ce0.8Sm0.2O1.9 anode, a YSZ/Ce0.8Sm0.2O1.9 bi-layer electrolyte, and a La0.6Sr0.4Co0.2Fe0.8O3-δ cathode. The ceria catalyst is incorporated into the porous YSZ supporter layer by a cerium nitrate impregnation. The effects of ceria on the microstructure and electrochemical performance of the tubular single cell are investigated with respect to the number of impregnations. The optimum number of impregnations is determined to be four based on the maximum power density and polarization property of the tubular single cell in hydrogen and methane fuels. At 700 °C, the tubular single cell shows similar maximum power densities of ˜260 mW cm-2 in hydrogen and methane fuels, respectively. Moreover, the ceria catalyst significantly improves the performance stability of the cell running on methane fuel. At a current density of 350 mA cm-2, the single cell shows a low degradation rate of 2.5 mV h-1 during the 13 h test in methane fuel. These results suggest the feasibility of applying the ceria catalyst to the inert-substrate supported tubular single cell for direct operation on methane fuel.

  6. Development of the Actinide-Lanthanide Separation (ALSEP) Process

    SciTech Connect

    Lumetta, Gregg J.; Carter, Jennifer C.; Niver, Cynthia M.; Gelis, Artem V.

    2014-09-30

    Separating the minor actinide elements (Am and Cm) from acidic high-level raffinates arising from the reprocessing of irradiated nuclear fuel is an important step in closing the nuclear fuel cycle. Most proposed approaches to this problem involve two solvent extraction steps: 1) co-extraction of the trivalent lanthanides and actinides, followed by 2) separation of the actinides from the lanthanides. The objective of our work is to develop a single solvent-extraction process for isolating the minor actinide elements. We report here a solvent containing N,N,N',N'-tetra(2 ethylhexyl)diglycolamide (T2EHDGA) combined with 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]) that can be used to separate the minor actinides in a single solvent-extraction process. T2EHDGA serves to co-extract the trivalent actinide and lanthanide ions from nitric acid solution. Switching the aqueous phase chemistry to a citrate buffered solution of N-(2-hydroxyethyl)ethylenediamine-N,N',N'-triacetic acid at pH 2.5 to 4 results in selective transfer of the actinides to the aqueous phase, thus affecting separation of the actinides from the lanthanides. Separation factors between the lanthanides and actinides are approximately 20 in the pH range of 3 to 4, and the distribution ratios are not highly dependent on the pH in this system.

  7. Luminescent chiral lanthanide(III) complexes as potential molecular probes

    PubMed Central

    Muller, Gilles

    2009-01-01

    This perspective gives an introduction into the design of luminescent lanthanide(III)-containing complexes possessing chiral properties and used to probe biological materials. The first part briefly describes general principles, focusing on the optical aspect (i.e. lanthanide luminescence, sensitization processes) of the most emissive trivalent lanthanide ions, europium and terbium, incorporated into molecular luminescent edifices. This is followed by a short discussion on the importance of chirality in the biological and pharmaceutical fields. The second part is devoted to the assessment of the chiroptical spectroscopic tools available (typically circular dichroism and circularly polarized luminescence) and the strategies used to introduce a chiral feature into luminescent lanthanide(III) complexes (chiral structure resulting from a chiral arrangement of the ligand molecules surrounding the luminescent center or presence of chiral centers in the ligand molecules). Finally, the last part illustrates these fundamental principles with recent selected examples of such chiral luminescent lanthanide-based compounds used as potential probes of biomolecular substrates. PMID:19885510

  8. 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

  9. A perfectly stoichiometric and flat CeO2(111) surface on a bulk-like ceria film

    PubMed Central

    Barth, C.; Laffon, C.; Olbrich, R.; Ranguis, A.; Parent, Ph.; Reichling, M.

    2016-01-01

    In surface science and model catalysis, cerium oxide (ceria) is mostly grown as an ultra-thin film on a metal substrate in the ultra-high vacuum to understand fundamental mechanisms involved in diverse surface chemistry processes. However, such ultra-thin films do not have the contribution of a bulk ceria underneath, which is currently discussed to have a high impact on in particular surface redox processes. Here, we present a fully oxidized ceria thick film (180 nm) with a perfectly stoichiometric CeO2(111) surface exhibiting exceptionally large, atomically flat terraces. The film is well-suited for ceria model studies as well as a perfect substitute for CeO2 bulk material. PMID:26879800

  10. Dynamic structural evolution of supported palladium–ceria core–shell catalysts revealed by in situ electron microscopy

    PubMed Central

    Zhang, Shuyi; Chen, Chen; Cargnello, Matteo; Fornasiero, Paolo; Gorte, Raymond J.; Graham, George W.; Pan, Xiaoqing

    2015-01-01

    The exceptional activity for methane combustion of modular palladium–ceria core–shell subunits on silicon-functionalized alumina that was recently reported has created renewed interest in the potential of core–shell structures as catalysts. Here we report on our use of advanced ex situ and in situ electron microscopy with atomic resolution to show that the modular palladium–ceria core–shell subunits undergo structural evolution over a wide temperature range. In situ observations performed in an atmospheric gas cell within this temperature range provide real-time evidence that the palladium and ceria nanoparticle constituents of the palladium–ceria core–shell participate in a dynamical process that leads to the formation of an unanticipated structure comprised of an intimate mixture of palladium, cerium, silicon and oxygen, with very high dispersion. This finding may open new perspectives about the origin of the activity of this catalyst. PMID:26160065

  11. Mixed lanthanide oxide nanoparticles as dual imaging agent in biomedicine

    NASA Astrophysics Data System (ADS)

    Xu, Wenlong; Bony, Badrul Alam; Kim, Cho Rong; Baeck, Jong Su; Chang, Yongmin; Bae, Ji Eun; Chae, Kwon Seok; Kim, Tae Jeong; Lee, Gang Ho

    2013-11-01

    There is no doubt that the molecular imaging is an extremely important technique in diagnosing diseases. Dual imaging is emerging as a step forward in molecular imaging technique because it can provide us with more information useful for diagnosing diseases than single imaging. Therefore, diverse dual imaging modalities should be developed. Molecular imaging generally relies on imaging agents. Mixed lanthanide oxide nanoparticles could be valuable materials for dual magnetic resonance imaging (MRI)-fluorescent imaging (FI) because they have both excellent and diverse magnetic and fluorescent properties useful for dual MRI-FI, depending on lanthanide ions used. Since they are mixed nanoparticles, they are compact, robust, and stable, which is extremely useful for biomedical applications. They can be also easily synthesized with facile composition control. In this study, we explored three systems of ultrasmall mixed lanthanide (Dy/Eu, Ho/Eu, and Ho/Tb) oxide nanoparticles to demonstrate their usefulness as dual T2 MRI-FI agents.

  12. Ultrasensitive DNAzyme beacon for lanthanides and metal speciation.

    PubMed

    Huang, Po-Jung Jimmy; Lin, Jenny; Cao, Jing; Vazin, Mahsa; Liu, Juewen

    2014-02-01

    Metal-ion detection and speciation analysis is crucial for environmental monitoring. Despite the importance of lanthanides, few sensors are available for their detection. DNAzymes have been previously used to detect divalent metals, while no analytical work was carried out for trivalent and tetravalent ions. Herein, in vitro selection was performed using a Ce(4+) salt as the target metal, and a new DNAzyme (named Ce13) with a bulged hairpin structure was isolated and characterized. Interestingly, Ce13 has almost no activity with Ce(4+) but is highly active with all trivalent lanthanides and Y(3+), serving as a general probe for rare earth metals (omitting Sc). A DNAzyme beacon was engineered detecting down to 1.7 nM Ce(3+) (240 parts per trillion), and other lanthanides showed similar sensitivity. The feasibility of metal speciation analysis was demonstrated by measuring the reduction of Ce(4+) to Ce(3+).

  13. Magnetic field alignable domains in phospholipid vesicle membranes containing lanthanides.

    PubMed

    Beck, Paul; Liebi, Marianne; Kohlbrecher, Joachim; Ishikawa, Takashi; Rüegger, Heinz; Zepik, Helmut; Fischer, Peter; Walde, Peter; Windhab, Erich

    2010-01-14

    Magnetic fields were applied as a structuring force on phospholipid-based vesicular systems, using paramagnetic lanthanide ions as magnetic handles anchored to the vesicle membrane. Different vesicle formulations were investigated using small angle neutron scattering (SANS) in a magnetic field of up to 8 T, cryo-transmission electron microscopy (cryo-TEM), (31)P NMR spectroscopy, dynamic light scattering (DLS), and permeability measurements with a fluorescent water-soluble marker (calcein). The investigated vesicle formulations consisted usually of 80 mol % of the phospholipid 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) and 20 mol % of a chelator lipid (DMPE-DTPA; 1,2-dimyristoyl-sn-glycero-3-phosphoethanolamine-diethylenetriaminepentaacetate) with complexed lanthanide ions (Tm(3+), Dy(3+), or La(3+)), and the total lipid concentration was 15 mM. Vesicles containing the paramagnetic lanthanide Tm(3+) or Dy(3+) exhibited a temperature-dependent response to magnetic fields, which can be explained by considering the formation of lipid domains, which upon reaching a critical size become alignable in a magnetic field. The features of this "magnetic field alignable domain model" are as follows: with decreasing temperature (from 30 to 2.5 degrees C) solid domains, consisting mainly of the higher melting phospholipid (DMPE-DTPA.lanthanide), begin to form and grow in size. The domains assemble the large magnetic moments conferred by the lanthanides and orient in magnetic fields. The direction of alignment depends on the type of lanthanide used. The domains orient with their normal parallel to the magnetic field with thulium (Tm(3+)) and perpendicular with dysprosium (Dy(3+)). No magnetic field alignable domains were observed if DMPE-DTPA is replaced either by POPE-DTPA (1-palmitoyl-2-oleoyl-sn-glycero-3-phosphoethanolamine-diethylenetriamine-pentaacetate) or by DMPC (1,2-dimyristoyl-sn-glycero-3-phosphocholine).

  14. Ceria coated Ni as anodes for direct utilization of methane in low-temperature solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Zhu, Wei; Xia, Changrong; Fan, Jue; Peng, Ranran; Meng, Guangyao

    A new type of anode, a Ni framework coated with Sm-doped ceria (SDC), was developed for direct utilization of methane fuel in low-temperature solid oxide fuel cells (SOFCs) with thin-film SDC electrolytes. The coated SDC was prepared with an ion impregnating method and the electrolyte films were fabricated with a co-pressing and co-firing technique. The impregnating process produced an ideal anode microstructure where nickel particles were effectively connected and uniformly covered with nanosized SDC. This anode microstructure was believed to enlarge the triple-phase boundaries and therefore enhance the anode performance. The cell performance was much higher than that of a conventional fuel cell with a Ni-SDC composite anode. In addition, the performance increased with impregnated SDC loading up to a maximum at 20 mg cm -2, indicating that the coated SDC is the contributing factor for the enhanced fuel cell performance. Power density as high as 571 and 353 mW cm -2 were obtained at 600 °C when humidified hydrogen and methane were used as fuels, respectively. The stability of the cell also increased with the SDC loading. No significant degradation was observed for anodes coated with 20 and 25 mg cm -2 SDC. This verifies that the coated SDC electrodes are very effective in suppressing catalytic carbon formation by blocking methane from approaching the Ni, which is catalytically active towards methane pyrolysis. The high performance of this anode shows high promise in the developing field of direct hydrocarbon SOFCs.

  15. Method for providing oxygen ion vacancies in lanthanide oxides

    DOEpatents

    Kay, D. Alan R.; Wilson, William G.

    1989-12-05

    A method for desulfurization of fuel gases resulting from the incomplete combustion of sulfur containing hydrocarbons whereby the gases are treated with lanthanide oxides containing large numbers of oxygen-ion vacancies providing ionic porosity which enhances the ability of the lanthanide oxides to react more rapidly and completely with the sulfur in the fuel gases whereby the sulfur in such gases is reduced to low levels suitable for fuels for firing into boilers of power plants generating electricity with steam turbine driven generators, gas turbines, fuel cells and precursors for liquid fuels such as methanol and the like.

  16. Plasma mass filtering for separation of actinides from lanthanides

    NASA Astrophysics Data System (ADS)

    Gueroult, R.; Fisch, N. J.

    2014-06-01

    Separating lanthanides from actinides is a key process in reprocessing nuclear spent fuel. Plasma mass filters, which operate on dissociated elements, offer conceptual advantages for such a task as compared with conventional chemical methods. The capabilities of a specific plasma mass filter concept, called the magnetic centrifugal mass filter, are analyzed within this particular context. Numerical simulations indicate separation of americium ions from a mixture of lanthanides ions for plasma densities of the order of 1012 cm-3, and ion temperatures of about 10 eV. In light of collision considerations, separating small fractions of heavy elements from a larger volume of lighter ones is shown to enhance the separation capabilities.

  17. Method for extracting lanthanides and actinides from acid solutions

    DOEpatents

    Horwitz, E. Philip; Kalina, Dale G.; Kaplan, Louis; Mason, George W.

    1985-01-01

    A process for the recovery of actinide and lanthanide values from aqueous acidic solutions with an organic extractant having the formula: ##STR1## where .phi. is phenyl, R.sup.1 is a straight or branched alkyl or alkoxyalkyl containing from 6 to 12 carbon atoms and R.sup.2 is an alkyl containing from 3 to 6 carbon atoms. The process is suitable for the separation of actinide and lanthanide values from fission product values found together in high level nuclear reprocessing waste solutions.

  18. Applications of DFT to Lanthanides and Precious Metal Complexes

    NASA Astrophysics Data System (ADS)

    Balboa, Alex; Hurley, Margaret; Jenkins, Amanda; None Collaboration; None Collaboration

    2014-03-01

    Density functional theory is widely used for computational characterization of novel materials. While study of materials containing the lighter elements is commonplace, the application of these methods to the bottom of the periodic table, including the lanthanides and the heavier precious metals such as Osmium, requires careful validation. Here we present results of recent quantum mechanical studies to characterize Lanthanide/Graphene Materials and assess the suitability of DFT for these systems. Additionally, we will present recent work on similar application of DFT to characterize Os bipridine complexes.

  19. SOLVENT EXTRACTION PROCESS FOR SEPARATING ACTINIDE AND LANTHANIDE METAL VALUES

    DOEpatents

    Hildebrandt, R.A.; Hyman, H.H.; Vogler, S.

    1962-08-14

    A process of countercurrently extracting an aqueous mineral acid feed solution for the separation of actinides from lanthanides dissolved therern is described. The feed solution is made acid-defrcient with alkali metal hydroxide prior to.contact with acid extractant; during extraction, however, acid is transferred from organic to aqueous solution and the aqueous solution gradually becomes acid. The acid-deficient phase ' of the process promotes the extraction of the actinides, while the latter acid phase'' of the process improves retention of the lanthanides in the aqueous solution. This provides for an improved separation. (AEC)

  20. Thermodynamical properties of liquid lanthanides-A variational approach

    SciTech Connect

    Patel, H. P.; Thakor, P. B.; Sonvane, Y. A.

    2015-06-24

    Thermodynamical properties like Entropy (S), Internal energy (E) and Helmholtz free energy (F) of liquid lanthanides using a variation principle based on the Gibbs-Bogoliubuv (GB) inequality with Percus Yevick hard sphere reference system have been reported in the present investigation. To describe electron-ion interaction we have used our newly constructed parameter free model potential along with Sarkar et al. local field correction function. Lastly, we conclude that our newly constructed model potential is capable to explain the thermodynamical properties of liquid lanthanides.

  1. Airplane dopes and doping

    NASA Technical Reports Server (NTRS)

    Smith, W H

    1919-01-01

    Cellulose acetate and cellulose nitrate are the important constituents of airplane dopes in use at the present time, but planes were treated with other materials in the experimental stages of flying. The above compounds belong to the class of colloids and are of value because they produce a shrinking action on the fabric when drying out of solution, rendering it drum tight. Other colloids possessing the same property have been proposed and tried. In the first stages of the development of dope, however, shrinkage was not considered. The fabric was treated merely to render it waterproof. The first airplanes constructed were covered with cotton fabric stretched as tightly as possible over the winds, fuselage, etc., and flying was possible only in fine weather. The necessity of an airplane which would fly under all weather conditions at once became apparent. Then followed experiments with rubberized fabrics, fabrics treated with glue rendered insoluble by formaldehyde or bichromate, fabrics treated with drying and nondrying oils, shellac, casein, etc. It was found that fabrics treated as above lost their tension in damp weather, and the oil from the motor penetrated the proofing material and weakened the fabric. For the most part the film of material lacked durability. Cellulose nitrate lacquers, however were found to be more satisfactory under varying weather conditions, added less weight to the planes, and were easily applied. On the other hand, they were highly inflammable, and oil from the motor penetrated the film of cellulose nitrate, causing the tension of the fabric to be relaxed.

  2. Highly Luminescent, Water-Soluble Lanthanide Fluorobenzoates: Syntheses, Structures and Photophysics, Part I: Lanthanide Pentafluorobenzoates.

    PubMed

    Kalyakina, Alena S; Utochnikova, Valentina V; Bushmarinov, Ivan S; Ananyev, Ivan V; Eremenko, Igor L; Volz, Daniel; Rönicke, Franziska; Schepers, Ute; Van Deun, Rik; Trigub, Alexander L; Zubavichus, Yan V; Kuzmina, Natalia P; Bräse, Stefan

    2015-12-01

    Highly luminescent, photostable, and soluble lanthanide pentafluorobenzoates have been synthesized and thoroughly characterized, with a focus on Eu(III) and Tb(III) complexes as visible emitters and Nd(III) , Er(III) , and Yb(III) complexes as infrared emitters. Investigation of the crystal structures of the complexes in powder form and as single crystals by using X-ray diffraction revealed five different structural types, including monomeric, dimeric, and polymeric. The local structure in different solutions was studied by using X-ray absorption spectroscopy. The photoluminescence quantum yields (PLQYs) of terbium and europium complexes were 39 and 15 %, respectively; the latter value was increased almost twice by using the heterometallic complex [Tb0.5 Eu0.5 (pfb)3 (H2 O)] (Hpfb=pentafluorobenzoic acid). Due to the effectively utilized sensitization strategy (pfb)(-) →Tb→Eu, a pure europium luminescence with a PLQY of 29 % was achieved. PMID:26489887

  3. Catalytic ozonation of sulfosalicylic acid over manganese oxide supported on mesoporous ceria.

    PubMed

    Xing, Shengtao; Lu, Xiaoyang; Liu, Jia; Zhu, Lin; Ma, Zichuan; Wu, Yinsu

    2016-02-01

    Manganese oxide supported on mesoporous ceria was prepared and used as catalyst for catalytic ozonation of sulfosalicylic acid (SA). Characterization results indicated that the manganese oxide was mostly incorporated into the pores of ceria. The synthesized catalyst exhibited high activity and stability for the mineralization of SA in aqueous solution by ozone, and more than 95% of total organic carbon was removed in 30 min under various conditions. Mechanism studies indicated that SA was mainly degraded by ozone molecules, and hydroxyl radical reaction played an important role for the degradation of its ozonation products (small molecular organic acids). The manganese oxide in the pores of CeO2 improved the adsorption of small molecular organic acids and the generation of hydroxyl radicals from ozone decomposition, resulting in high TOC removal efficiency.

  4. Oxychlorination-Dehydrochlorination Chemistry on Bifunctional Ceria Catalysts for Intensified Vinyl Chloride Production.

    PubMed

    Scharfe, Matthias; Lira-Parada, Pedro A; Paunović, Vladimir; Moser, Maximilian; Amrute, Amol P; Pérez-Ramírez, Javier

    2016-02-24

    Ceria catalyzes the one-step production of the vinyl chloride monomer (VCM) from ethylene with a high yield because of its bifunctional character: redox centers oxychlorinate ethylene to ethylene dichloride (EDC), which is subsequently dehydrochlorinated to VCM over strong acid sites generated in situ. Nanocrystalline CeO2 and CeO2-ZrO2 lead to a VCM yield of 25 % in a single pass, outperforming the best reported systems and reaching industrially attractive levels. The use of CeO2 intensifies the current two-step process within PVC production encompassing CuCl2 -catalyzed oxychlorination and thermal cracking. In addition, ceria-based materials offer stability advantages with respect to the archetypical CuCl2 -based catalysts.

  5. (Gold core)@(ceria shell) nanostructures for plasmon-enhanced catalytic reactions under visible light.

    PubMed

    Li, Benxia; Gu, Ting; Ming, Tian; Wang, Junxin; Wang, Peng; Wang, Jianfang; Yu, Jimmy C

    2014-08-26

    Driving catalytic reactions with sunlight is an excellent example of sustainable chemistry. A prerequisite of solar-driven catalytic reactions is the development of photocatalysts with high solar-harvesting efficiencies and catalytic activities. Herein, we describe a general approach for uniformly coating ceria on monometallic and bimetallic nanocrystals through heterogeneous nucleation and growth. The method allows for control of the shape, size, and type of the metal core as well as the thickness of the ceria shell. The plasmon shifts of the Au@CeO2 nanostructures resulting from the switching between Ce(IV) and Ce(III) are observed. The selective oxidation of benzyl alcohol to benzaldehyde, one of the fundamental reactions for organic synthesis, performed under both broad-band and monochromatic light, demonstrates the visible-light-driven catalytic activity and reveals the synergistic effect on the enhanced catalysis of the Au@CeO2 nanostructures.

  6. Dehydrogenation of methanol to formaldehyde catalyzed by pristine and defective ceria surfaces

    DOE PAGES

    Beste, Ariana; Overbury, Steven H.

    2016-03-09

    We have explored the dehydrogenation of methoxy on pristine and defective (111), (100), and (110) ceria surfaces with density functional methods. Methanol conversion is used as a probe reaction to understand structure sensitivity of the oxide catalysis. Differences in reaction selectivity have been observed experimentally as a function of crystallographically exposed faces and degree of reduction. We find that the barrier for carbon-hydrogen cleavage in methoxy is similar for the pristine and defective (111), (100), and (110) surfaces. However, there are large differences in the stability of the surface intermediates on the different surfaces. The variations in experimentally observed productmore » selectivities are a consequence of the interplay between barrier controlled bond cleavage and desorption processes. Ultimately, subtle differences in activation energies for carbon-hydrogen cleavage on the different crystallographic faces of ceria could not be correlated with structural or electronic descriptors.« less

  7. Creating single-atom Pt-ceria catalysts by surface step decoration

    PubMed Central

    Dvořák, Filip; Farnesi Camellone, Matteo; Tovt, Andrii; Tran, Nguyen-Dung; Negreiros, Fabio R.; Vorokhta, Mykhailo; Skála, Tomáš; Matolínová, Iva; Mysliveček, Josef; Matolín, Vladimír; Fabris, Stefano

    2016-01-01

    Single-atom catalysts maximize the utilization of supported precious metals by exposing every single metal atom to reactants. To avoid sintering and deactivation at realistic reaction conditions, single metal atoms are stabilized by specific adsorption sites on catalyst substrates. Here we show by combining photoelectron spectroscopy, scanning tunnelling microscopy and density functional theory calculations that Pt single atoms on ceria are stabilized by the most ubiquitous defects on solid surfaces—monoatomic step edges. Pt segregation at steps leads to stable dispersions of single Pt2+ ions in planar PtO4 moieties incorporating excess O atoms and contributing to oxygen storage capacity of ceria. We experimentally control the step density on our samples, to maximize the coverage of monodispersed Pt2+ and demonstrate that step engineering and step decoration represent effective strategies for understanding and design of new single-atom catalysts. PMID:26908356

  8. Higher ionic conductive ceria-based electrolytes for solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Omar, Shobit; Wachsman, Eric D.; Nino, Juan C.

    2007-10-01

    Codoping is used to enhance the ionic conductivity of ceria-based electrolytes. Sm3+ and Nd3+ were selected as codopants to promote low migration energy paths for oxygen vacancy diffusion, thereby increasing the ionic conductivity. Moreover, the use of codopants also increases the pre-exponential factor in the Arrhenius relationship, thus further improving the ionic conductivity. The ionic conductivity of SmxNdxCe1-2xO2-δ solid solutions is measured using electrochemical impedance spectroscopy. It was observed that for Sm0.075Nd0.075Ce0.85O2-δ, the grain ionic conductivity was 14.0×10-3Scm-1 at 550°C, which makes it one of the most promising ceria-based electrolytes for intermediate temperature solid oxide fuel cells.

  9. Creating single-atom Pt-ceria catalysts by surface step decoration.

    PubMed

    Dvořák, Filip; Farnesi Camellone, Matteo; Tovt, Andrii; Tran, Nguyen-Dung; Negreiros, Fabio R; Vorokhta, Mykhailo; Skála, Tomáš; Matolínová, Iva; Mysliveček, Josef; Matolín, Vladimír; Fabris, Stefano

    2016-02-24

    Single-atom catalysts maximize the utilization of supported precious metals by exposing every single metal atom to reactants. To avoid sintering and deactivation at realistic reaction conditions, single metal atoms are stabilized by specific adsorption sites on catalyst substrates. Here we show by combining photoelectron spectroscopy, scanning tunnelling microscopy and density functional theory calculations that Pt single atoms on ceria are stabilized by the most ubiquitous defects on solid surfaces--monoatomic step edges. Pt segregation at steps leads to stable dispersions of single Pt(2+) ions in planar PtO4 moieties incorporating excess O atoms and contributing to oxygen storage capacity of ceria. We experimentally control the step density on our samples, to maximize the coverage of monodispersed Pt(2+) and demonstrate that step engineering and step decoration represent effective strategies for understanding and design of new single-atom catalysts.

  10. Catalytically Active and Spectator Ce(3+) in Ceria-Supported Metal Catalysts.

    PubMed

    Kopelent, René; van Bokhoven, Jeroen A; Szlachetko, Jakub; Edebeli, Jacinta; Paun, Cristina; Nachtegaal, Maarten; Safonova, Olga V

    2015-07-20

    Identification of active species and the rate-determining reaction steps are crucial for optimizing the performance of oxygen-storage materials, which play an important role in catalysts lowering automotive emissions, as electrode materials for fuel cells, and as antioxidants in biomedicine. We demonstrated that active Ce(3+) species in a ceria-supported platinum catalyst during CO oxidation are short-lived and therefore cannot be observed under steady-state conditions. Using time-resolved resonant X-ray emission spectroscopy, we quantitatively correlated the initial rate of Ce(3+) formation under transient conditions to the overall rate of CO oxidation under steady-state conditions and showed that ceria reduction is a kinetically relevant step in CO oxidation, whereas a fraction of Ce(3+) was present as spectators. This approach can be applied to various catalytic processes involving oxygen-storage materials and reducible oxides to distinguish between redox and nonredox catalytic mechanisms.

  11. Dynamic formation of single-atom catalytic active sites on ceria-supported gold nanoparticles

    PubMed Central

    Wang, Yang-Gang; Mei, Donghai; Glezakou, Vassiliki-Alexandra; Li, Jun; Rousseau, Roger

    2015-01-01

    Catalysis by gold supported on reducible oxides has been extensively studied, yet issues such as the nature of the catalytic site and the role of the reducible support remain fiercely debated topics. Here we present ab initio molecular dynamics simulations of an unprecedented dynamic single-atom catalytic mechanism for the oxidation of carbon monoxide by ceria-supported gold clusters. The reported dynamic single-atom catalytic mechanism results from the ability of the gold cation to strongly couple with the redox properties of the ceria in a synergistic manner, thereby lowering the energy of redox reactions. The gold cation can break away from the gold nanoparticle to catalyse carbon monoxide oxidation, adjacent to the metal/oxide interface and subsequently reintegrate back into the nanoparticle after the reaction is completed. Our study highlights the importance of the dynamic creation of active sites under reaction conditions and their essential role in catalysis. PMID:25735407

  12. Involvement of lanthanides in the free radicals homeostasis.

    PubMed

    Valcheva-Traykova, Maria; Saso, Luciano; Kostova, Irena

    2014-01-01

    Lanthanides are group of rare-earth elements with growing applications both in the industry and healthcare. Their unique properties impose various possibilities for involvement in electron transfer reactions essential for the cellular survival and health on general. The intensified contact of people with lanthanides and the expanding medicinal applications of their compounds insist more profound knowledge on the involvement in biologically relevant electron transfer reactions. It is well known that the balance between formation and elimination of free radicals in a living body is essential for its health and survival. Any internal or environmental factor that alters this balance alters the homeostasis and this way altering the health status. In the present review, the possibilities of changing the balance between formation and elimination of free radicals, due to introduction of different lanthanides and their complexes with organic ligands, were explored, based on the available information in the literature. It was observed that lanthanides may act either as antioxidants or pro-oxidants, depending on the environment, the nature of the bonding in their compounds, and concentration in the tissues. The opportunities for their application in medicine were related with the abilities to control over their involvement in the overall oxidative status of the body.

  13. Luminescent Lanthanide Reporters for High-Sensitivity Novel Bioassays.

    SciTech Connect

    Anstey, Mitchell R.; Fruetel, Julia A.; Foster, Michael E.; Hayden, Carl C.; Buckley, Heather L.; Arnold, John

    2013-09-01

    Biological imaging and assay technologies rely on fluorescent organic dyes as reporters for a number of interesting targets and processes. However, limitations of organic dyes such as small Stokes shifts, spectral overlap of emission signals with native biological fluorescence background, and photobleaching have all inhibited the development of highly sensitive assays. To overcome the limitations of organic dyes for bioassays, we propose to develop lanthanide-based luminescent dyes and demonstrate them for molecular reporting applications. This relatively new family of dyes was selected for their attractive spectral and chemical properties. Luminescence is imparted by the lanthanide atom and allows for relatively simple chemical structures that can be tailored to the application. The photophysical properties offer unique features such as narrow and non-overlapping emission bands, long luminescent lifetimes, and long wavelength emission, which enable significant sensitivity improvements over organic dyes through spectral and temporal gating of the luminescent signal.Growth in this field has been hindered due to the necessary advanced synthetic chemistry techniques and access to experts in biological assay development. Our strategy for the development of a new lanthanide-based fluorescent reporter system is based on chelation of the lanthanide metal center using absorbing chromophores. Our first strategy involves "Click" chemistry to develop 3-fold symmetric chelators and the other involves use of a new class of tetrapyrrole ligands called corroles. This two-pronged approach is geared towards the optimization of chromophores to enhance light output.

  14. Experimental and Theoretical Studies on Biologically Active Lanthanide (III) Complexes

    NASA Astrophysics Data System (ADS)

    Kostova, I.; Trendafilova, N.; Georgieva, I.; Rastogi, V. K.; Kiefer, W.

    2008-11-01

    The complexation ability and the binding mode of the ligand coumarin-3-carboxylic acid (HCCA) to La(III), Ce(III), Nd(III), Sm(III), Gd(III) and Dy(III) lanthanide ions (Ln(III)) are elucidated at experimental and theoretical level. The complexes were characterized using elemental analysis, DTA and TGA data as well as 1H NMR and 13C NMR spectra. FTIR and Raman spectroscopic techniques as well as DFT quantum chemical calculations were used for characterization of the binding mode and the structures of lanthanide(III) complexes of HCCA. The metal—ligand binding mode is predicted through molecular modeling and energy estimation of different Ln—CCA structures using B3LYP/6-31G(d) method combined with a large quasi-relativistic effective core potential for lanthanide ion. The energies obtained predict bidentate coordination of CCA- to Ln(III) ions through the carbonylic oxygen and the carboxylic oxygen. Detailed vibrational analysis of HCCA, CCA- and Ln(III) complexes based on both calculated and experimental frequencies confirms the suggested metal—ligand binding mode. The natural bonding analysis predicts strongly ionic character of the Ln(III)-CCA bonding in the- complexes studied. With the relatively resistant tumor cell line K-562 we obtained very interesting in-vitro results which are in accordance with our previously published data concerning the activity of lanthanide(III) complexes with other coumarin derivatives.

  15. On the Suitability of Lanthanides as Actinide Analogs

    SciTech Connect

    Szigethy, Geza; Raymond, Kenneth N.

    2008-04-11

    With the current level of actinide materials used in civilian power generation and the need for safe and efficient methods for the chemical separation of these species from their daughter products and for long-term storage requirements, a detailed understanding of actinide chemistry is of great importance. Due to the unique bonding properties of the f-elements, the lanthanides are commonly used as structural and chemical models for the actinides, but differences in the bonding between these 4f and 5f elements has become a question of immediate applicability to separations technology. This brief overview of actinide coordination chemistry in the Raymond group at UC Berkeley/LBNL examines the validity of using lanthanide analogs as structural models for the actinides, with particular attention paid to single crystal X-ray diffraction structures. Although lanthanides are commonly accepted as reasonable analogs for the actinides, these comparisons suggest the careful study of actinide materials independent of their lanthanide analogs to be of utmost importance to present and future efforts in nuclear industries.

  16. Heat capacities of lanthanide and actinide monazite-type ceramics

    NASA Astrophysics Data System (ADS)

    Kowalski, Piotr M.; Beridze, George; Vinograd, Victor L.; Bosbach, Dirk

    2015-09-01

    (Ln, An)xPO4 monazite-type ceramics are considered as potential matrices for the disposal of nuclear waste. In this study we computed the heat capacities and the standard entropies of these compounds using density functional perturbation theory. The calculations of lanthanide monazites agree well with the existing experimental data and provide information on the variation of the standard heat capacities and entropies along the lanthanide series. The results for AnPO4 monazites are similar to those obtained for the isoelectronic lanthanide compounds. This suggests that the missing thermodynamic data on actinide monazites could be similarly computed or assessed based on the properties of their lanthanide analogs. However, the computed heat capacity of PuPO4 appear to be significantly lower than the measured data. We argue that this discrepancy might indicate potential problems with the existing experimental data or with their interpretation. This shows a need for further experimental studies of the heat capacities of actinide-bearing, monazite-type ceramics.

  17. Detection of Bacterial Spores with Lanthanide-Macrocycle Binary Complexes

    PubMed Central

    Cable, Morgan L.; Kirby, James P.; Levine, Dana J.; Manary, Micah J.; Gray, Harry B.; Ponce, Adrian

    2009-01-01

    The detection of bacterial spores via dipicolinate-triggered lanthanide luminescence has been improved in terms of detection limit, stability, and susceptibility to interferents by use of lanthanide-macrocycle binary complexes. Specifically, we compared the effectiveness of Sm, Eu, Tb and Dy complexes with the macrocycle 1,4,7,10-tetraazacyclododecane-1,7-diacetate (DO2A) to the corresponding lanthanide aquo ions. The Ln(DO2A)+ binary complexes bind dipicolinic acid (DPA), a major constituent of bacterial spores, with greater affinity and demonstrate significant improvement in bacterial spore detection. Of the four luminescent lanthanides studied, the terbium complex exhibits the greatest dipicolinate binding affinity (100-fold greater than Tb3+ alone, and 10-fold greater than other Ln(DO2A)+ complexes) and highest quantum yield. Moreover, the inclusion of DO2A extends the pH range over which Tb-DPA coordination is stable, reduces the interference of calcium ions nearly 5-fold, and mitigates phosphate interference 1000-fold compared to free terbium alone. In addition, detection of Bacillus atrophaeus bacterial spores was improved by the use of Tb(DO2A)+, yielding a 3-fold increase in the signal-to-noise ratio over Tb3+. Out of the eight cases investigated, the Tb(DO2A)+ binary complex is best for the detection of bacterial spores. PMID:19537757

  18. Luminescent 1-hydroxy-2-pyridinone chelates of lanthanides

    DOEpatents

    Raymond, Kenneth N.; Xu, Jide; Moore, Evan G.; Werner, Eric J.

    2013-10-15

    The present invention provides luminescent complexes between a lanthanide ion and an organic ligand which contains 1,2-hydroxypyridinone units. The complexes of the invention are stable in aqueous solutions and are useful as molecular probes, for example in medical diagnostics and bioanalytical assay systems. The invention also provides methods of using the complexes of the invention.

  19. Charge distribution and transport properties in reduced ceria phases: A review

    NASA Astrophysics Data System (ADS)

    Shoko, E.; Smith, M. F.; McKenzie, Ross H.

    2011-12-01

    The question of the charge distribution in reduced ceria phases (CeO2-x) is important for understanding the microscopic physics of oxygen storage capacity, and the electronic and ionic conductivities in these materials. All these are key properties in the application of these materials in catalysis and electrochemical devices. Several approaches have been applied to study this problem, including ab initio methods. Recently [1], we applied the bond valence model (BVM) to discuss the charge distribution in several different crystallographic phases of reduced ceria. Here, we compare the BVM results to those from atomistic simulations to determine if there is consistency in the predictions of the two approaches. Our analysis shows that the two methods give a consistent picture of the charge distribution around oxygen vacancies in bulk reduced ceria phases. We then review the transport theory applicable to reduced ceria phases, providing useful relationships which enable comparison of experimental results obtained by different techniques. In particular, we compare transport parameters obtained from the observed optical absorption spectrum, α(ω), dc electrical conductivity with those predicted by small polaron theory and the Harrison method. The small polaron energy is comparable to that estimated from α(ω). However, we found a discrepancy between the value of the electron hopping matrix element, t, estimated from the Marcus-Hush formula and that obtained by the Harrison method. Part of this discrepancy could be attributed to the system lying in the crossover region between adiabatic and nonadiabatic whereas our calculations assumed the system to be nonadiabatic. Finally, by considering the relationship between the charge distribution and electronic conductivity, we suggest the possibility of low temperature metallic conductivity for intermediate phases, i.e., x˜0.3. This has not yet been experimentally observed.

  20. Morphology control of ceria nanocrystals for catalytic conversion of CO2 with methanol

    NASA Astrophysics Data System (ADS)

    Wang, Shengping; Zhao, Lifang; Wang, Wei; Zhao, Yujun; Zhang, Guanglin; Ma, Xinbin; Gong, Jinlong

    2013-05-01

    This paper describes the synthesis of ceria catalysts with octahedron, nanorod, nanocube and spindle-like morphologies via a template-free hydrothermal method. The surface morphologies, crystal plane and physical-chemical structures were investigated via field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD) and temperature-programmed desorption of ammonia and carbon dioxide (NH3-TPD and CO2-TPD). The catalytic performance over these ceria catalysts with different exposed planes were tested for dimethyl carbonate (DMC) synthesis from CO2 and methanol. The results showed that the spindle-like CeO2 showed the highest DMC yields, followed by nano-rods, nano-cubes and nano-octahedrons. A synergism among the exposed (111) plane, defect sites, and acid-basic sites was proposed to be crucial to obtaining the high reactivity of DMC formation.This paper describes the synthesis of ceria catalysts with octahedron, nanorod, nanocube and spindle-like morphologies via a template-free hydrothermal method. The surface morphologies, crystal plane and physical-chemical structures were investigated via field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD) and temperature-programmed desorption of ammonia and carbon dioxide (NH3-TPD and CO2-TPD). The catalytic performance over these ceria catalysts with different exposed planes were tested for dimethyl carbonate (DMC) synthesis from CO2 and methanol. The results showed that the spindle-like CeO2 showed the highest DMC yields, followed by nano-rods, nano-cubes and nano-octahedrons. A synergism among the exposed (111) plane, defect sites, and acid-basic sites was proposed to be crucial to obtaining the high reactivity of DMC formation. Electronic supplementary information (ESI) available. See DOI

  1. Enhancement of Anion Binding in Lanthanide Optical Sensors

    PubMed Central

    Cable, Morgan L.; Kirby, James P.; Gray, Harry B.; Ponce, Adrian

    2013-01-01

    In the design of molecular sensors, researchers exploit binding interactions that are usually defined in terms of topology and charge complementarity. The formation of complementary arrays of highly cooperative, noncovalent bonding networks facilitates protein-ligand binding, leading to motifs such as the ‘lock-and-key.’ Synthetic molecular sensors often employ metal complexes as key design elements as a way to construct a binding site with the desired shape and charge to achieve target selectivity. In transition metal complexes, coordination number, structure and ligand dynamics are governed primarily by a combination of inner-sphere covalent and outer-sphere noncovalent interactions. These interactions provide a rich variable space that researchers can use to tune structure, stability and dynamics. In contrast, lanthanide(III)-ligand complex formation and ligand-exchange dynamics are dominated by reversible electrostatic and steric interactions, because the unfilled f shell is shielded by the larger, filled d shell. Luminescent lanthanides such as terbium, europium, dysprosium and samarium display many photophysical properties that make them excellent candidates for molecular sensor applications. Complexes of lanthanide ions act as receptors that exhibit a detectable change in metal-based luminescence upon binding of an anion. In our work on sensors for detection of dipicolinate, the unique biomarker of bacterial spores, we discovered that the incorporation of an ancillary ligand (AL) can enhance binding constants of target anions to lanthanide ions by as much as two orders of magnitude. In this Account, we show that selected ALs in lanthanide/anion systems greatly improve sensor performance for medical, planetary science and biodefense applications. We suggest that the observed anion binding enhancement could result from an AL-induced increase in positive charge at the lanthanide ion binding site. This effect depends on lanthanide polarizability, which can

  2. Segregation and Migration of the Oxygen Vacancies in the 3 (111) Tilt Grain Boundaries of Ceria

    DOE PAGES

    Yuan, Fenglin; Liu, Bin; Zhang, Yanwen; Weber, William J.

    2016-03-01

    In nanocrystalline materials, defect-grain boundary (GB) interaction plays a key role in determining the structure stability, as well as size-dependent ionic, electronic, magnetic and chemical properties. In this study, we systematically investigated using density functional theory segregation and migration of oxygen vacancies at the Σ3 [110] / (111) grain boundary of ceria. Three oxygen layers near the GB are predicted to be segregation sites for oxygen vacancies. Moreover, the presence of oxygen vacancies stabilizes this tilt GB at a low Fermi level and/or oxygen poor conditions. An atomic strain model was proposed to rationalize layer dependency of the relaxation energymore » for +2 charged oxygen vacancy. The structural origin of large relaxation energies at layers 1 and 2 was determined to be free-volume space that induces ion relaxation towards the GB. Our results not only pave the way for improving the oxygen transport near GBs of ceria, but also provide important insights into engineering the GB structure for better ionic, magnetic and chemical properties of nanocrystalline ceria.« less

  3. Thermodynamic Analysis of Isothermal Redox Cycling of Ceria for Solar Fuel Production

    SciTech Connect

    Bader, R; Venstrom, LJ; Davidson, JH; Lipinski, W

    2013-09-01

    A thermodynamic analysis of continuous fuel production by redox cycling of ceria in a single solar reactor under isothermal conditions is presented. Ceria is partially reduced in a sweep gas flow of purified nitrogen and reoxidized with either steam or carbon dioxide to produce hydrogen or carbon monoxide, respectively. The sweep gas and oxidizer flows are preheated by the product gases. The influence of selected process parameters, including operating temperature, pressure, and the effectiveness of heat recovery, on the solar-to-fuel conversion efficiency is determined. For a solar concentration ratio of 3000, typical of state-of-the-art solar dish concentrators, and operating temperature of 1773 K, 95.5% of the available gas-phase heat must be recovered to reach conversion efficiencies of 10% and 18% for hydrogen and carbon monoxide production, respectively, assuming the flow rate of inert sweep gas is equivalent to that in a counter-current flow arrangement of gas and ceria. The efficiency depends strongly on the gas-phase heat recovery effectiveness and the sweep gas flow rate. Introducing a temperature swing of 150 K between reduction and oxidation steps strongly reduces the sweep gas flow rate and increases the efficiency from 10% to 31.6% for hydrogen production.

  4. Simulation of the f—d transitions of lanthanide ions in YPO4 using quantum-chemical calculations

    NASA Astrophysics Data System (ADS)

    Hu, Liu-Sen; Wen, Jun; Yin, Min; Xia, Shang-Da

    2012-01-01

    We constructed an effective one-electron Hamiltonian by using the 4f/5d energies and eigenvectors obtained from the first-principles calculation with the relativistic self-consistent discrete variational Slater software package (DV-Xα). From the effective Hamiltonian, we obtained the crystal-field and spin-orbit interaction parameters for the 4f and 5d electrons of lanthanide ions (Ce3+, Pr3+, Nd3+ and Eu3+) doped in YPO4, and these parameters were used to calculate the 4fN-4fN-15d transition. Comparison with experiments shows that the obtained parameters are reasonable and the excitation spectra can be well predicted.

  5. r-PROCESS LANTHANIDE PRODUCTION AND HEATING RATES IN KILONOVAE

    SciTech Connect

    Lippuner, Jonas; Roberts, Luke F.

    2015-12-20

    r-process nucleosynthesis in material ejected during neutron star mergers may lead to radioactively powered transients called kilonovae. The timescale and peak luminosity of these transients depend on the composition of the ejecta, which determines the local heating rate from nuclear decays and the opacity. Kasen et al. and Tanaka and Hotokezaka pointed out that lanthanides can drastically increase the opacity in these outflows. We use the new general-purpose nuclear reaction network SkyNet to carry out a parameter study of r-process nucleosynthesis for a range of initial electron fractions Y{sub e}, initial specific entropies s, and expansion timescales τ. We find that the ejecta is lanthanide-free for Y{sub e} ≳ 0.22−0.30, depending on s and τ. The heating rate is insensitive to s and τ, but certain, larger values of Y{sub e} lead to reduced heating rates, due to individual nuclides dominating the heating. We calculate approximate light curves with a simplified gray radiative transport scheme. The light curves peak at about a day (week) in the lanthanide-free (-rich) cases. The heating rate does not change much as the ejecta becomes lanthanide-free with increasing Y{sub e}, but the light-curve peak becomes about an order of magnitude brighter because it peaks much earlier when the heating rate is larger. We also provide parametric fits for the heating rates between 0.1 and 100 days, and we provide a simple fit in Y{sub e}, s, and τ to estimate whether or not the ejecta is lanthanide-rich.

  6. Lanthanide sorption on smectitic clays in presence of cement leachates

    NASA Astrophysics Data System (ADS)

    Galunin, Evgeny; Alba, María D.; Santos, Maria J.; Abrão, Taufik; Vidal, Miquel

    2010-02-01

    Due to their potential retention capacity, clay minerals have been proposed for use in the engineered barriers for the storage of high-level radioactive actinides in deep geological waste repositories. However, there is still a lack of data on the sorption of actinides in clays in conditions simulating those of the repositories. The present article examines the sorption of two lanthanides (actinide analogues) in a set of smectitic clays (FEBEX bentonite, MX80 bentonite, hectorite, saponite, Otay montmorillonite, and Texas montmorillonite). Distribution coefficients ( Kd) were determined in two media: water and 0.02 mol L -1 Ca, the latter representing the cement leachates that may modify the chemical composition of the water in contact with the clay. The Kd values of the lanthanides used in the experiments (La and Lu) varied greatly (25-50 000 L kg -1) depending on the ionic medium (higher values in water than in the Ca medium), the initial lanthanide concentration (up to three orders of magnitude decrease inversely with lanthanide concentration), and the examined clay (up to one order of magnitude for the same lanthanide and sorption medium). Freundlich and Langmuir isotherms were used to fit sorption data to allow comparison of the sorption parameters among smectites. The model based on the two-site Langmuir isotherms provided the best fit of the sorption data, confirming the existence of sorption sites with different binding energies. The sites with higher sorption affinity were about 6% of the total sorption capacity in the water medium, and up to 17% in the Ca medium, although in this latter site sorption selectivity was lower. The wide range of Kd values obtained regarding the factors examined indicated that the retention properties of the clays should also be considered when selecting a suitable clay for engineered barriers.

  7. Bispyrene/surfactant-assembly-based fluorescent sensor array for discriminating lanthanide ions in aqueous solution.

    PubMed

    Wang, Shihuai; Ding, Liping; Fan, Junmei; Wang, Zhongxiu; Fang, Yu

    2014-09-24

    Lanthanides are valuable nonrenewable resources and widely used in a variety of industries. Detection and identification of lanthanide ions are in high demand but challenging because of the similarity among lanthanide ions. In the present work, a fluorescent sensor array of three cationic bispyrene derivatives mixed with anionic surfactant assemblies was developed. The sensor array exhibits cross-reactive responses to lanthanide ions when tested in aqueous solution. The combination of fluorescence variations at both monomer and excimer emission of each of the bispyrene sensor elements provides a six-signal recognition pattern for lanthanide ions. Principle component analysis illustrates that the sensor array could at least identify 6 of the 14 similar lanthanide ions including La(3+), Pr(3+), Nd(3+), Eu(3+), Ho(3+), and Er(3+). UV-vis absorption measurements rule out the possibility of binding lanthanides with fluorophores. Fluorescence titration experiments in both cationic and neutral surfactant aqueous solutions reveal that the three fluorophores show slight fluorescence responses to the lanthanide ions, indicating that electrostatic attraction between lanthanide ions and anionic surfactant plays an important role in the sensing behavior of the sensor array. Control experiments with divalent metal ions find no cross-reactive responses, suggesting that the stronger electrostatic interaction with trivalent lanthanide ions is responsible for the multiple fluorescence responses. PMID:25188720

  8. Feasibility of the electrochemical way in molten fluorides for separating thorium and lanthanides and extracting lanthanides from the solvent

    NASA Astrophysics Data System (ADS)

    Chamelot, P.; Massot, L.; Hamel, C.; Nourry, C.; Taxil, P.

    2007-01-01

    An alternative way of reprocessing nuclear fuel by hydrometallurgy could be using treatment with molten salts, particularly fluoride melts. Moreover, one of the six concepts chosen for GEN IV nuclear reactors (Technology Roadmap - http://gif.inel.gov/roadmap/) is the molten salt reactor (MSR). The originality of the concept is the use of molten salts as liquid fuel and coolant. During the running of the reactor, fission products, particularly lanthanides, accumulate in the melt and have to be eliminated to optimise reactor operation. This study concerns the feasibility of the separation actinides-lanthanides-solvent by selectively electrodepositing the elements to be separated on an inert (Mo, Ta) or a reactive (Ni) cathodic substrate in molten fluoride media. The main results of this work lead to the conclusions that: The solvents to be used for efficient separation must be fluoride media containing lithium as cation. Inert substrates are suitable for actinide/lanthanide separation; nickel substrate is more suitable for the extraction of lanthanides from the solvent, owing to the depolarisation occurring in the cathodic process through alloy formation.

  9. Catalytic propane reforming mechanism over Mn-Doped CeO2 (111)

    NASA Astrophysics Data System (ADS)

    Krcha, Matthew D.; Janik, Michael J.

    2015-10-01

    MnOx/CeOx mixed oxide systems exhibit encouraging hydrocarbon oxidation activity, without the inclusion of a noble metal. Using density functional theory (DFT) methods, we examined the oxidative reforming path of propane over the Mn-doped CeO2 (1 1 1) surface. A plausible set of elementary reaction steps are identified for conversion of propane to CO/CO2 and H2/H2O over the oxide surface. The rate-limiting reaction process may vary with redox conditions, with C-H dissociation limiting under more oxidizing conditions and more complex reaction sequences, including surface re-oxidation, limiting under highly reducing conditions. The possibility of intermediate desorption from the surface during the reforming process is low, with desorption energies of the intermediates being much less favorable than further surface reactions until CO/CO2 products are formed. The reforming paths over Mn-doped ceria are similar to those previously identified over Zr-doped ceria. The extent of surface reduction and the electronic structure of the surface intermediates are examined.

  10. Lanthanide-containing polycations for monitoring polyplex dynamics via lanthanide resonance energy transfer.

    PubMed

    Kelkar, Sneha S; Xue, Lian; Turner, S Richard; Reineke, Theresa M

    2014-05-12

    Theranostic nanomaterials have emerged in the past decade that combine therapeutic delivery and diagnostic imaging into one package. Such materials offer the opportunity to aid diagnosis, track therapeutic biodistribution, and monitor drug release. We have developed a series of nucleic acid delivery polymers containing oligoethylene amines that are able to be protonated at physiological pH (for binding/compacting pDNA) and a lanthanide-chelating domain, which imparts diagnostic functionality. Diamine monomers (containing between 3 and 6 Boc-protected ethyleneamines) were prepared via a multistep procedure involving the selective protection and deprotection of primary and secondary amines. The polymer structures were then synthesized by step-growth polymerization of the oligoethylene diamines with a bisanhydride of diethylenetriamine pentaacetic acid (DTPA-BA), yielding degrees of polymerization between 18 and 24. Chelation of the polymers with gadolinium and terbium was performed to offer MRI contrast agent and luminescence properties, respectively. All of the polymer chelates were found to house approximately one water coordination site, as calculated by the Horrock's equation and possess longitudinal relaxivities (r1, on a per Gd basis) at least twice that of Magnevist, a clinical contrast agent. All the structures formed polyplexes with pDNA with highly positive zeta potentials and hydrodynamic diameters around 50-80 nm. Lanthanide resonance energy transfer (LRET) was used to monitor polyplex association and dissociation. Polyplexes were formed using the donor-acceptor pair comprising of terbium-chelated polymer with five ethyleneamines within the repeat unit (6c-Tb) and tetramethyl rhodamine (TMR)-labeled pDNA. Association/dissociation in the presence of heparin and NaCl was monitored. The effect of amine number along the polymer backbone on transfection efficiency and cytotoxicity was also investigated. None of the polymers revealed cytotoxic effects with

  11. Luminescent hybrid lanthanide sulfates and lanthanide sulfonate-carboxylates with 1,10-phenanthroline involving in-situ oxidation of 2-mercaptonbenzoic acid

    SciTech Connect

    Zhong, Jie-Cen; Wan, Fang; Sun, Yan-Qiong; Chen, Yi-Ping

    2015-01-15

    A series of lanthanide sulfates and lanthanide sulfonate-carboxylates, [Ln{sub 2}(phen){sub 2}(SO{sub 4}){sub 3}(H{sub 2}O){sub 2}]{sub n} (I:Ln=Nd(1a), Sm(1b), Eu(1c), phen=1,10-phenanthroline) and [Ln(phen)(2-SBA)(BZA)]{sub n} (II: Ln=Sm(2a), Eu(2b), Dy(2c), 2-SBA=2-sulfobenzoate, BZA=benzoate) have been hydrothermally synthesized from lanthanide oxide, 2-mercaptonbenzoic acid with phen as auxiliary ligand and characterized by single-crystal X-ray diffraction, elemental analyses, IR spectra, TG analyses and luminescence spectroscopy. Interestingly, SO{sub 4}{sup 2−} anions in I came from the in situ deep oxidation of thiol groups of 2-mercaptonbenzoic acid while 2-sulfobenzoate and benzoate ligands in II from the middle oxidation and desulfuration reactions of 2-mercaptonbenzoic acid. Compounds I are organic–inorganic hybrid lanthanide sulfates, which have rare one-dimensional column-like structures. Complexes II are binuclear lanthanide sulfonate-carboxylates with 2-sulfobenzoate and benzoate as bridges and 1,10-phenanthroline as terminal. Photoluminescence studies reveal that complexes I and II exhibit strong lanthanide characteristic emission bands in the solid state at room temperature. - Graphical abstract: Lanthanide sulfates and lanthanide sulfonate-carboxylates have been hydrothermally synthesized. Interestingly, sulfate anions, 2-sulfobenzoate and benzoate ligands came from the in situ oxidation and desulfuration reactions of 2-mercaptonbenzoic acid. - Highlights: • In situ oxidation and desulfuration reactions of 2-mercaptonbenzoic acid. • The organic–inorganic hybrid lanthanide sulfates with one-dimensional column-like structure. • The dinuclear lanthanide sulfonate-carboxylates. • The emission spectra exhibit the characteristic transition of {sup 5}D{sub 0}→{sup 7}F{sub J} (J=0–4) of the Eu(III)

  12. Dynamic tests for actinide/lanthanide separation by CMPO solvent in fluorinated diluents

    SciTech Connect

    Tkachenko, L.; Babain, V.; Alyapyshev, M.; Vizniy, A.; Il'in, A.; Shadrin, A.

    2013-07-01

    Actinide and lanthanide extraction by new solvent: 0.2 M phenyl-octyl-N,N-diiso-butylcarbamoyl-phosphine oxide (CMPO) + 30% TBP + formal of octafluoro-pentanol was studied. A dynamic test with this solvent was performed. It was shown that americium and lanthanides are effectively extracted from PUREX process raffinate. The separation of americium from light lanthanides was confirmed in the modified SETFICS flowsheet with this new solvent. (authors)

  13. Extraction of trivalent lanthanides and actinides by ``CMPO-like`` calixarenes

    SciTech Connect

    Delmau, L.H.; Simon, N.; Schwing-Weill, M.J.

    1999-04-01

    Extractive properties of calix[4]arenes bearing carbamoylmethylphosphine oxide moieties on their upper rim toward trivalent lanthanide and actinide cations were investigated. The study revealed that these molecules selectively extract light lanthanides and actinides from heavy lanthanides. All parameters present in the extraction system were varied to determine the origin of the selectivity. It was found that this selectivity requires a calix[4]arene platform and acetamidophosphine oxide groups containing phenyl substituents on the four phosphorus atoms.

  14. The lanthanides and yttrium in minerals of the apatite group; a review

    USGS Publications Warehouse

    Fleischer, Michael; Altschuler, Z.S.

    1982-01-01

    More than 1000 analyses have been tabulated of the distribution of the lanthanides and yttrium in minerals of the apatite group, recalculated to atomic percentages. Average compositions have been calculated for apatites from 14 types of rocks. These show a progressive change of composition from apatites of granitic pegmatites, highest in the heavy lanthanides and yttrium, to those from alkalic pegmatites, highest in the light lanthanides and lowest in yttrium. This progression is clearly shown in plots of S (= at % La+Ce+Pr) vs the ratio La/Nd and of S vs the ratio 100Y/(Y+Ln), where Ln is the sum of the lanthanides. Apatites of sedimentary phosphorites occupy a special position, being relatively depleted in Ce and relatively enriched in yttrium and the heavy lanthanides, consequences of deposition from sea water. Apatites associated with iron ores are close in composition to apatites of carbonatites, alkalic ultramafic, and ultramafic rocks, being enriched in the light lanthanides and depleted in the heavy lanthanides. Their compositions do not support the hypothesis of Parak that the Kiruna-type ores are of sedimentary origin. Table 9 and Figures 1-3 show the dependence of lanthanide distribution on the nature of the host rock. Although a given analysis of the lanthanides does not unequivocally permit certain identification of the host rock, it can indicate a choice of highly probable host rocks.

  15. Lanthanide Selective Sorbents: Self-Assembled Monolayers on Mesoporous Supports (SAMMS)

    SciTech Connect

    Fryxell, Glen E.; Wu, Hong; Lin, Yuehe; Shaw, Wendy J.; Birnbaum, Jerome C.; Linehan, John C.; Nie, Zimin; Kemner, Kenneth M.; Kelly, Shelley

    2004-11-01

    Through the marriage of mesoporous ceramics with self-assembled monolayer chemistry, the genesis of a powerful new class of environmental sorbent materials has been realized. By coating the mesoporous ceramic backbone with a monolayer terminated with a lanthanide-specific ligand, it is possible to couple high lanthanide binding affinity with the high loading capacity (resulting from the extremely high surface area of the support). This lanthanide-specific ligand field is created by pairing a “hard” anionic Lewis base with a suitable synergistic ligand, in a favorable chelating geometry. Details of the synthesis, characterization, lanthanide binding studies, binding kinetics, competition experiments and sorbent regeneration studies are summarized.

  16. Lanthanide Selective Sorbents: Self-Assembled Monolayers on Mesoporous Supports (SAMMS)

    SciTech Connect

    Fryxell, Glen E.; Wu, Hong; Lin, Yuehe; Shaw, Wendy J.; Birnbaum, Jerome C.; Linehan, John C.; Nie, Zimin; Kemner, K. M.; Kelly, Shelley

    2004-11-01

    Through the marriage of mesoporous ceramics with self-assembled monolayer chemistry, the genesis of a powerful new class of environmental sorbent materials has been realized. By coating the mesoporous ceramic backbone with a monolayer terminated with a lanthanide-specific ligand, it is possible to couple high lanthanide binding affinity with the high loading capacity (resulting from the extremely high surface area of the support). This lanthanide-specific ligand field is created by pairing a ''hard'' anionic Lewis base with a suitable synergistic ligand, in a favorable chelating geometry. Details of the synthesis, characterization, lanthanide binding studies, binding kinetics, competition experiments and sorbent regeneration studies are summarized

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

    SciTech Connect

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

    2015-07-15

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

  18. Subsurface defect characterization and laser-induced damage performance of fused silica optics polished with colloidal silica and ceria

    NASA Astrophysics Data System (ADS)

    Xiang, He; Gang, Wang; Heng, Zhao; Ping, Ma

    2016-04-01

    This paper mainly focuses on the influence of colloidal silica polishing on the damage performance of fused silica optics. In this paper, nanometer sized colloidal silica and micron sized ceria are used to polish fused silica optics. The colloidal silica polished samples and ceria polished samples exhibit that the root-mean-squared (RMS) average surface roughness values are 0.7 nm and 1.0 nm, respectively. The subsurface defects and damage performance of the polished optics are analyzed and discussed. It is revealed that colloidal silica polishing will introduce much fewer absorptive contaminant elements and subsurface damages especially no trailing indentation fracture. The 355-nm laser damage test reveals that each of the fused silica samples polished with colloidal silica has a much higher damage threshold and lower damage density than ceria polished samples. Colloidal silica polishing is potential in manufacturing high power laser optics.

  19. Advancing the scientific basis of trivalent actinide-lanthanide separations

    SciTech Connect

    Nash, K.L.

    2013-07-01

    For advanced fuel cycles designed to support transmutation of transplutonium actinides, several options have been demonstrated for process-scale aqueous separations for U, Np, Pu management and for partitioning of trivalent actinides and fission product lanthanides away from other fission products. The more difficult mutual separation of Am/Cm from La-Tb remains the subject of considerable fundamental and applied research. The chemical separations literature teaches that the most productive alternatives to pursue are those based on ligand donor atoms less electronegative than O, specifically N- and S-containing complexants and chloride ion (Cl{sup -}). These 'soft-donor' atoms have exhibited usable selectivity in their bonding interactions with trivalent actinides relative to lanthanides. In this report, selected features of soft donor reagent design, characterization and application development will be discussed. The roles of thiocyanate, aminopoly-carboxylic acids and lactate in separation processes are detailed. (authors)

  20. Superabsorbing gel for actinide, lanthanide, and fission product decontamination

    DOEpatents

    Kaminski, Michael D.; Mertz, Carol J.

    2016-06-07

    The present invention provides an aqueous gel composition for removing actinide ions, lanthanide ions, fission product ions, or a combination thereof from a porous surface contaminated therewith. The composition comprises a polymer mixture comprising a gel forming cross-linked polymer and a linear polymer. The linear polymer is present at a concentration that is less than the concentration of the cross-linked polymer. The polymer mixture is at least about 95% hydrated with an aqueous solution comprising about 0.1 to about 3 percent by weight (wt %) of a multi-dentate organic acid chelating agent, and about 0.02 to about 0.6 molar (M) carbonate salt, to form a gel. When applied to a porous surface contaminated with actinide ions, lanthanide ions, and/or other fission product ions, the aqueous gel absorbs contaminating ions from the surface.

  1. Deep-UV biological imaging by lanthanide ion molecular protection

    PubMed Central

    Kumamoto, Yasuaki; Fujita, Katsumasa; Smith, Nicholas Isaac; Kawata, Satoshi

    2015-01-01

    Deep-UV (DUV) light is a sensitive probe for biological molecules such as nucleobases and aromatic amino acids due to specific absorption. However, the use of DUV light for imaging is limited because DUV can destroy or denature target molecules in a sample. Here we show that trivalent ions in the lanthanide group can suppress molecular photodegradation under DUV exposure, enabling a high signal-to-noise ratio and repetitive DUV imaging of nucleobases in cells. Underlying mechanisms of the photodegradation suppression can be excitation relaxation of the DUV-absorptive molecules due to energy transfer to the lanthanide ions, and/or avoiding ionization and reactions with surrounding molecules, including generation of reactive oxygen species, which can modify molecules that are otherwise transparent to DUV light. This approach, directly removing excited energy at the fundamental origin of cellular photodegradation, indicates an important first step towards the practical use of DUV imaging in a variety of biological applications. PMID:26819825

  2. A TRUEX-based separation of americium from the lanthanides

    SciTech Connect

    Bruce J. Mincher; Nicholas C. Schmitt; Mary E. Case

    2011-03-01

    Abstract: The inextractability of the actinide AnO2+ ions in the TRUEX process suggests the possibility of a separation of americium from the lanthanides using oxidation to Am(V). The only current method for the direct oxidation of americium to Am(V) in strongly acidic media is with sodium bismuthate. We prepared Am(V) over a wide range of nitric acid concentrations and investigated its solvent extraction behavior for comparison to europium. While a separation is achievable in principal, the presence of macro amounts of cerium competes for the sparingly soluble oxidant and the oxidant itself competes for CMPO complexation. These factors conspire to reduce the Eu/Am separation factor from ~40 using tracer solutions to ~5 for extractions from first cycle raffinate simulant solution. To separate pentavalent americium directly from the lanthanides using the TRUEX process, an alternative oxidizing agent will be necessary.

  3. Lanthanides caged by the organic chelates; structural properties.

    PubMed

    Smentek, Lidia

    2011-04-13

    The structure, in particular symmetry, geometry and morphology of organic chelates coordinated with the lanthanide ions are analyzed in the present review. This is the first part of a complete presentation of a theoretical description of the properties of systems, which are widely used in technology, but most of all, in molecular biology and medicine. The discussion is focused on the symmetry and geometry of the cages, since these features play a dominant role in the spectroscopic activity of the lanthanides caged by organic chelates. At the same time, the spectroscopic properties require more formal presentation in the language of Racah algebra, and deserve a separate analysis. In addition to the parent systems of DOTA, DOTP, EDTMP and CDTMP presented here, their modifications by various antennas are analyzed. The conclusions that have a strong impact upon the theory of the energy transfer and the sensitized luminescence of these systems are based on the results of numerical density functional theory calculations.

  4. A self-assembling lanthanide molecular nanoparticle for optical imaging†

    PubMed Central

    Brown, Katherine A.; Yang, Xiaoping; Schipper, Desmond; Hall, Justin W.; DePue, Lauren J.; Gnanam, Annie J.; Arambula, Jonathan F.; Jones, Jessica N.; Swaminathan, Jagannath; Dieye, Yakhya; Vadivelu, Jamuna; Chandler, Don J.; Marcotte, Edward M.; Sessler, Jonathan L.; Ehrlich, Lauren I. R.; Jones, Richard A.

    2015-01-01

    Chromophores that incorporate f-block elements have considerable potential for use in bioimaging applications because of their advantageous photophysical properties compared to organic dye, which are currently widely used. We are developing new classes of lanthanide-based self-assembling molecular nanoparticles as reporters for imaging and as multi-functional nanoprobes or nanosensors for use with biological samples. One class of these materials, which we call lanthanide “nano-drums”, are homogeneous 4d–4f clusters approximately 25 to 30 Å in diameter. These are capable of emitting from the visible to near-infrared wavelengths. Here, we present the synthesis, crystal structure, photophysical properties and comparative cytotoxicity data for a 32 metal Eu-Cd nano-drum [Eu8Cd24L12(OAc)48] (1). We also explored the imaging capabilities of this nano-drum using epifluorescence, TIRF, and two-photon microscopy platforms. PMID:25512085

  5. Magnetic hysteresis in a lanthanide molecular magnet dimer system

    NASA Astrophysics Data System (ADS)

    Atkinson, James; Cebulka, Rebecca; Del Barco, Enrique; Roubeau, Olivier; Velasco, Veronica; Barrios, Leo; Aromi, Guillem

    Molecular magnets present a wonderful means for studying the dynamics of spin. Often synthesized as a crystal lattice of identical systems, ensemble measurements enable thorough detailing of the internal degrees of freedom. Here we present the results of characterization performed on a dimer system, CeTm(HL)2(H2L)NO3pyH2O (L = ligand, C45H31O15N3), consisting of two lanthanide spins (Cerium and Thulium) with expected local axial anisotropies tilted with respect to each other. Microwave EPR spectroscopy at low temperature reveals hysteresis in observed absorption features, with angle dependence studies indicating the presence of several ``easy axis'' orientations. We attempt to understand this system through modelling via a spin Hamiltonian, and to determine the strength and nature of the coupling between the lanthanide centers. This research was funded through NSF Grant # 24086159.

  6. Lanthanides caged by the organic chelates; structural properties

    NASA Astrophysics Data System (ADS)

    Smentek, Lidia

    2011-04-01

    The structure, in particular symmetry, geometry and morphology of organic chelates coordinated with the lanthanide ions are analyzed in the present review. This is the first part of a complete presentation of a theoretical description of the properties of systems, which are widely used in technology, but most of all, in molecular biology and medicine. The discussion is focused on the symmetry and geometry of the cages, since these features play a dominant role in the spectroscopic activity of the lanthanides caged by organic chelates. At the same time, the spectroscopic properties require more formal presentation in the language of Racah algebra, and deserve a separate analysis. In addition to the parent systems of DOTA, DOTP, EDTMP and CDTMP presented here, their modifications by various antennas are analyzed. The conclusions that have a strong impact upon the theory of the energy transfer and the sensitized luminescence of these systems are based on the results of numerical density functional theory calculations.

  7. Interfacial Structure in Silicon Nitride Sintered with Lanthanide Oxide

    SciTech Connect

    Dwyer, C.; Ziegler, A.; Shibata, Naoya; Winkelman, G. B.; Satet, R. L.; Hoffmann, M. J.; Cinibulk, M. K.; Becher, Paul F; Painter, Gayle S; Browning, N. D.; Cockayne, D.J.H.; Ritchie, R O; Pennycook, Stephen J

    2006-01-01

    Three independent research groups present a comparison of their structural analyses of prismatic interfaces in silicon nitride densified with the aid of lanthanide oxide Ln{sub 2}O{sub 3}. All three groups obtained scanning transmission electron microscope images which clearly reveal the presence of well-defined Ln segregation sites at the interfaces, and, moreover, reveal that these segregation sites are element-specific. While some results differ across the three research groups, the vast majority exhibits good reproducibility.

  8. Lanthanide ions as spectral converters for solar cells.

    PubMed

    van der Ende, Bryan M; Aarts, Linda; Meijerink, Andries

    2009-12-21

    The use of lanthanide ions to convert photons to different, more useful, wavelengths is well-known from a wide range of applications (e.g. fluorescent tubes, lasers, white light LEDs). Recently, a new potential application has emerged: the use of lanthanide ions for spectral conversion in solar cells. The main energy loss in the conversion of solar energy to electricity is related to the so-called spectral mismatch: low energy photons are not absorbed by a solar cell while high energy photons are not used efficiently. To reduce the spectral mismatch losses both upconversion and downconversion are viable options. In the case of upconversion two low energy infrared photons that cannot be absorbed by the solar cell, are added up to give one high energy photon that can be absorbed. In the case of downconversion one high energy photon is split into two lower energy photons that can both be absorbed by the solar cell. The rich and unique energy level structure arising from the 4f(n) inner shell configuration of the trivalent lanthanide ions gives a variety of options for efficient up- and downconversion. In this perspective an overview will be given of recent work on photon management for solar cells. Three topics can be distinguished: (1) modelling of the potential impact of spectral conversion on the efficiency of solar cells; (2) research on up- and downconversion materials based on lanthanides; and (3) proof-of-principle experiments. Finally, an outlook will be given, including issues that need to be resolved before wide scale application of up- and downconversion materials can be anticipated.

  9. Ultracold lanthanides: from optical clock to a quantum simulator

    NASA Astrophysics Data System (ADS)

    Vishnyakova, G. A.; Golovizin, A. A.; Kalganova, E. S.; Sorokin, V. N.; Sukachev, D. D.; Tregubov, D. O.; Khabarova, K. Yu; Kolachevsky, N. N.

    2016-02-01

    We review the current research on precision spectroscopy and quantum optics applications of laser-cooled lanthanides. We discuss the specific electronic structure of hollow atoms, which determine prospects for application in optical frequency standards and in quantum simulators based on spin interactions in optical lattices. Using the example of the thulium atom, we describe the specifics of laser cooling, optical lattice trapping techniques, and clock transition spectroscopy using spectrally narrow lasers.

  10. Charge transfer and formation of reduced Ce{sup 3+} upon adsorption of metal atoms at the ceria (110) surface

    SciTech Connect

    Nolan, Michael

    2012-04-07

    The modification of cerium dioxide with nanoscale metal clusters is intensely researched for catalysis applications, with gold, silver, and copper having been particularly well studied. The interaction of the metal cluster with ceria is driven principally by a localised interaction between a small number of metal atoms (as small as one) and the surface and understanding the fundamentals of the interaction of metal atoms with ceria surfaces is therefore of great interest. Much attention has been focused on the interaction of metals with the (111) surface of ceria, since this is the most stable surface and can be grown as films, which are probed experimentally. However, nanostructures exposing other surfaces such as (110) show high activity for reactions including CO oxidation and require further study; these nanostructures could be modified by deposition of metal atoms or small clusters, but there is no information to date on the atomic level details of metal-ceria interactions involving the (110) surface. This paper presents the results of density functional theory (DFT) corrected for on-site Coulomb interactions (DFT+U) calculations of the adsorption of a number of different metal atoms at an extended ceria (110) surface; the metals are Au, Ag, Cu, Al, Ga, In, La, Ce, V, Cr, and Fe. Upon adsorption all metals are oxidised, transferring electron(s) to the surface, resulting in localised surface distortions. The precise details depend on the identity of the metal atom. Au, Ag, Cu each transfer one electron to the surface, reducing one Ce ion to Ce{sup 3+}, while of the trivalent metals, Al and La are fully oxidised, but Ga and In are only partially oxidised. Ce and the transition metals are also partially oxidised, with the number of reduced Ce ions possible in this surface no more than three per adsorbed metal atom. The predicted oxidation states of the adsorbed metal atoms should be testable in experiments on ceria nanostructures modified with metal atoms.

  11. Charge transfer and formation of reduced Ce3+ upon adsorption of metal atoms at the ceria (110) surface.

    PubMed

    Nolan, Michael

    2012-04-01

    The modification of cerium dioxide with nanoscale metal clusters is intensely researched for catalysis applications, with gold, silver, and copper having been particularly well studied. The interaction of the metal cluster with ceria is driven principally by a localised interaction between a small number of metal atoms (as small as one) and the surface and understanding the fundamentals of the interaction of metal atoms with ceria surfaces is therefore of great interest. Much attention has been focused on the interaction of metals with the (111) surface of ceria, since this is the most stable surface and can be grown as films, which are probed experimentally. However, nanostructures exposing other surfaces such as (110) show high activity for reactions including CO oxidation and require further study; these nanostructures could be modified by deposition of metal atoms or small clusters, but there is no information to date on the atomic level details of metal-ceria interactions involving the (110) surface. This paper presents the results of density functional theory (DFT) corrected for on-site Coulomb interactions (DFT+U) calculations of the adsorption of a number of different metal atoms at an extended ceria (110) surface; the metals are Au, Ag, Cu, Al, Ga, In, La, Ce, V, Cr, and Fe. Upon adsorption all metals are oxidised, transferring electron(s) to the surface, resulting in localised surface distortions. The precise details depend on the identity of the metal atom. Au, Ag, Cu each transfer one electron to the surface, reducing one Ce ion to Ce(3+), while of the trivalent metals, Al and La are fully oxidised, but Ga and In are only partially oxidised. Ce and the transition metals are also partially oxidised, with the number of reduced Ce ions possible in this surface no more than three per adsorbed metal atom. The predicted oxidation states of the adsorbed metal atoms should be testable in experiments on ceria nanostructures modified with metal atoms.

  12. Citrate based ``TALSPEAK`` lanthanide-actinide separation process

    SciTech Connect

    Del Cul, G.D.; Bond, W.D.; Toth, L.M.; Davis, G.D.; Dai, S.; Metcalf, D.H.

    1994-09-01

    The potential hazard posed to future generations by long-lived radionuclides such as the transuranic elements (TRU) is perceived as a major problem associated with the use of nuclear power. TRU wastes have to remain isolated from the environment for ``geological`` periods of time. The costs of building, maintaining, and operating a ``geological TRU repository`` can be very high. Therefore, there are significant economical advantages in segregating the relatively low volume of TRU wastes from other nuclear wastes. The chemical behavior of lanthanides and actinides, 4f and 5f elements respectively, is rather similar. As a consequence, the separation of these two groups is difficult. The ``TALSPEAK`` process (Trivalent Actinide Lanthanide Separations by Phosphorus-reagent Extraction from Aqueous Complexes) is one of the few means available to separate the trivalent actinides from the lanthanides. The method is based on the preferential complexation of the trivalent actinides by an aminopolyacetic acid. Cold experiments showed that by using citric acid the deleterious effects produced by impurities such as zirconium are greatly reduced.

  13. Enhanced Luminescence of Lanthanides: Determination of Europium by Enhanced Luminescence

    NASA Astrophysics Data System (ADS)

    Jenkins, Amanda L.; Murray, George M.

    1998-02-01

    An experiment has been developed to teach the principles of molecular luminescence spectroscopy. This laboratory experiment is designed for upper-level undergraduates as a less toxic alternative to current fluorescence experiments. It combines elements of physical and inorganic as well as analytical chemistry. The experiment can be performed on a variety of rudimentary fluorescence instrumentation and still give good analytical figures of merit. The object of the experiment is to measure the luminescent enhancement that is achieved when a lanthanide such as Eu(III) or Tb(III) is complexed with appropriate organic ligands, in this case 2,6 pyridinedicarboxylic acid. The importance of pH on metal ion coordination is also explored via luminescence intensity. This approach provides several advantages over current luminescence experiments. These advantages include limited toxicity and flammability of the chemicals involved, a large luminescence linear dynamic range, and low detection limits (parts per trillion). These low detection limits, achieved using modest equipment, allow the determination of the europium concentration in a variety of samples, such as tap water. The narrow lanthanide luminescent bands also permit incorporation of qualitative analysis of a mixture of lanthanides.

  14. Magnetic ordering in lanthanide-molybdenum oxide nanostructure arrays

    NASA Astrophysics Data System (ADS)

    Hagmann, Joseph; Le, Son; Schneemeyer, Lynn; Olsen, Patti; Besara, Tiglet; Siegrist, Theo; Seiler, David; Richter, Curt

    Reduced ternary molybdenum oxides, or bronzes, offer an attractive materials platform to study a wide variety of remarkable physical phenomena in a system with highly varied structural chemistry. Interesting electronic behaviors, such as superconductivity, charge density waves, and magnetism, in these materials arise from the strong hybridization of the 4d states of high-valent Mo with O p orbitals. We investigate a series of molybdenum bronze materials with Lanthanide-Mo16O44 composition that can be described as a three-dimensional array of metallic Mo8O32 nanostructures computationally predicted to contain a single charge with spin 1/2 separated by insulating MoO4 tetrahedra. This study reveals novel magnetic ordering in Lanthanide-Mo16O44 systems arising, not from the inclusion of magnetic elements, but rather from an exchange interaction between cubic Mo8O32 units. Here, we report the magnetometry and transport behaviors of a series of Lanthanide-Mo16O44 materials, emphasizing an observed low-temperature phase transition signifying the onset of antiferromagnetic ordering between the arrayed nanostructures, and relate these behaviors to their experimentally-characterized structures to reveal the intriguing physics of these correlated electronic systems.

  15. Characterization and Classification of Lanthanides by Multivariate-Analysis Methods

    NASA Astrophysics Data System (ADS)

    Horovitz, Ossi; Sârbu, Costel

    2005-03-01

    A chemometric study was conducted on a data set consisting of 18 characteristics, mainly physical properties of the 14 lanthanides and lanthanum, including Sc and Y. Classical methods of multivariate analysis, namely, principal component analysis (PCA) and cluster analysis (CA) were applied. The results obtained by using the Statistica software package are presented and discussed concerning the correlations between the properties and those between the elements themselves. The discussion and findings are based on the tables of correlation, the eigenvectors and eigenvalues of PCA, the 2D- and 3D-representations of the loadings of variables and scores of the elements corresponding to the first principal components, including also the dendrograms obtained by using CA. Loadings scatterplots are used as a display tool for examining the relationships between properties, looking for trends, grouping, or outliers. In the same way, the scatterplots of scores emphasized the difference between La and the lanthanides on the one side and Sc and Y on the other and support setting Lu as their homologue, rather than La. On the basis of these findings, a ”periodic system“ of the lanthanides is suggested that agrees well with chemical intuition.

  16. Ceria based inverse opals for thermochemical fuel production: Quantification and prediction of high temperature behavior

    NASA Astrophysics Data System (ADS)

    Casillas, Danielle Courtney

    Solar energy has the potential to supply more than enough energy to meet humanity's energy demands. Here, a method for thermochemical solar energy storage through fuel production is presented. A porous non-stoichiometric oxide, ceria, undergoes partial thermal reduction and oxidation with concentrated solar energy as a heat source, and water as an oxidant. The resulting yields for hydrogen fuel and oxygen are produced in two discrete steps, while the starting material maintains its original phase. Ordered porosity has been shown superior to random porosity for thermochemical fuel production applications, but stability limits for these structures are currently undefined. Ceria-based inverse opals are currently being investigated to assess the architectural influence on thermochemical hydrogen production. Low tortuosity and continuous interconnected pore network allow for facile gas transport and improved reaction kinetics. Ceria-based ordered materials have recently been shown to increase maximum hydrogen production over non-ordered porous ceria. Thermal stability of ordered porosity was quantified using quantitative image analysis. Fourier analysis was applied to SEM images of the material. The algorithm results in an order parameter gamma that describes the degree of long range order maintained by these structures, where gamma>4 signifies ordered porosity. According to this metric, a minimum zirconium content of 20 atomic percent (at%) is necessary for these architectures to survive aggressive annealing up to 1000°C. Zirconium substituted ceria (ZSC) with Zr loadings in excess of 20at% developed undesired tetragonal phases. Through gamma, we were able to find a balance between the benefit of zirconium additions on structural stability and its negative impact on phase. This work demonstrates the stability of seemingly delicate architectures, and the operational limit for ceria based inverse opals to be 1000°C for 1microm pore size. Inverse opals having sub

  17. Selective Removal of Lanthanides from Natural Waters, Acidic Streams and Dialysate

    SciTech Connect

    Yantasee, Wassana; Fryxell, Glen E.; Addleman, Raymond S.; Wiacek, Robert J.; Koonsiripaiboon, View; Pattamakomsan, Kanda; Sukwarotwat, Vichaya; Xu, Jide; Raymond, Kenneth N.

    2009-09-15

    The increased demand for the lanthanides in commercial products result in increased production of lanthanide containing ores, increasing public exposure to the lanthanides, both from various commercial products and from production wastes/effluents. This work investigates lanthanide (La, Ce, Pr, Nd, Eu, Gd, Lu) binding properties of self-assembled monolayers on mesoporous silica supports (SAMMS®) that were functionalized with diphosphonic acid (DiPhos), acetamide phosphonic acid (AcPhos), propionamide phosphonic acid (ProPhos), and 1-hydroxy-2-pyridinone (1,2-HOPO) from natural waters (river, ground, and sea waters), acid solutions (to mimic certain industrial process streams), and dialysate and compares their performance to a high surface area activated carbon. The properties include sorption affinity, capacity, and sorption kinetics. Stability and regenerability of SAMMS materials were also investigated. Going from the acid side over to the alkaline side, the AcPhos- and DiPhos-SAMMS maintain their outstanding affinity for lanthanides, which enable the use of the materials in the systems where the pH may fluctuate. While the activated carbon is as effective as 1,2-HOPO-SAMMS for capturing lanthanides in natural (alkaline) waters, it has no affinity in acid solutions (pH 2.4) and low affinity in carbonate-rich dialysate. Over 99% of 100 ug/L of Gd in dialysate was removed by the ProPhos-SAMMS after ten minutes. SAMMS can be regenerated with an acid wash (0.5 M HCl) without losing the binding properties, for a number of regeneration cycles. In acid solutions, PhoPhos- and 1,2-HOPO-SAMMS have differing affinity along the lanthanide series, suggesting their potential for chromatographic lanthanide separations. Thus, SAMMS materials have a great potential to be used as sorbents in large scale treatment of lanthanides, lanthanide separation prior to analytical instruments, and sorbent dialyzers for lanthanide clearances.

  18. Selective removal of lanthanides from natural waters, acidic streams and dialysate

    PubMed Central

    Yantasee, Wassana; Fryxell, Glen E.; Addleman, R. Shane; Wiacek, Robert J.; Koonsiripaiboon, View; Pattamakomsan, Kanda; Sukwarotwat, Vichaya; Xu, Jide; Raymond, Kenneth N.

    2009-01-01

    The increased demand for the lanthanides in commercial products result in increased production of lanthanide containing ores, which increases public exposure to the lanthanides, both from various commercial products and from production wastes/effluents. This work investigates lanthanide (La, Ce, Pr, Nd, Eu, Gd and Lu) binding properties of self-assembled monolayers on mesoporous silica supports (SAMMS™), that were functionalized with diphosphonic acid (DiPhos), acetamide phosphonic acid (AcPhos), propionamide phosphonic acid (Prop-Phos), and 1-hydroxy-2-pyridinone (1,2-HOPO), from natural waters (river, ground and sea waters), acid solutions (to mimic certain industrial process streams), and dialysate. The affinity, capacity, and kinetics of the lanthanide sorption, as well as regenerability of SAMMS materials were investigated. Going from the acid side over to the alkaline side, the AcPhos- and DiPhos-SAMMS maintain their outstanding affinity for lanthanides, which enable the use of the materials in the systems where the pH may fluctuate. In acid solutions, Prop-Phos- and 1,2-HOPO-SAMMS have differing affinity along the lanthanide series, suggesting their use in chromatographic lanthanide separation. Over 95% of 100 µg/L of Gd in dialysate was removed by the Prop-Phos-SAMMS after 1 min and 99% over 10 min. SAMMS can be regenerated with an acid wash (0.5 M HCl) without losing the binding properties. Thus, they have a great potential to be used as in large-scale treatment of lanthanides, lanthanide separation prior to analytical instruments, and in sorbent dialyzers for treatment of acute lanthanide poisoning. PMID:19345006

  19. Semiempirical quantum chemistry model for the lanthanides: RM1 (Recife Model 1) parameters for dysprosium, holmium and erbium.

    PubMed

    Filho, Manoel A M; Dutra, José Diogo L; Rocha, Gerd B; Simas, Alfredo M; Freire, Ricardo O

    2014-01-01

    Complexes of dysprosium, holmium, and erbium find many applications as single-molecule magnets, as contrast agents for magnetic resonance imaging, as anti-cancer agents, in optical telecommunications, etc. Therefore, the development of tools that can be proven helpful to complex design is presently an active area of research. In this article, we advance a major improvement to the semiempirical description of lanthanide complexes: the Recife Model 1, RM1, model for the lanthanides, parameterized for the trications of Dy, Ho, and Er. By representing such lanthanide in the RM1 calculation as a three-electron atom with a set of 5 d, 6 s, and 6 p semiempirical orbitals, the accuracy of the previous sparkle models, mainly concentrated on lanthanide-oxygen and lanthanide-nitrogen distances, is extended to other types of bonds in the trication complexes' coordination polyhedra, such as lanthanide-carbon, lanthanide-chlorine, etc. This is even more important as, for example, lanthanide-carbon atom distances in the coordination polyhedra of the complexes comprise about 30% of all distances for all complexes of Dy, Ho, and Er considered. Our results indicate that the average unsigned mean error for the lanthanide-carbon distances dropped from an average of 0.30 Å, for the sparkle models, to 0.04 Å for the RM1 model for the lanthanides; for a total of 509 such distances for the set of all Dy, Ho, and Er complexes considered. A similar behavior took place for the other distances as well, such as lanthanide-chlorine, lanthanide-bromine, lanthanide, phosphorus and lanthanide-sulfur. Thus, the RM1 model for the lanthanides, being advanced in this article, broadens the range of application of semiempirical models to lanthanide complexes by including comprehensively many other types of bonds not adequately described by the previous models.

  20. Semiempirical Quantum Chemistry Model for the Lanthanides: RM1 (Recife Model 1) Parameters for Dysprosium, Holmium and Erbium

    PubMed Central

    Filho, Manoel A. M.; Dutra, José Diogo L.; Rocha, Gerd B.; Simas, Alfredo M.; Freire, Ricardo O.

    2014-01-01

    Complexes of dysprosium, holmium, and erbium find many applications as single-molecule magnets, as contrast agents for magnetic resonance imaging, as anti-cancer agents, in optical telecommunications, etc. Therefore, the development of tools that can be proven helpful to complex design is presently an active area of research. In this article, we advance a major improvement to the semiempirical description of lanthanide complexes: the Recife Model 1, RM1, model for the lanthanides, parameterized for the trications of Dy, Ho, and Er. By representing such lanthanide in the RM1 calculation as a three-electron atom with a set of 5 d, 6 s, and 6 p semiempirical orbitals, the accuracy of the previous sparkle models, mainly concentrated on lanthanide-oxygen and lanthanide-nitrogen distances, is extended to other types of bonds in the trication complexes’ coordination polyhedra, such as lanthanide-carbon, lanthanide-chlorine, etc. This is even more important as, for example, lanthanide-carbon atom distances in the coordination polyhedra of the complexes comprise about 30% of all distances for all complexes of Dy, Ho, and Er considered. Our results indicate that the average unsigned mean error for the lanthanide-carbon distances dropped from an average of 0.30 Å, for the sparkle models, to 0.04 Å for the RM1 model for the lanthanides; for a total of 509 such distances for the set of all Dy, Ho, and Er complexes considered. A similar behavior took place for the other distances as well, such as lanthanide-chlorine, lanthanide-bromine, lanthanide, phosphorus and lanthanide-sulfur. Thus, the RM1 model for the lanthanides, being advanced in this article, broadens the range of application of semiempirical models to lanthanide complexes by including comprehensively many other types of bonds not adequately described by the previous models. PMID:24497945

  1. Periodic behavior of lanthanide coordination within reverse micelles.

    PubMed

    Ellis, Ross J; Meridiano, Yannick; Chiarizia, Renato; Berthon, Laurence; Muller, Julie; Couston, Laurent; Antonio, Mark R

    2013-02-18

    Trends in lanthanide(III) (Ln(III)) coordination were investigated within nanoconfined solvation environments. Ln(III) ions were incorporated into the cores of reverse micelles (RMs) formed with malonamide amphiphiles in n-heptane by contact with aqueous phases containing nitrate and Ln(III); both insert into pre-organized RM units built up of DMDOHEMA (N,N'-dimethyl-N,N'-dioctylhexylethoxymalonamide) that are either relatively large and hydrated or small and dry, depending on whether the organic phase is acidic or neutral, respectively. Structural aspects of the Ln(III) complex formation and the RM morphology were obtained by use of XAS (X-ray absorption spectroscopy) and SAXS (small-angle X-ray scattering). The Ln(III) coordination environments were determined through use of L(3)-edge XANES (X-ray absorption near edge structure) and EXAFS (extended X-ray absorption fine structure), which provide metrical insights into the chemistry across the period. Hydration numbers for the Eu species were measured using TRLIFS (time-resolved laser-induced fluorescence spectroscopy). The picture that emerges from a system-wide perspective of the Ln-O interatomic distances and number of coordinating oxygen atoms for the extracted complexes of Ln(III) in the first half of the series (i.e., Nd, Eu) is that they are different from those in the second half of the series (i.e., Tb, Yb): the number of coordinating oxygen atoms decrease from 9O for early lanthanides to 8O for the late ones--a trend that is consistent with the effect of the lanthanide contraction. The environment within the RM, altered by either the presence or absence of acid, also had a pronounced influence on the nitrate coordination mode; for example, the larger, more hydrated, acidic RM core favors monodentate coordination, whereas the small, dry, neutral core favors bidentate coordination to Ln(III). These findings show that the coordination chemistry of lanthanides within nanoconfined environments is neither

  2. Sub-nA spatially resolved conductivity profiling of surface and interface defects in ceria films

    DOE PAGES

    Farrow, Tim; Yang, Nan; Doria, Sandra; Belianinov, Alex; Jesse, Stephen; Arruda, Thomas M.; Balestrino, Giuseppe; Kalinin, Sergei V.; Kumar, Amit

    2015-03-17

    Spatial variability of conductivity in ceria is explored using scanning probe microscopy with galvanostatic control. Ionically blocking electrodes are used to probe the conductivity under opposite polarities to reveal possible differences in the defect structure across a thin film of CeO2. Data suggest the existence of a large spatial inhomogeneity that could give rise to constant phase elements during standard electrochemical characterization, potentially affecting the overall conductivity of films on the macroscale. The approach discussed here can also be utilized for other mixed ionic electronic conductor systems including memristors and electroresistors, as well as physical systems such as ferroelectric tunnelingmore » barriers« less

  3. Sub-nA spatially resolved conductivity profiling of surface and interface defects in ceria films

    SciTech Connect

    Farrow, Tim; Yang, Nan; Doria, Sandra; Belianinov, Alex; Jesse, Stephen; Arruda, Thomas M.; Balestrino, Giuseppe; Kalinin, Sergei V.; Kumar, Amit

    2015-03-17

    Spatial variability of conductivity in ceria is explored using scanning probe microscopy with galvanostatic control. Ionically blocking electrodes are used to probe the conductivity under opposite polarities to reveal possible differences in the defect structure across a thin film of CeO2. Data suggest the existence of a large spatial inhomogeneity that could give rise to constant phase elements during standard electrochemical characterization, potentially affecting the overall conductivity of films on the macroscale. The approach discussed here can also be utilized for other mixed ionic electronic conductor systems including memristors and electroresistors, as well as physical systems such as ferroelectric tunneling barriers

  4. Sub-nA spatially resolved conductivity profiling of surface and interface defects in ceria films

    SciTech Connect

    Farrow, Tim; Kumar, Amit; Yang, Nan; Doria, Sandra; Balestrino, Giuseppe; Belianinov, Alex; Jesse, Stephen; Kalinin, Sergei V.; Arruda, Thomas M.

    2015-03-01

    Spatial variability of conductivity in ceria is explored using scanning probe microscopy with galvanostatic control. Ionically blocking electrodes are used to probe the conductivity under opposite polarities to reveal possible differences in the defect structure across a thin film of CeO{sub 2}. Data suggest the existence of a large spatial inhomogeneity that could give rise to constant phase elements during standard electrochemical characterization, potentially affecting the overall conductivity of films on the macroscale. The approach discussed here can also be utilized for other mixed ionic electronic conductor systems including memristors and electroresistors, as well as physical systems such as ferroelectric tunneling barriers.

  5. Fungus-promoted transformation of lanthanides during the biooxidation of divalent manganese

    NASA Astrophysics Data System (ADS)

    Yu, Qianqian; Ohnuki, Toshihiko; Tanaka, Kazuya; Kozai, Naofumi; Yamasaki, Shinya; Sakamoto, Fuminori; Tani, Yukinori

    2016-02-01

    Although microorganisms possess high sorption capability for lanthanides, the effect of their biological response on lanthanides migration is unclear. Using active fungus Acremonium strictum KR21-2, supplied with nutrients, this study compared the transformation of lanthanides during the biooxidation of Mn(II) in the absence and presence of trisodium citrate. In the absence of trisodium citrate, lanthanides were rapidly sorbed on fungal cells within 24 h, followed by the preferential desorption of Ce over other lanthanides as Mn oxide formed. Most of the desorbed Ce was in the colloidal phase and associated with a biomolecule produced by the active fungus. In contrast, neither desorption of Ce nor release of this biomolecule occurred in the presence of trisodium citrate. Most importantly, the Ce-binding biomolecule was not found to associate with any other trivalent lanthanides tested or with Fe. The biomolecule was characterized as c.a. 4700 Da in size, and it contains saccharides that differed from those non-nuclide-specific organic substances released from resting cells, as reported previously. This study highlights the importance of biotic reactions between lanthanides and microbial cells, which may affect the migration of lanthanides at the water-Mn oxide interface.

  6. Lanthanides in Metallic Nuclear Fuels: Their Behavior and Methods for Their Control

    SciTech Connect

    Robert D. Mariani; Douglas L. Porter; Thomas P. O'Holleran; Steven L. Hayes; J. Rory Kennedy

    2011-12-01

    The thermodynamic and experimental basis is given for using dopant additives to bind lanthanides as intermetallic compounds in metallic nuclear fuels. Lanthanide fission products are a major factor in limiting the lifetime of the fuel, because they migrate to the fuel slug peripheral surface where they participate in fuel-cladding chemical interactions (FCCI) with the steel cladding. Lanthanide carryover in recycled metal fuels can accelerate FCCI, as recycled lanthanides would likely segregate from the fuel phase, putting the lanthanides in prompt contact with the cladding. In out-of-pile tests we examined the use of Pd for binding the lanthanides, with Pd selected because of its known metallurgical properties in fuel related systems and because of its known behavior in irradiated EBR-II fuels. Initial results confirmed that palladium may be expected to mitigate FCCI arising from lanthanides, and it has been recommended for in-pile tests. We also evaluated transport phenomena responsible for lanthanide migration, and identified liquid-like behaviors as being dominant. Liquid-like behaviors include transport with liquid metals, liquid metal solutions, and rapid surface transport of alloys/metals near their melting temperatures. The analysis led to establishing general criteria for selecting alternate dopant additives, and identifying Sn, Sb, and Te as alternates for further testing.

  7. Development of highly luminescent and water-dispersible lanthanide-based nanomaterials for potential bio-medical imaging

    NASA Astrophysics Data System (ADS)

    Attanayake, Gayanthi Kumari

    Lanthanide metal ions exhibit fascinating optical and magnetic properties. Lanthanide-based nanomaterials have potential applications in optical devices, telecommunication, electroluminescent devices, bio-analytical sensors, and bio-medical imaging technology. Despite the recent developments, low luminescence characteristics, poor water solubility, and poor cell selectivity of lanthanide-based materials limit their use in bio-medical applications. This project is designed to mainly improve the luminescence properties of Eu(III)-based nanomaterials for their potential use in biomedical applications. In addition, we explore synthetic methods to enhance the water dispersibility and melanoma cell selectivity of the nanoparticles. Current research is designed to address the above mentioned drawbacks of lanthanide-based nanomaterials. Two different nanoparticle systems were developed in this project. i. europium (Eu)-based down-converting nanoparticles, ii. ytterbium (Yb)- erbium (Er)-based upconverting nanoparticles. Many down-converting nanoparticle systems suffer from low-luminescence efficiencies due to their poor light absorption by direct excitation of the lanthanide ions. In order to improve the luminescence characteristics, we have designed a novel nanomaterial by surface-coating it with organic chromophores having strong light absorption properties. LaEuF3.AEP (La=lanthanum, AEP = aminoethyl phosphate) nanoparticles were successfully synthesized using a low temperature heating method and Eu-based NaYF4 nanoparticles were synthesized using a high temperature heating method. A ligand exchange procedure was developed to functionalize the surface of the nanoparticles with an organic chromophore, TTA (thenoyltrifluoroacetone). The TTA functionalized Eu(III)-based nanoparticles exhibit impressive luminescence enhancements utilizing the sensitization effect. Poor water solubility is the main drawback of the upconverting nanoparticles for bio-medical applications. We

  8. Gene doping.

    PubMed

    Harridge, Stephen D R; Velloso, Cristiana P

    2008-01-01

    Gene doping is the misuse of gene therapy to enhance athletic performance. It has recently been recognised as a potential threat and subsequently been prohibited by the World Anti-Doping Agency. Despite concerns with safety and efficacy of gene therapy, the technology is progressing steadily. Many of the genes/proteins which are involved in determining key components of athletic performance have been identified. Naturally occurring mutations in humans as well as gene-transfer experiments in adult animals have shown that altered expression of these genes does indeed affect physical performance. For athletes, however, the gains in performance must be weighed against the health risks associated with the gene-transfer process, whereas the detection of such practices will provide new challenges for the anti-doping authorities.

  9. Performance of colloidal silica and ceria based slurries on CMP of Si-face 6H-SiC substrates

    NASA Astrophysics Data System (ADS)

    Chen, Guomei; Ni, Zifeng; Xu, Laijun; Li, Qingzhong; Zhao, Yongwu

    2015-12-01

    Colloidal silica and ceria based slurries, both using KMnO4 as an oxidizer, for chemical mechanical polishing (CMP) of Si-face (0 0 0 1) 6H-SiC substrate, were investigated to obtain higher material removal rate (MRR) and ultra-smooth surface. The results indicate that there was a significant difference in the CMP performance of 6H-SiC between silica and ceria based slurries. For the ceria based slurries, a higher MRR was obtained, especially in strong acid KMnO4 environment, and the maximum MRR (1089 nm/h) and a smoother surface with an average roughness Ra of 0.11 nm was achieved using slurries containing 2 wt% colloidal ceria, 0.05 M KMnO4 at pH 2. In contrast, due to the attraction between negative charged silica particles and positive charged SiC surface below pH 5, the maximum MRR of silica based slurry was only 185 nm/h with surface roughness Ra of 0.254 nm using slurries containing 6 wt% colloidal silica, 0.05 M KMnO4 at pH 6. The polishing mechanism was discussed based on the zeta potential measurements of the abrasives and the X-ray photoelectron spectroscopy (XPS) analysis of the polished SiC surfaces.

  10. Influence of Ce/Zr ratio on CO oxidation activity of ceria-zirconia supported Cu catalyst

    NASA Astrophysics Data System (ADS)

    Hattori, Masatomo; Haneda, Masaaki; Ozawa, Masakuni

    2016-01-01

    The influence of Ce/Zr ratios in the cerium-rich region on the dispersibility and reduction property of Cu catalysts supported on ceria-zirconia composite oxides was investigated. In the catalysts, the dispersibility of copper oxide species on ceria-zirconia supports was different depending on Ce/Zr ratio. The particle size of copper oxide species on Ce0.7Zr0.3O2 was smaller than that on Ce0.5Zr0.5O2. CO oxidation activity of 1.0 wt % Cu/Ce0.7Zr0.3O2 was higher than that of 1.0 wt % Cu/Ce0.5Zr0.5O2. Temperature programmed reduction by CO (CO-TPR) measurement revealed that the reducibility of Cu/Ce0.7Zr0.3O2 was higher than that of Cu/Ce0.5Zr0.5O2. The temperature of the first peak in CO-TPR profiles for both catalysts was in good agreement with the temperature at which the conversion of CO reached 50% (T50). It is suggested that the copper oxide species — ceria-zirconia interaction influences the activation of oxygen at the interface between copper oxide species and ceria-zirconia, resulting in different catalytic performance for CO oxidation.

  11. Surface and redox properties of cobalt-ceria binary oxides: On the effect of Co content and pretreatment conditions

    NASA Astrophysics Data System (ADS)

    Konsolakis, Michalis; Sgourakis, Michalis; Carabineiro, Sónia A. C.

    2015-06-01

    Ceria-based transition metal catalysts have recently received considerable attention both in heterogeneous catalysis and electro-catalysis fields, due to their unique physicochemical characteristics. Their catalytic performance is greatly affected by the surface local chemistry and oxygen vacancies. The present study aims at investigating the impact of Co/Ce ratio and pretreatment conditions on the surface and redox properties of cobalt-ceria binary oxides. Co-ceria mixed oxides with different Co content (0, 20, 30, 60, 100 wt.%) were prepared by impregnation method and characterized by means of N2 adsorption at -196 °C, X-ray diffraction (XRD), H2 temperature-programmed reduction (H2-TPR) and X-ray photoelectron spectroscopy (XPS). The results shown the improved reducibility of Co/CeO2 mixed oxides compared to single oxides, due to a synergistic interaction between cobalt and cerium. Oxidation pretreatment results in a preferential localization of cerium species on the outer surface. In contrast, a uniform distribution of cobalt and cerium species over the entire catalyst surface is obtained by the reduction process, which facilitates the formation of oxygen vacancies though Co3+/Co2+ and Ce3+/Ce4+ redox cycles. Fundamental insights toward tuning the surface chemistry of cobalt-ceria binary oxides are provided, paving the way for real-life industrial applications.

  12. Magnetically recyclable magnetite-ceria (Nanocat-Fe-Ce) nanocatalysts - applications in multicomponent reactions under benign conditions

    EPA Science Inventory

    A novel magnetite nanoparticle-supported ceria catalyst (Nanocat-Fe-Ce) has been successfully prepared by simple impregnation method and was well characterized by XRD, SIMS, FEG-SEM-EDS, and TEM. The exact nature of Nanocat-Fe-Ce was confirmed by X-ray photoelectron spectroscopy ...

  13. Ceria nanoclusters on graphene/Ru(0001): A new model catalyst system

    DOE PAGES

    Novotny, Z.; Netzer, F. P.; Dohnalek, Z.

    2016-03-22

    In this study, the growth of ceria nanoclusters on single-layer graphene on Ru(0001) has been examined, with a view towards fabricating a stable system for model catalysis studies. The surface morphology and cluster distribution as a function of oxide coverage and substrate temperature has been monitored by scanning tunneling microscopy (STM), whereas the chemical composition of the cluster deposits has been determined by Auger electron spectroscopy (AES). The ceria nanoparticles are of the CeO2(111)-type and are anchored at the intrinsic defects of the graphene surface, resulting in a variation of the cluster densities across the macroscopic sample surface. The ceriamore » clusters on graphene display a remarkable stability against reduction in ultrahigh vacuum up to 900 K, but some sintering of clusters is observed for temperatures > 450 K. The evolution of the cluster size distribution suggests that the sintering proceeds via a Smoluchowski ripening mechanism, i.e. diffusion and aggregation of entire clusters.« less

  14. Support effect in oxide catalysis: methanol oxidation on vanadia/ceria.

    PubMed

    Kropp, Thomas; Paier, Joachim; Sauer, Joachim

    2014-10-15

    Density functional theory is used for periodic models of monomeric vanadia species deposited on the CeO2(111) surface to study dissociative adsorption of methanol and its subsequent dehydrogenation to formaldehyde. Dispersion-corrected PBE+U calculations are performed and compared with HSE and B3LYP results. Dissociative adsorption of methanol at different sites on VO2·CeO2(111) is highly exothermic with adsorption energies of 1.8 to 1.9 eV (HSE+D). Two relevant pathways for desorption of formaldehyde are found with intrinsic barriers for the redox step of 1.0 and 1.4 eV (HSE+D). The calculated desorption temperatures (370 and 495 K) explain the peaks observed in temperature-programmed desorption experiments. Different sites of the supported catalyst system are involved in the two pathways: (i) methanol can chemisorb on the CeO2 surface filling a so-called pseudovacancy and the H atom is transferred to an V-O-Ce interphase bond or (ii) CH3OH may chemisorb at the V-O-Ce interphase bond and form a V-OCH3 species from which H is transferred to the ceria surface, providing evidence for true cooperativity. In both cases, ceria is directly involved in the redox process, as two electrons are accommodated in Ce f states forming two Ce(3+) ions whereas vanadium remains fully oxidized (V(5+)). PMID:25275568

  15. Controlling Heteroepitaxy by Oxygen Chemical Potential: Exclusive Growth of (100) Oriented Ceria Nanostructures on Cu(111)

    DOE PAGES

    Höcker, Jan; Duchoň, Tomáš; Veltruská, Kateřina; Matolín, Vladimír; Falta, Jens; Senanayake, Sanjaya D.; Flege, J. Ingo

    2016-01-06

    We present a novel and simple method for the preparation of a well-defined CeO2(100) model system on Cu(111) based on the adjustment of the Ce/O ratio during growth. The method yields micrometer-sized, several nanometers high, single-phase CeO2(100) islands with controllable size and surface termination that can be benchmarked against the known (111) nanostructured islands on Cu(111). We also demonstrate the ability to adjust the Ce to O stoichiometry from CeO2(100) (100% Ce4+) to c-Ce2O3(100) (100% Ce3+), which can be readily recognized by characteristic surface reconstructions observed by low-energy electron diffraction. Finally, the discovery of the highly stable CeOx(100) phase onmore » a hexagonally close packed metal surface represents an unexpected growth mechanism of ceria on Cu(111), and it provides novel opportunities to prepare more elaborate models, benchmark surface chemical reactivity, and thus gain valuable insights into the redox chemistry of ceria in catalytic processes.« less

  16. Ceria-thoria pellet manufacturing in preparation for plutonia-thoria LWR fuel production

    NASA Astrophysics Data System (ADS)

    Drera, Saleem S.; Björk, Klara Insulander; Sobieska, Matylda

    2016-10-01

    Thorium dioxide (thoria) has potential to assist in niche roles as fuel for light water reactors (LWRs). One such application for thoria is its use as the fertile component to burn plutonium in a mixed oxide fuel (MOX). Thor Energy and an international consortium are currently irradiating plutonia-thoria (Th-MOX) fuel in an effort to produce data for its licensing basis. During fuel-manufacturing research and development (R&D), surrogate materials were utilized to highlight procedures and build experience. Cerium dioxide (ceria) provides a good surrogate platform to replicate the chemical nature of plutonium dioxide. The project's fuel manufacturing R&D focused on powder metallurgical techniques to ensure manufacturability with the current commercial MOX fuel production infrastructure. The following paper highlights basics of the ceria-thoria fuel production including powder milling, pellet pressing and pellet sintering. Green pellets and sintered pellets were manufactured with average densities of 67.0% and 95.5% that of theoretical density respectively.

  17. Magnetic colorimetric immunoassay for human interleukin-6 based on the oxidase activity of ceria spheres.

    PubMed

    Peng, Juan; Guan, Jufang; Yao, Huiqin; Jin, Xiaoyong

    2016-01-01

    A novel magnetic colorimetric immunoassay strategy was designed for sensitive detection of human interleukin-6 (IL-6) using ceria spheres as labels. Ceria spheres showed excellent oxidase activity, which can directly catalyze the oxidation of substrate o-phenylenediamine (OPD) to a stable yellow product, 2,3-diaminophenazine (oxOPD). The absorbance of oxOPD was recorded to reflect the level of IL-6. The relatively mild conditions made the immunoassay strategy more robust, reliable, and easy. A linear relationship between absorbance intensity and the logarithm of IL-6 concentrations was obtained in the range of 0.0001-10 ng mL(-1) with a detection limit of 0.04 pg mL(-1) (S/N = 3). The colorimetric immunoassay exhibited high sensitivity and specificity for the detection of IL-6. This immunoassay has been successfully applied in the detection of IL-6 in serum samples and can be readily extended toward the on-site monitoring of cancer biomarkers in serum samples. PMID:26416691

  18. Design of a Solar Reactor to Split CO2 Via Isothermal Redox Cycling of Ceria

    SciTech Connect

    Bader, R; Chandran, RB; Venstrom, LJ; Sedler, SJ; Krenzke, PT; De Smith, RM; Banerjee, A; Chase, TR; Davidson, JH; Lipinski, W

    2014-12-23

    The design procedure for a 3 kWth prototype solar thermochemical reactor to implement isothermal redox cycling of ceria for CO2 splitting is presented. The reactor uses beds of mm-sized porous ceria particles contained in the annulus of concentric alumina tube assemblies that line the cylindrical wall of a solar cavity receiver. The porous particle beds provide high surface area for the heterogeneous reactions, rapid heat and mass transfer, and low pressure drop. Redox cycling is accomplished by alternating flows of inert sweep gas and CO2 through the bed. The gas flow rates and cycle step durations are selected by scaling the results from small-scale experiments. Thermal and thermo-mechanical models of the reactor and reactive element tubes are developed to predict the steady-state temperature and stress distributions for nominal operating conditions. The simulation results indicate that the target temperature of 1773K will be reached in the prototype reactor and that the Mohr-Coulomb static factor of safety is above two everywhere in the tubes, indicating that thermo-mechanical stresses in the tubes remain acceptably low.

  19. Fast vacancy-mediated oxygen ion incorporation across the ceria-gas electrochemical interface.

    PubMed

    Feng, Zhuoluo A; El Gabaly, Farid; Ye, Xiaofei; Shen, Zhi-Xun; Chueh, William C

    2014-07-09

    Electrochemical incorporation reactions are ubiquitous in energy storage and conversion devices based on mixed ionic and electronic conductors, such as lithium-ion batteries, solid-oxide fuel cells and water-splitting membranes. The two-way traffic of ions and electrons across the electrochemical interface, coupled with the bulk transport of mass and charge, has been challenging to understand. Here we report an investigation of the oxygen-ion incorporation pathway in CeO2-δ (ceria), one of the most recognized oxygen-deficient compounds, during hydrogen oxidation and water splitting. We probe the response of surface oxygen vacancies, electrons and adsorbates to the electrochemical polarization at the ceria-gas interface. We show that surface oxygen-ion transfer, mediated by oxygen vacancies, is fast. Furthermore, we infer that the electron transfer between cerium cations and hydroxyl ions is the rate-determining step. Our in operando observations reveal the precise roles of surface oxygen vacancy and electron defects in determining the rate of surface incorporation reactions.

  20. Near-ambient XPS characterization of interfacial copper species in ceria-supported copper catalysts.

    PubMed

    Monte, Manuel; Munuera, Guillermo; Costa, Dominique; Conesa, José C; Martínez-Arias, Arturo

    2015-11-28

    Catalysts based on combinations of copper and cerium oxides are interesting alternatives to noble metal ones for processes involved in the production/purification of hydrogen produced from hydrocarbons or biomass like the water-gas shift or the preferential oxidation of CO reactions. Active sites for such processes have been proposed to correspond to reduced species formed at the interface between both oxides. The present work provides direct evidence of reduced copper species located at the interface and observed during the course of near-ambient XPS experiments performed over samples of copper oxide supported on ceria nanospheres and nanocubes subjected to interaction with CO at different temperatures. The analysis of XPS results is based on DFT+U calculations employed as a complementary method for the analysis of redox properties of the catalysts and core-level shifts produced upon such redox changes. Differences observed in interfacial redox properties as a function of the ceria support morphology appear to be most useful to explain catalytic properties of this type of system for mentioned processes.

  1. Pulsed Laser Deposited Dysprosium-Doped Gadolinium-Vanadate Thin Films for Noncontact, Self-Referencing Luminescence Thermometry.

    PubMed

    Antić, Željka; Dramićanin, Miroslav D; Prashanthi, Kovur; Jovanović, Dragana; Kuzman, Sanja; Thundat, Thomas

    2016-09-01

    Lanthanide-doped vanadate thin films offer (i) a promising platform for luminescence-based noncontact temperature sensing; (ii) ratiometric/self-referencing absolute measurements; (iii) exceptional repeatability and reversibility for multirun uses and a long life cycle; (iv) 2% K(-1) maximum temperature sensitivity (among the highest recorded for inorganic nanothermometers); (v) a temperature resolution greater than 0.5 K; and (vi) the potential for high-resolution 2D temperature mapping.

  2. Novel states of matter with ultracold magnetic lanthanides

    NASA Astrophysics Data System (ADS)

    Kotochigova, Svetlana

    2016-05-01

    Ultracold atomic physics is now poised to enter a new regime, where far-more complex atomic species can be cooled and studied. Magnetic lanthanide atoms with their large magnetic moment and large orbital momentum are extreme examples of such species. In fact, ultracold gases of magnetic lanthanides provide the opportunity to examine strongly correlated matter, creating a platform to explore exotic many-body phases such as quantum ferrofluids, quantum liquid crystals, and supersolids. Experimental advances in trapping and cooling magnetic Dy and Er atoms are paving the way towards these goals. Over the last few years we have developed a framework for understanding the complex anisotropic interactions between magnetic lanthanide atoms. Our theoretical model uses novel tools and advanced numerical treatments to describe the underlying mechanism that generates correlations and chaos in dipolar scattering and bridges the enormous conceptual gap between simple atoms and complex molecules. This allows us to explain the origin of the dense spectra and statistics of the observed Er and Dy collisional resonances due to the anisotropy of the short- and long-range interactions between the atoms. We also study the distribution of the values of the molecular wave functions to isolate Anderson-type localized states within chaotic structures and confirm the existence of an intermediate chaotic regime. In addition, our model for the three-body recombination via the formation of a resonant trimer has identified the origin of the temperature-sensitive resonance density observed in both Er and Dy collisions as due to d-wave entrance channel collisions. This work is supported by AFOSR (No. FA9550-14-1-0321) and NSF (No. PHY-1308573) grants.

  3. Centrifugal atomization of lanthanide materials for cryogenic coolers

    SciTech Connect

    Osborne, M.G.

    1994-01-04

    Until recently, Pb was the preferred heat exchanger matrix material used in low temperature cryocoolers; however, the heat capacity of Pb drops drastically below {approximately}15K and new matrix materials based on the lanthanide elements have been developed. These materials magnetically order at low temperatures and the entropy change associated with ordering contributes to the materials` heat capacities. The drawback to widespread use of lanthanide intermetallic compounds in cryocoolers has been the difficulty in manufacturing high-quality particulates. The purpose of this project was to develop a technique for producing high-quality powders of lanthanide metals and lanthanide intermetallic compounds for use in cryocooler heat exchangers. A series of atomization experiments was performed using Er{sub 3}Ni, Nd, Nd{sub 3}Ni, and (Er{sub 0.5}Nd{sub 0.5}){sub 3}Ni. Atomization of these materials resulted in particles ranging from mostly spherical to extremely flattened. Analyses of size distributions for the experiments indicate that increased atomization disk speed and superheat result in smaller mean particle diameters and narrower size distributions. Chemical analyses of the atomized powders indicate that the CA/RQB technique produces particulate with much lower interstitial contamination than other techniques. The Er{sub 3}Ni and Nd{sub 3}Ni powders were predominantly of the desired phase and the (Er{sub 0.5}Nd{sub 0.5}){sub 3}Ni powder had one major and possibly three minor phases. The solidification morphology is typically fine dendritic or cellular with finer microstructure spacings near the particle surfaces. The Er{sub 3}Ni powders have higher heat capacities than gas atomized powders reported in literature. The heat capacity of Nd{sub 3}Ni has a peak which does not degrade dramatically with processing. The (Er{sub 0.5}Nd{sub 0.5}){sub 3}Ni material has a higher heat capacity compared to Er{sub 3}Ni, Nd{sub 3}Ni, and Nd at temperatures above 10K.

  4. A lanthanide complex for metal encapsulations and anion exchanges.

    PubMed

    Sun, Yan-Qiong; Wan, Fang; Li, Xin-Xiong; Lin, Jian; Wu, Tao; Zheng, Shou-Tian; Bu, Xianhui

    2016-08-01

    A cationic lanthanide metalloligand with 3 dangling carboxylate groups on its periphery co-assembles with nitrate into a porous thermochromic solid responsive to both external cations and anions, owing to the presence of exchangeable NO3(-) as well as cation cavities arising from cooperative orientation of free carboxylate groups. An especially interesting feature is the structural memory effect during crystallization exhibited by the metalloligand, even after dissolution and binding to secondary cations (Cu(2+), Cd(2+)…). Moreover, the porous solid can undergo ion-exchange with various anions, leading to tunable thermochromic temperature and color range. PMID:27463609

  5. Surface X-ray emission from lanthanide metals

    NASA Astrophysics Data System (ADS)

    Hübinger, F.; Shulakov, A. S.; Starke, K.; Grigoriev, A.; Kaindl, G.

    2003-02-01

    O 3 X-ray emission (XE) upon 5p 3/2 electron-impact ionization of La(0 0 0 1) and Sm(0 0 0 1) metal surfaces exhibits up to 30% spectral intensity from the topmost atomic surface layer. The energy separation of surface and bulk XE peaks is explained by the surface core-level shift of La and the surface valence transition of Sm. While the bulk XE spectra are in reasonable agreement with theoretical sd partial density of states (DOS), the experimental access to the partial surface-layer DOS opens new opportunities in studying surface phenomena in lanthanide metals and compounds.

  6. Active Gold-Ceria and Gold-Ceria/titania Catalysts for CO Oxidation. From Single-Crystal Model Catalysts to Powder Catalysts

    SciTech Connect

    Rodriguez, Jose A.; Si, Rui; Evans, Jaime; Xu, Wenqian; Hanson, Jonathan C.; Tao, Jing; Zhu, Yimei

    2014-07-23

    We studied CO oxidation on model and powder catalysts of Au-CeO2 and Au-CeOx/TiO2. Phenomena observed in Au-CeO2(1 1 1) and Au-CeO2/TiO2(1 1 0) provided useful concepts for designing and preparing highly active and stable Au-CeOx/TiO2 powder catalysts for CO oxidation. Small particles of Au dispersed on CeO2(1 1 1) displayed high catalytic activity, making Au-CeO2(1 1 1) a better CO oxidation catalyst than Au-TiO2(1 1 0) or Au-MgO(1 0 0). An excellent support for gold was found after depositing nanoparticles of ceria on TiO2(1 1 0). The CeOx nanoparticles act as nucleation centers for gold, improving dispersion of the supported metal and helping in the creation of reaction sites efficient for the adsorption of CO and the dissociation of the O2 molecule. High-surface area catalysts were prepared by depositing gold on ceria nanorods and CeOx/TiO2 powders. The samples were tested for the low-temperature (10–70 °C) oxygen-rich (1%CO/4%O2/He) CO oxidation reaction after pre-oxidation (20%O2/He, 300 °C) and pre-reduction (5%H2/He, 300 °C) treatments. Moreover, synchrotron-based operando X-ray diffraction (XRD) and X-ray absorption (XAS) spectroscopy were used to study the Au-CeO2 and Au-CeOx/TiO2 catalysts under reaction conditions. Our operando findings indicate that the most active phase of these catalysts for low-temperature CO oxidation consist of small particles of metallic Au dispersed on CeO2 or CeOx/TiO2.

  7. Growth mechanism of thin films of yttria-stabilized zirconia by chemical vapor infiltration using NiO-ceria substrate as oxygen source

    NASA Astrophysics Data System (ADS)

    Kikuchi, Kenji; Okada, Koji; Mineshige, Atsushi

    The deposition of yttria-stabilized zirconia films on a NiO-ceria substrate by chemical vapor infiltration (CVI) using ZrCl 4 and YCl 3 as metal sources and NiO-ceria as oxygen source was studied. The resultant films were cubic YSZ with a Y 2O 3 content of 3.7-4.2 mol%, and were transparent and strong. A NiO content of NiO-ceria above 60 mol% increases the growth rate of the YSZ film from about 5 to 25 μm over 2 h, indicating that chemical vapor deposition (CVD) occurred in addition to electrochemical vapor deposition (EVD), whereas NiO contents below 60 mol% does not affect the growth rate, indicating that only electrochemical vapor deposition occurred. The growth mechanism of the YSZ film is determined and a YSZ thin film is successfully fabricated on NiO-ceria to improve mechanical strength.

  8. Thermodynamics and extraction modeling of trivalent lanthanides in the nuclear fuel cycle

    SciTech Connect

    Levitskaia, T.G.; Chatterjee, S.; Valerio, E.L.; Robinson, T.A.

    2013-07-01

    In this investigation, a combination of VPO (Vapor Pressure Osmometry) and water activity methods was applied to measure water activity and osmotic coefficients of binary lanthanide nitrate solutions at a temperature of 25 C. degrees. It was observed that the nature of the lanthanide nitrate has pronounced effect on the water activity in solution. In the solutions with the same Ln(NO{sub 3}){sub 3} molality, water activity is decreased in the order from the light to heavy lanthanides. This trend was explained by the contraction of the lanthanide ionic radii in the same order resulting in the [Ln(H{sub 2}O){sub n}]{sup 3+} (aq) hydration number of 9 for the early (La-Sm) and 8 for the late (Dy-Lu) lanthanides, with the intermediate metals exhibiting a mixture of eight and nine coordinate molecules. This results in the dissimilar effect of the light and heavy lanthanides on the water structure manifesting in the systematic changes of the water activity in the series of concentrated lanthanide solutions. Experimental water activity and osmotic coefficient data agree well with the literature for both 1:1 and 3:1 electrolyte systems. The Pitzer parameters obtained fitting these data are in an excellent agreement with the literature reported values for Ln(NO{sub 3}){sub 3} solutions.

  9. Thermochemistry of Lanthana- and Yttria- Doped Thoria

    SciTech Connect

    Aizenshtein, Michael; Shvareva, Tatiana Y.; Navrotsky, Alexandra

    2010-09-29

    Lanthanide-doped thoria is relevant both to nuclear energy and to solid oxide fuel cell technology. It is also a simple model system in which oxygen vacancy concentration is directly proportional to doping with no complication from oxidation–reduction reactions, ordered phases, or phase transitions in the tetravalent oxide. Despite this relevance, only few thermodynamic data are available for such systems. In the present study, La xTh1-xO2-0.5x (0< x <0.50) and Yx Th1-x O2-0.5x (0 < x < 0.18) have been synthesized, characterized, and systematically studied for the first time using high-temperature oxide melt solution calorimetry. Two competing effects contribute to the energetics: endothermic deviation from ideality related to cation size difference and partial stabilization of the system due to the exothermic formation of defect clusters. The former can be described by endothermic regular solution interaction parameters of 119.3 ± 11.4 kJ/mol for the yttria system and 27.8 ± 4.1 kJ/mol for the lanthana system. The latter can be described by exothermic vacancy clustering or defect association energies of –116.3 ± 23.3 kJ/mol for yttria-doped thoria and –98.6 ± 19.7 kJ/mol for lanthana-doped thoria.

  10. Stabilization of actinides and lanthanides in unusually high oxidation states

    SciTech Connect

    Eller, P.G.; Penneman, R.A.

    1986-01-01

    Chemical environments can be chosen which stabilize actinides and lanthanides in unusually high or low oxidation states and in unusual coordination. In many cases, one can rationalize the observed species as resulting from strong charge/size influences provided by specific sites in host lattices (e.g., Tb(IV) in BaTbO/sub 3/ or Am(IV) in polytungstate anions). In other cases, the unusual species can be considered from an acid-base viewpoint (e.g., U(III) in AsF/sub 5//HF solution or Pu(VII) in Li/sub 5/PuO/sub 6/). In still other cases, an interplay of steric and redox effects can lead to interesting comparisons (e.g., instability of double fluoride salts of Pu(V) and Pu(VI) relative to U, Np, and Am analogues). Generalized ways to rationalize compounds containing actinides and lanthanides in unusual valences (particularly high valences), including the above and numerous other examples, will form the focus of this paper. Recently developed methods for synthesizing high valent f-element fluorides using superoxidizers and superacids at low temperatures will also be described. 65 refs., 8 figs., 9 tabs.

  11. Lessons learned from dinuclear lanthanide nano-magnets.

    PubMed

    Habib, Fatemah; Murugesu, Muralee

    2013-04-21

    The quest for higher density information storage has led to the investigation of Single-Molecule Magnets (SMMs) as potential molecules to be applied in materials such as hard discs. In order for this to occur, one must first design metal complexes which can retain magnetic information at temperatures where these applications become possible. This can only be achieved through answering and understanding fundamental questions regarding the observed physical properties of SMMs. While mononuclear lanthanide complexes have shown promise in obtaining high energy barriers for the reversal of the magnetisation they are limited to Single-Ion Magnet behaviour intrinsic to one metal centre with a limited number of unpaired electrons. As a way of increasing the effective anisotropic barrier, systems with higher nuclearity have been sought to increase the spin ground state of the molecule. Dinuclear complexes are presented as key compounds in studying and understanding the nature of magnetic interactions between metal ions. This tutorial review will span a number of dinuclear 4f complexes which have been critical in our understanding of the way in which lanthanide centres in a complex interact magnetically. It will examine key bridging moieties from the more common oxygen-based groups to newly discovered radical-based bridges and draw conclusions regarding the most effective superexchange pathways allowing the most efficient intracomplex interactions. PMID:23334210

  12. Lanthanide-IMAC enrichment of carbohydrates and polyols.

    PubMed

    Schemeth, Dieter; Rainer, Matthias; Messner, Christoph B; Rode, Bernd M; Bonn, Günther K

    2014-03-01

    In this study a new type of immobilized metal ion affinity chromatography resin for the enrichment of carbohydrates and polyols was synthesized by radical polymerization reaction of vinyl phosphonic acid and 1,4-butandiole dimethacrylate using azo-bis-isobutyronitrile as radical initiator. Interaction between the chelated trivalent lanthanide ions and negatively charged hydroxyl groups of carbohydrates and polyols was observed by applying high pH values. The new method was evaluated by single standard solutions, mixtures of standards, honey and a more complex extract of Cynara scolymus. The washing step was accomplished by acetonitrile in excess volumes. Elution of enriched carbohydrates was successfully performed with deionized water. The subsequent analysis was carried out with matrix-free laser desorption/ionization-time of flight mass spectrometry involving a TiO2 -coated steel target, especially suitable for the measurement of low-molecular-weight substances. Quantitative analysis of the sugar alcohol xylitol as well as the determination of the maximal loading capacity was performed by gas chromatography in conjunction with mass spectrometric detection after chemical derivatization. In a parallel approach quantum mechanical geometry optimizations were performed in order to compare the coordination behavior of various trivalent lanthanide ions. PMID:24097333

  13. Lanthanide-IMAC enrichment of carbohydrates and polyols.

    PubMed

    Schemeth, Dieter; Rainer, Matthias; Messner, Christoph B; Rode, Bernd M; Bonn, Günther K

    2014-03-01

    In this study a new type of immobilized metal ion affinity chromatography resin for the enrichment of carbohydrates and polyols was synthesized by radical polymerization reaction of vinyl phosphonic acid and 1,4-butandiole dimethacrylate using azo-bis-isobutyronitrile as radical initiator. Interaction between the chelated trivalent lanthanide ions and negatively charged hydroxyl groups of carbohydrates and polyols was observed by applying high pH values. The new method was evaluated by single standard solutions, mixtures of standards, honey and a more complex extract of Cynara scolymus. The washing step was accomplished by acetonitrile in excess volumes. Elution of enriched carbohydrates was successfully performed with deionized water. The subsequent analysis was carried out with matrix-free laser desorption/ionization-time of flight mass spectrometry involving a TiO2 -coated steel target, especially suitable for the measurement of low-molecular-weight substances. Quantitative analysis of the sugar alcohol xylitol as well as the determination of the maximal loading capacity was performed by gas chromatography in conjunction with mass spectrometric detection after chemical derivatization. In a parallel approach quantum mechanical geometry optimizations were performed in order to compare the coordination behavior of various trivalent lanthanide ions.

  14. Basic understanding of the lanthanide related upconversion emissions

    NASA Astrophysics Data System (ADS)

    Dong, Hao; Sun, Ling-Dong; Yan, Chun-Hua

    2013-06-01

    With abundant energy levels of 4f electron configurations, trivalent lanthanide ions (Ln3+) are endowed with unique and fascinating luminescent properties. Inheriting the native transition behaviour of the lanthanide ions, Ln3+ based nanomaterials have aroused great interest for a wide range of applications, including lighting and displays, optical fibers and amplifiers, responsive luminescent stains for biomedical analysis, in vivo and in vitro imaging, and enhancement for silicon solar cell devices. It should be noted that the application depends completely on the corresponding luminescent behaviour. To deepen the understanding of the luminescent mechanism is important for the developing of the field and the design of new Ln3+ based luminescent materials toward applications. In this review, we focused mainly on the recent developments on upconversion (UC) emission studies. Firstly, the emphasis was put on the introduction of basic luminescent properties of Ln3+ with f-f transitions, and then the corresponding mechanisms and properties of UC emission were discussed in detail, the potential researches with respect to UC mechanisms and properties were finally outlined.

  15. Purification of lanthanides for double beta decay experiments

    NASA Astrophysics Data System (ADS)

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

    2013-08-01

    There are several potentially double beta active isotopes among the lanthanide elements. However, even high purity grade lanthanide compounds contain 238U, 226Ra and 232,228Th typically on the level of ˜ (0.1 - 1) Bq/kg. The liquid-liquid extraction technique was used to remove traces of U, Ra and Th from CeO2, Nd2O3 and Gd2O3. The radioactive contamination of the samples before and after the purification was tested by using ultra-low-background HPGe γ spectrometry at the underground Gran Sasso National Laboratories of the INFN (Italy). After the purification the radioactive contamination of gadolinium oxide by Ra and Th was decreased at least one order of magnitude. The efficiency of the approach to purify cerium oxide from Ra was on same level, while the radioactive contamination of neodymium sample before and after the purification is below the sensitivity of analytical methods. The purification method is much less efficient for chemically very similar radioactive elements like lanthanum, lutetium and actinium. R&D of the methods to remove the pollutions with improved efficiency is in progress.

  16. Magnetic Interactions in a Series of Homodinuclear Lanthanide Complexes.

    PubMed

    Comba, Peter; Großhauser, Michael; Klingeler, Rüdiger; Koo, Changhyun; Lan, Yanhua; Müller, Dennis; Park, Jaena; Powell, Annie; Riley, Mark J; Wadepohl, Hubert

    2015-12-01

    A series of seven isostructural homodinuclear lanthanide complexes are reported. The magnetic properties (ac and dc SQUID measurements) are discussed on the basis of the X-ray structural properties which show that the two lanthanide sites are structurally different. MCD spectroscopy of the dysprosium(III) and neodymium(III) complexes ([Dy(III)2(L)(OAc)4](+) and [Nd(III)2(L)(OAc)4](+)) allowed us to thoroughly analyze the ligand field, and high-frequency EPR spectroscopy of the gadolinium(III) species ([Gd(III)2(L)(OAc)4](+)) showed the importance of dipolar coupling in these systems. An extensive quantum-chemical analysis of the dysprosium(III) complex ([Dy(III)2(L)(OAc)4](+)), involving an ab initio (CASSCF) wave function, explicit spin-orbit coupling (RASSI-SO), and a ligand field analysis (Lines model and Stevens operators), is in full agreement with all experimental data (SQUID, HF-EPR, MCD) and specifically allowed us to accurately simulate the experimental χT versus T data, which therefore allowed us to establish a qualitative model for all relaxation pathways. PMID:26588004

  17. Energetic lanthanide complexes: coordination chemistry and explosives applications

    NASA Astrophysics Data System (ADS)

    Manner, V. W.; Barker, B. J.; Sanders, V. E.; Laintz, K. E.; Scott, B. L.; Preston, D. N.; Sandstrom, M.; Reardon, B. L.

    2014-05-01

    Metals are generally added to organic molecular explosives in a heterogeneous composite to improve overall heat and energy release. In order to avoid creating a mixture that can vary in homogeneity, energetic organic molecules can be directly bonded to high molecular weight metals, forming a single metal complex with Angstrom-scale separation between the metal and the explosive. To probe the relationship between the structural properties of metal complexes and explosive performance, a new series of energetic lanthanide complexes has been prepared using energetic ligands such as NTO (5-nitro-2,4-dihydro-1,2,4-triazole-3-one). These are the first examples of lanthanide NTO complexes where no water is coordinated to the metal, demonstrating novel control of the coordination environment. The complexes have been characterized by X-ray crystallography, NMR and IR spectroscopies, photoluminescence, and sensitivity testing. The structural and energetic properties are discussed in the context of enhanced blast effects and detection. Cheetah calculations have been performed to fine-tune physical properties, creating a systematic method for producing explosives with 'tailor made' characteristics. These new complexes will be benchmarks for further study in the field of metalized high explosives.

  18. Energetic Lanthanide Complexes: Coordination Chemistry and Explosives Applications

    NASA Astrophysics Data System (ADS)

    Manner, Virginia; Barker, Beau; Sanders, Eric; Laintz, Kenneth; Scott, Brian; Preston, Daniel; Sandstrom, Mary; Reardon, Bettina

    2013-06-01

    Metals are generally added to organic molecular explosives in a heterogeneous composite to improve overall heat and energy release. In order to avoid creating a mixture that can vary in homogeneity, energetic organic molecules can be directly bonded to high molecular weight metals, forming a single metal complex with Angstrom-scale separation between the metal and the explosive. To probe the relationship between the structural properties of metal complexes and explosive performance, a new series of energetic lanthanide complexes has been prepared using energetic ligands such as NTO (5-nitro-2,4-dihydro-1,2,4-triazole-3-one). These are the first examples of lanthanide NTO complexes where no water is coordinated to the metal, demonstrating novel control of the coordination environment. The complexes have been characterized by X-ray crystallography, NMR and IR spectroscopies, photoluminescence, and sensitivity testing. The structural and energetic properties are discussed in the context of enhanced blast effects and detection. Cheetah calculations have been performed to fine-tune physical properties, creating a systematic method for producing explosives with ``tailor made'' characteristics. These new complexes will be benchmarks for further study in the field of metalized high explosives.

  19. Purification of lanthanides for double beta decay experiments

    SciTech Connect

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

    2013-08-08

    There are several potentially double beta active isotopes among the lanthanide elements. However, even high purity grade lanthanide compounds contain {sup 238}U, {sup 226}Ra and {sup 232,228}Th typically on the level of ∼ (0.1 - 1) Bq/kg. The liquid-liquid extraction technique was used to remove traces of U, Ra and Th from CeO{sub 2}, Nd{sub 2}O{sub 3} and Gd{sub 2}O{sub 3}. The radioactive contamination of the samples before and after the purification was tested by using ultra-low-background HPGe γ spectrometry at the underground Gran Sasso National Laboratories of the INFN (Italy). After the purification the radioactive contamination of gadolinium oxide by Ra and Th was decreased at least one order of magnitude. The efficiency of the approach to purify cerium oxide from Ra was on same level, while the radioactive contamination of neodymium sample before and after the purification is below the sensitivity of analytical methods. The purification method is much less efficient for chemically very similar radioactive elements like lanthanum, lutetium and actinium. R and D of the methods to remove the pollutions with improved efficiency is in progress.

  20. Lanthanide Hydroxide Nanoparticles Induce Angiogenesis via ROS-Sensitive Signaling.

    PubMed

    Zhao, Haishan; Osborne, Olivia J; Lin, Sijie; Ji, Zhaoxia; Damoiseux, Robert; Wang, Yuqiang; Nel, André E; Lin, Shuo

    2016-08-01

    Recent studies suggest that the nanorods consisting of europium hydroxide could promote angiogenesis. In this study, it is sought to determine if additional types of nanoparticles are capable of enhancing angiogenesis and in addition, understand the underlying mechanisms. For this reason, a method is employed that combines a high throughput in vitro cell based screen coupled with an in vivo validation using vascular specific green fluorescent protein reporter transgenic zebrafish for examining proangiogenesis activity. After screening multiple types of nanoparticles, it is discovered that four of them, Eu(III) (OH)3 rods (Eu rods), Eu(III) (OH)3 spheres (Eu spheres), Tb(III) (OH)3 rods (Tb rods), and Tb(III) (OH)3 spheres (Tb spheres), are the most effective in promoting angiogenesis. It is also showed that ionic forms of europium nitrate [Eu(NO3 )3 ] (Eu) and terbium nitrate [Tb(NO3 )3 ] (Tb), the two lanthanide elements for these four nanoparticles, are also capable of enhancing angiogenesis. However, this effect is further enhanced by nanoparticle synthesis. Finally, it is demonstrated that reactive oxygen species H2 O2 is a key factor in the process of proangiogenesis by lanthanide elemental nanoparticles. PMID:27383397

  1. Molecular lanthanide single-ion magnets: from bulk to submonolayers.

    PubMed

    Dreiser, J

    2015-05-13

    Single-ion magnets (SIMs) are mononuclear molecular complexes exhibiting slow relaxation of magnetization. They are currently attracting a lot of interest because of potential applications in spintronics and quantum information processing. However, exploiting SIMs in, e.g. molecule-inorganic hybrid devices requires a fundamental understanding of the effects of molecule-substrate interactions on the SIM magnetic properties. In this review the properties of lanthanide SIMs in the bulk crystalline phase and deposited on surfaces in the (sub)monolayer regime are discussed. As a starting point trivalent lanthanide ions in a ligand field will be described, and the challenges in characterizing the ligand field are illustrated with a focus on several spectroscopic techniques which are able to give direct information on the ligand-field split energy levels. Moreover, the dominant mechanisms of magnetization relaxation in the bulk phase are discussed followed by an overview of SIMs relevant for surface deposition. Further, a short introduction will be given on x-ray absorption spectroscopy, x-ray magnetic circular dichroism and scanning tunneling microscopy. Finally, the recent experiments on surface-deposited SIMs will be reviewed, along with a discussion of future perspectives.

  2. Water-gas shift reaction over gold nanoparticles dispersed on nanostructured CeOx-TiO2(110) surfaces: Effects of high ceria coverage

    NASA Astrophysics Data System (ADS)

    Grinter, D. C.; Park, J. B.; Agnoli, S.; Evans, J.; Hrbek, J.; Stacchiola, D. J.; Senanayake, S. D.; Rodriguez, J. A.

    2016-08-01

    Scanning tunnelling microscopy has been used to study the morphology of an overlayer of ceria in contact with a TiO2(110) substrate. Two types of domains were observed after ceria deposition. An ordered ceria film covered half of the surface and high-resolution imaging suggested a near-c(6 × 2) relationship to the underlying TiO2(110)-(1 × 1). The other half of the surface comprised CeOx nanoparticles and reconstructed TiOx supported on TiO2(110)-(1 × 1). Exposure to a small amount of gold resulted in the formation of isolated gold atoms and small clusters on the ordered ceria film and TiO2(110)-(1 × 1) areas, which exhibited significant sintering at 500 K and showed strong interaction between the sintered gold clusters and the domain boundaries of the ceria film. The Au/CeOx/TiO2(110) model system proved to be a good catalyst for the water-gas shift (WGS) exhibiting much higher turnover frequencies (TOFs) than Cu(111) and Pt(111) benchmarks, or the individual Au/TiO2(110) and Au/CeO2(111) systems. For Au/CeOx/TiO2(110) catalysts, there was a decrease in catalytic activity with increasing ceria coverage that correlates with a reduction in the concentration of Ce3 + formed during WGS reaction conditions.

  3. Fluoride Binding and Crystal-Field Analysis of Lanthanide Complexes of Tetrapicolyl-Appended Cyclen.

    PubMed

    Blackburn, Octavia A; Kenwright, Alan M; Jupp, Andrew R; Goicoechea, Jose M; Beer, Paul D; Faulkner, Stephen

    2016-06-20

    Lanthanide complexes of tetrapicolyl cyclen displayed remarkably high affinities for fluoride (log K≈5) in water, and were shown to form 1:1 complexes. The behaviour of these systems can be rationalised by changes to the magnitude of the crystal-field parameter, B20 . However, such changes are not invariably accompanied by a change in sign of this parameter: for early lanthanides, the N8 donor set with a coordinated axial water molecule ensures that the magnetic anisotropy has the opposite sense to that observed in the analogous dehydrated lanthanide complexes. PMID:27167830

  4. Features of the reaction of heterocyclic analogs of chalcone with lanthanide shift reagents

    SciTech Connect

    Turov, A.V.; Khilya, V.P.

    1994-10-01

    The PMR spectra of heterocyclic analogs of 2-hydroxychalcone containing thiazole, benzofuran, triazole, imidazole, benzodioxane, or pyridine rings in the presence of lanthanide shift reagents are studied. It is found that the most effective reagent for modifying the spectra of these compounds is Yb(fod)3. The broadening of the spectra of 2-hydroxy chalcones in the presence of lanthanide shift reagents is explained by the dynamic effects of complex formation. An example is given of the determination of the conformation of molecules of 2-hydroxychalcone by the simultaneous use of lanthanide shift reagents and the homonuclear Overhauser effect. 9 refs., 1 fig., 1 tab.

  5. The separation of lanthanides and actinides in supercritical fluid carbon dioxide

    SciTech Connect

    Mincher, Bruce J.; Wai, Chien M.; Fox, Robert V.; Baek, Donna L.; Yen, Clive; Case, Mary E.

    2015-10-28

    Supercritical fluid carbon dioxide presents an attractive alternative to conventional solvents for recovery of the actinides and lanthanides. Carbon dioxide is a good solvent for fluorine and phosphate-containing ligands, including the traditional tributylphosphate ligand used in process-scale uranium separations. Actinide and lanthanide oxides may even be directly dissolved in carbon dioxide containing the complexes formed between these ligands and mineral acids, obviating the need for large volumes of acids for leaching and dissolution, and the corresponding organic liquid–liquid solvent extraction solutions. As a result, examples of the application of this novel technology for actinide and lanthanide separations are presented.

  6. Impact of deposition parameters on the performance of ceria based resistive switching memories

    NASA Astrophysics Data System (ADS)

    Zhang, Lepeng; Younis, Adnan; Chu, Dewei; Li, Sean

    2016-07-01

    Resistive-switching memories stacked in a metal–insulator–metal (MIM) like structure have shown great potential for next generation non-volatile memories. In this study, ceria based resistive memory stacks are fabricated by implementing different sputter conditions (temperatures and powers). The films deposited at low temperatures were found to have random grain orientations, less porosity and dense structure. The effect of deposition conditions on resistive switching characteristics of as-prepared films were also investigated. Improved and reliable resistive switching behaviors were achieved for the memory devices occupying less porosity and densely packed structures prepared at low temperatures. Finally, the underlying switching mechanism was also explained on the basis of quantitative analysis.

  7. Pathways for Ethanol Dehydrogenation and Dehydration Catalyzed by Ceria (111) and (100) Surfaces

    DOE PAGES

    Beste, Ariana; Steven Overbury

    2015-01-08

    We have performed computations to better understand how surface structure affects selectivity in dehydrogenation and dehydration reactions of alcohols. Ethanol reactions on the (111) and (100) ceria surfaces were studied starting from the dominant surface species, ethoxy. We used DFT (PBE+U) to explore reaction pathways leading to ethylene and acetaldehyde and calculated estimates of rate constants employing transition state theory. To assess pathway contributions, we carried out kinetic analysis. Our results show that intermediate and transition state structures are stabilized on the (100) surface compared to the (111) surface. Formation of acetaldehyde over ethylene is kinetically and thermodynamically preferred onmore » both surfaces. Our results are consistent with temperature programmed surface reaction and steady-state experiments, where acetaldehyde was found as the main product and evidence was presented that ethylene formation at higher temperature originates from changes in adsorbate and surface structure.« less

  8. Pathways for Ethanol Dehydrogenation and Dehydration Catalyzed by Ceria (111) and (100) Surfaces

    SciTech Connect

    Beste, Ariana; Steven Overbury

    2015-01-08

    We have performed computations to better understand how surface structure affects selectivity in dehydrogenation and dehydration reactions of alcohols. Ethanol reactions on the (111) and (100) ceria surfaces were studied starting from the dominant surface species, ethoxy. We used DFT (PBE+U) to explore reaction pathways leading to ethylene and acetaldehyde and calculated estimates of rate constants employing transition state theory. To assess pathway contributions, we carried out kinetic analysis. Our results show that intermediate and transition state structures are stabilized on the (100) surface compared to the (111) surface. Formation of acetaldehyde over ethylene is kinetically and thermodynamically preferred on both surfaces. Our results are consistent with temperature programmed surface reaction and steady-state experiments, where acetaldehyde was found as the main product and evidence was presented that ethylene formation at higher temperature originates from changes in adsorbate and surface structure.

  9. Laser assisted modification and chemical metallization of electron-beam deposited ceria thin films

    NASA Astrophysics Data System (ADS)

    Krumov, E.; Starbov, N.; Starbova, K.; Perea, A.; Solis, J.

    2009-11-01

    Excimer laser processing is applied for tailoring the surface morphology and phase composition of CeO 2 ceramic thin films. E-beam evaporation technique is used to deposit samples on stainless steel and silicate glass substrates. The films are then irradiated with ArF* excimer laser pulses under different exposure conditions. Scanning electron microscopy, optical spectrophotometry, X-ray diffractometry and EDS microanalysis are used to characterize the non-irradiated and laser-processed films. Upon UV laser exposure there is large increase of the surface roughness that is accompanied by photo-darkening and ceria reduction. It is shown that the laser induced changes in the CeO 2 films facilitate the deposition of metal nano-aggregates in a commercial copper electroless plating bath. The significance of laser modification as a novel approach for the production of CeO 2 based thin film catalysts is discussed.

  10. Cell membrane penetration and mitochondrial targeting by platinum-decorated ceria nanoparticles

    NASA Astrophysics Data System (ADS)

    Torrano, Adriano A.; Herrmann, Rudolf; Strobel, Claudia; Rennhak, Markus; Engelke, Hanna; Reller, Armin; Hilger, Ingrid; Wixforth, Achim; Bräuchle, Christoph

    2016-07-01

    In this work we investigate the interaction between endothelial cells and nanoparticles emitted by catalytic converters. Although catalyst-derived particles are recognized as growing burden added to environmental pollution, very little is known about their health impact. We use platinum-decorated ceria nanoparticles as model compounds for the actual emitted particles and focus on their fast uptake and association with mitochondria, the cell's powerhouse. Using live-cell imaging and electron microscopy we clearly show that 46 nm platinum-decorated ceria nanoparticles can rapidly penetrate cell membranes and reach the cytosol. Moreover, if suitably targeted, these particles are able to selectively attach to mitochondria. These results are complemented by cytotoxicity assays, thus providing insights into the biological effects of these particles on cells. Interestingly, no permanent membrane disruption or any other significant adverse effects on cells were observed. The unusual uptake behavior observed for 46 nm nanoparticles was not observed for equivalent but larger 143 nm and 285 nm platinum-decorated particles. Our results demonstrate a remarkable particle size effect in which particles smaller than ~50-100 nm escape the usual endocytic pathway and translocate directly into the cytosol, while particles larger than ~150 nm are internalized by conventional endocytosis. Since the small particles are able to bypass endocytosis they could be explored as drug and gene delivery vehicles. Platinum-decorated nanoparticles are therefore highly interesting in the fields of nanotoxicology and nanomedicine.In this work we investigate the interaction between endothelial cells and nanoparticles emitted by catalytic converters. Although catalyst-derived particles are recognized as growing burden added to environmental pollution, very little is known about their health impact. We use platinum-decorated ceria nanoparticles as model compounds for the actual emitted particles and

  11. Ceria loaded nanoreactors: a nontoxic superantioxidant system with high stability and efficacy

    NASA Astrophysics Data System (ADS)

    Spulber, M.; Baumann, P.; Liu, J.; Palivan, C. G.

    2015-01-01

    Medical applications of the superantioxidant ceria nanoparticles (CeNP) are limited due to their high toxicity and low stability. CeNP toxicity is related to their aggregation in solution, and the possible generation of reactive oxygen species (ROS) by a Fenton-like reaction. For the efficient medical application of CeNP, it is necessary to find new solutions, which simultaneously reduce their inherent toxicity while preserving their unique catalytic regenerative qualities. Here we introduce a straightforward strategy based on CeNP encapsulation in polymer vesicles which reduces their toxicity, but preserves their superantioxidant character. We have engineered antioxidant nanoreactors, which serve the dual purpose of: (i) separation of CeNP, which inhibits aggregate formation, and (ii) protection of CeNP from hydrogen peroxide, thus eliminating the Fenton-like reaction which induces cytotoxicity. Nanoreactors containing CeNP possess a higher scavenging activity than free CeNP for both hydroxyl and superoxide radicals, as indicated by spin trapping EPR. Due to the regenerative redox chemistry of ceria, the nanoreactors are active for long periods of time, without requiring additional reducing agents. Upon uptake by cells, the nanoreactors show almost no toxicity compared with the free CeNP after a long term exposure, thus proving their high efficacy as ROS scavengers. Our strategy of engineering CeNP-containing nanoreactors represents a versatile, simple and economical solution to reduce CeNP toxicity, while preserving their functionality; thus nanoreactors are the ideal candidates for fighting oxidative stress in a large variety of medical situations.Medical applications of the superantioxidant ceria nanoparticles (CeNP) are limited due to their high toxicity and low stability. CeNP toxicity is related to their aggregation in solution, and the possible generation of reactive oxygen species (ROS) by a Fenton-like reaction. For the efficient medical application of Ce

  12. Investigation of combined S02/N0x Removal by Ceria Sorbents

    SciTech Connect

    Ates Akyurtlu; Jale F. Akyurtlu

    1996-11-01

    This final report describes the work done under the sponsorship of the U.S. DOE for the support of advanced fossil resource utilization research at historically black colleges and universities, Grant No. DE-Ps22-92MT920 on "Investigation of Combined S02/NOx Removal by Ceria Sorbents". The work was conducted at the Department of Chemical Engineering of Hampton University. The industrial partner was Malcolm Pirnie,Inc. Environmental Engineers, Scientists and Planners, who handled the metal analysis and XRD measurements on the solid sorbents; they have also supplied the flyash used in the experimental program. The development of a commercial process concept, economic analysis, and evaluation of process alternatives were undertaken by TECOGEN of Waltham, MA.

  13. Synthesis and Electrochemical Behavior of Ceria Based Bi-Layer Films by Dip Coating Technique.

    PubMed

    Chinnu, M Karl; Anand, K Vijai; Kumar, R Mohan; Alagesan, T; Jayavel, R

    2015-01-01

    Ceria based bi-layer films of CeO2-CdS and CeO2-TiO2 were prepared by sol-gel based hydrothermal route combined with dip-coating. The synthesized samples were subjected to various characterizations such as X-ray diffraction, Field emission scanning electron microscopy, thermo-gravimetric analysis, UV-Vis absorption and photoluminescence studies. The prepared materials were dissolved in naffion solution and disposed as a thin film on glassy carbon electrode by dip coating technique. Electrochemical Li+ intercalation/deintercalation was performed by cyclic voltammetry and these results indicate that the CeO2/LiClO4 system is electrochemically reversible. The total intercalation/deintercalation of the CeO2 film, CeO2-CdS and CeO2-TiO2 bi-layer films was determined by cyclic voltammetry, which showed increased charge storage capacity.

  14. Vacancy–Vacancy Interaction Induced Oxygen Diffusivity Enhancement in Undoped Nonstoichiometric Ceria

    SciTech Connect

    Yuan, Fenglin; Zhang, Yanwen; Weber, William J.

    2015-05-19

    In this paper, molecular dynamics simulations and molecular static calculations have been used to systematically study oxygen vacancy transport in undoped nonstoichiometric ceria. A strong oxygen diffusivity enhancement appears in the vacancy concentration range of 2–4% over the temperature range from 1000 to 2000 K. An Arrhenius ion diffusion mechanism by vacancy hopping along the (100) direction is unambiguously identified, and an increasing trend of both the oxygen migration barrier and the prefactor with increasing vacancy concentration is observed. Within the framework of classical diffusion theory, a weak concentration dependence of the prefactor in oxygen vacancy migration is shown to be crucial for explaining the unusual fast oxygen ion migration in the low concentration range and consequently the appearance of a maximum in oxygen diffusivity. Finally, a representative (100) direction interaction model is constructed to identify long-range vacancy–vacancy interaction as the structural origin of the positive correlation between oxygen migration barrier and vacancy concentration.

  15. Hydrodeoxygenation of vicinal OH groups over heterogeneous rhenium catalyst promoted by palladium and ceria support.

    PubMed

    Ota, Nobuhiko; Tamura, Masazumi; Nakagawa, Yoshinao; Okumura, Kazu; Tomishige, Keiichi

    2015-02-01

    Heterogeneous ReOx-Pd/CeO2 catalyst showed excellent performance for simultaneous hydrodeoxygenation of vicinal OH groups. High yield (>99%), turnover frequency (300 h(-1)), and turnover number (10,000) are achieved in the reaction of 1,4-anhydroerythritol to tetrahydrofuran. This catalyst can be applied to sugar alcohols, and mono-alcohols and diols are obtained in high yields (≥85%) from substrates with even and odd numbers of OH groups, respectively. The high catalytic performance of ReOx-Pd/CeO2 can be assigned to rhenium species with +4 or +5 valence state, and the formation of this species is promoted by H2/Pd and the ceria support.

  16. Carbon deposition behaviour in metal-infiltrated gadolinia doped ceria electrodes for simulated biogas upgrading in solid oxide electrolysis cells

    NASA Astrophysics Data System (ADS)

    Duboviks, V.; Lomberg, M.; Maher, R. C.; Cohen, L. F.; Brandon, N. P.; Offer, G. J.

    2015-10-01

    One of the attractive applications for reversible Solid Oxide Cells (SOCs) is to convert CO2 into CO via high temperature electrolysis, which is particularly important for biogas upgrading. To improve biogas utility, the CO2 component can be converted into fuel via electrolysis. A significant issue for SOC operation on biogas is carbon-induced catalyst deactivation. Nickel is widely used in SOC electrodes for reasons of cost and performance, but it has a low tolerance to carbon deposition. Two different modes of carbon formation on Ni-based electrodes are proposed in the present work based on ex-situ Raman measurements which are in agreement with previous studies. While copper is known to be resistant towards carbon formation, two significant issues have prevented its application in SOC electrodes - namely its relatively low melting temperature, inhibiting high temperature sintering, and low catalytic activity for hydrogen oxidation. In this study, the electrodes were prepared through a low temperature metal infiltration technique. Since the metal infiltration technique avoids high sintering temperatures, Cu-Ce0.9Gd0.1O2-δ (Cu-CGO) electrodes were fabricated and tested as an alternative to Ni-CGO electrodes. We demonstrate that the performance of Cu-CGO electrodes is equivalent to Ni-CGO electrodes, whilst carbon formation is fully suppressed when operated on biogas mixture.

  17. Preparation and characterization of ceria-zirconia ceramics using a sol-gel process

    SciTech Connect

    Zhu Bin |; Xia Changrong; Luo Xiaoguang; Meng Guangyao

    1997-10-01

    Both powder and thin film CeO{sub 2}-ZrO{sub 2} ceramic materials have been successfully prepared via a sol-gel process. In this process, Zr and Ce hydroxide-mixed sols were prepared by hydrolysis of Zr oxychloride and Ce nitrate. The thin films were coated on glass or alumina plates and also alumina tubes by a spin- or dip-coating procedure. The structure and phase of the powder or thin-film CeO{sub 2}-ZrO{sub 2} have been characterized by X-ray diffraction (XRD). Electrical properties were measured by means of complex impedance analyses. The cyclic voltammogram measurements were performed for the ITO glass-supported CeO{sub 2}-ZrO{sub 2} thin films. Powder CeO{sub 2}-ZrO{sub 2} solid solutions having the tetragonal polymorph of zirconia are obtained for ceria contents up to 50 mol%, whereas for a ceria content more than 50 mol%, the CeO{sub 2}-ZrO{sub 2} is stabilized in the cubic fluorite structure. The thin-film CeO{sub 2}-ZrO{sub 2} usually has a cubic structural characteristic. Both powder and thin-film CeO{sub 2}-ZrO{sub 2} materials are nanostructured with an average grain size of 10 nm, and they have shown very different electrical properties. The CeO{sub 2}-ZrO{sub 2} thin films have great potential for applications in various electrochemical or optoionic devices, such as fuel cells, electrochromic devices, and so forth.

  18. Color-center production and recovery in electron-irradiated magnesium aluminate spinel and ceria

    NASA Astrophysics Data System (ADS)

    Costantini, Jean-Marc; Lelong, Gérald; Guillaumet, Maxime; Weber, William J.; Takaki, Seiya; Yasuda, Kazuhiro

    2016-08-01

    Single crystals of magnesium aluminate spinel (MgAl2O4) with (1 0 0) or (1 1 0) orientations and cerium dioxide or ceria (CeO2) were irradiated by 1.0 MeV and 2.5 MeV electrons in a high-fluence range. Point-defect production was studied by off-line UV–visible optical spectroscopy after irradiation. For spinel, regardless of both crystal orientation and electron energy, two characteristic broad bands centered at photon energies of 5.4 eV and 4.9 eV were assigned to F and F+ centers (neutral and singly ionized oxygen vacancies), respectively, on the basis of available literature data. No clear differences in color-center formation were observed for the two crystal orientations. Using calculations from displacement cross sections by elastic collisions, these results are consistent with a very large threshold displacement energy (200 eV) for oxygen atoms at room temperature. A third very broad band centered at 3.7 eV might be attributed either to an oxygen hole center (V-type center) or an F2 dimer center (oxygen di-vacancy). The onset of recovery of these color centers took place at 200 °C with almost full bleaching at 600 °C. Activation energies (~0.3–0.4 eV) for defect recovery were deduced from the isochronal annealing data by using a first-order kinetics analysis. For ceria, a sub-band-gap absorption feature, which peaked at ~3.1 eV, was recorded for 2.5 MeV electron irradiation only. Assuming a ballistic process, we suggest that the latter defect might result from cerium atom displacement on the basis of computed cross sections.

  19. Color-center production and recovery in electron-irradiated magnesium aluminate spinel and ceria.

    PubMed

    Costantini, Jean-Marc; Lelong, Gérald; Guillaumet, Maxime; Weber, William J; Takaki, Seiya; Yasuda, Kazuhiro

    2016-08-17

    Single crystals of magnesium aluminate spinel (MgAl2O4) with (1 0 0) or (1 1 0) orientations and cerium dioxide or ceria (CeO2) were irradiated by 1.0 MeV and 2.5 MeV electrons in a high-fluence range. Point-defect production was studied by off-line UV-visible optical spectroscopy after irradiation. For spinel, regardless of both crystal orientation and electron energy, two characteristic broad bands centered at photon energies of 5.4 eV and 4.9 eV were assigned to F and F(+) centers (neutral and singly ionized oxygen vacancies), respectively, on the basis of available literature data. No clear differences in color-center formation were observed for the two crystal orientations. Using calculations from displacement cross sections by elastic collisions, these results are consistent with a very large threshold displacement energy (200 eV) for oxygen atoms at room temperature. A third very broad band centered at 3.7 eV might be attributed either to an oxygen hole center (V-type center) or an F2 dimer center (oxygen di-vacancy). The onset of recovery of these color centers took place at 200 °C with almost full bleaching at 600 °C. Activation energies (~0.3-0.4 eV) for defect recovery were deduced from the isochronal annealing data by using a first-order kinetics analysis. For ceria, a sub-band-gap absorption feature, which peaked at ~3.1 eV, was recorded for 2.5 MeV electron irradiation only. Assuming a ballistic process, we suggest that the latter defect might result from cerium atom displacement on the basis of computed cross sections. PMID:27319289

  20. Behaviour of ceria nanoparticles in standardized test media - influence on the results of ecotoxicological tests

    NASA Astrophysics Data System (ADS)

    Manier, Nicolas; Garaud, Maël; Delalain, Patrice; Aguerre-Chariol, Olivier; Pandard, Pascal

    2011-07-01

    The main objectives of this work were to establish the behaviour of a ceria nanopowder in different ecotoxicological media commonly used in standardized aquatic ecotoxicity tests and consequently to assess the acute and chronic ecotoxicity in two micro-invertebrates: Daphnia magna and Ceriodaphnia dubia and in a freshwater green algae: Pseudokirchneriella subcapitata. Different approaches to disperse the ceria nanoparticles (i.e. stirring, use of probe sonication, addition of humic acids) were tested and the influence on the biological endpoints was investigated. Despite the agglomeration phenomena observed in all the tested media, the results obtained indicated higher stability in the lower ionic strength media with addition of humic acid (2 mg.L-1 TOC). No acute toxicity were observed with D. magna, whatever the dispersal method performed and the nCeO2 concentration tested (up to 1000 mg.L-1), as no acute toxicity was recorded with C. dubia following exposure to the stirring suspensions. On contrary, acute toxicity was recorded in C. dubia with EC50 values comprise between 11.9 and 25.3 mg.L-1 using the probe sonicated suspension with or without humic acids addition. Significant chronic effect on the reproduction capability was also recorded in C. dubia. The estimated EC10 values were comprised between 2.1 and 2.9 mg.L-1. Focusing on P. subcapitata, despite the different agglomerate size recorded in the tested media at the end of the exposure periods, results obtained were similar. Adverse effect on algal growth around 5 mg.L-1 were reported (mean EC10 = 4 ± 1.8 mg.L-1). Those results suggested the needed for standardized testing protocol concerning the aqueous media used or the sample preparation for laboratory testing.

  1. Color-center production and recovery in electron-irradiated magnesium aluminate spinel and ceria.

    PubMed

    Costantini, Jean-Marc; Lelong, Gérald; Guillaumet, Maxime; Weber, William J; Takaki, Seiya; Yasuda, Kazuhiro

    2016-08-17

    Single crystals of magnesium aluminate spinel (MgAl2O4) with (1 0 0) or (1 1 0) orientations and cerium dioxide or ceria (CeO2) were irradiated by 1.0 MeV and 2.5 MeV electrons in a high-fluence range. Point-defect production was studied by off-line UV-visible optical spectroscopy after irradiation. For spinel, regardless of both crystal orientation and electron energy, two characteristic broad bands centered at photon energies of 5.4 eV and 4.9 eV were assigned to F and F(+) centers (neutral and singly ionized oxygen vacancies), respectively, on the basis of available literature data. No clear differences in color-center formation were observed for the two crystal orientations. Using calculations from displacement cross sections by elastic collisions, these results are consistent with a very large threshold displacement energy (200 eV) for oxygen atoms at room temperature. A third very broad band centered at 3.7 eV might be attributed either to an oxygen hole center (V-type center) or an F2 dimer center (oxygen di-vacancy). The onset of recovery of these color centers took place at 200 °C with almost full bleaching at 600 °C. Activation energies (~0.3-0.4 eV) for defect recovery were deduced from the isochronal annealing data by using a first-order kinetics analysis. For ceria, a sub-band-gap absorption feature, which peaked at ~3.1 eV, was recorded for 2.5 MeV electron irradiation only. Assuming a ballistic process, we suggest that the latter defect might result from cerium atom displacement on the basis of computed cross sections.

  2. Ceria loaded nanoreactors: a nontoxic superantioxidant system with high stability and efficacy.

    PubMed

    Spulber, M; Baumann, P; Liu, J; Palivan, C G

    2015-01-28

    Medical applications of the superantioxidant ceria nanoparticles (CeNP) are limited due to their high toxicity and low stability. CeNP toxicity is related to their aggregation in solution, and the possible generation of reactive oxygen species (ROS) by a Fenton-like reaction. For the efficient medical application of CeNP, it is necessary to find new solutions, which simultaneously reduce their inherent toxicity while preserving their unique catalytic regenerative qualities. Here we introduce a straightforward strategy based on CeNP encapsulation in polymer vesicles which reduces their toxicity, but preserves their superantioxidant character. We have engineered antioxidant nanoreactors, which serve the dual purpose of: (i) separation of CeNP, which inhibits aggregate formation, and (ii) protection of CeNP from hydrogen peroxide, thus eliminating the Fenton-like reaction which induces cytotoxicity. Nanoreactors containing CeNP possess a higher scavenging activity than free CeNP for both hydroxyl and superoxide radicals, as indicated by spin trapping EPR. Due to the regenerative redox chemistry of ceria, the nanoreactors are active for long periods of time, without requiring additional reducing agents. Upon uptake by cells, the nanoreactors show almost no toxicity compared with the free CeNP after a long term exposure, thus proving their high efficacy as ROS scavengers. Our strategy of engineering CeNP-containing nanoreactors represents a versatile, simple and economical solution to reduce CeNP toxicity, while preserving their functionality; thus nanoreactors are the ideal candidates for fighting oxidative stress in a large variety of medical situations.

  3. Color-center production and recovery in electron-irradiated magnesium aluminate spinel and ceria

    NASA Astrophysics Data System (ADS)

    Costantini, Jean-Marc; Lelong, Gérald; Guillaumet, Maxime; Weber, William J.; Takaki, Seiya; Yasuda, Kazuhiro

    2016-08-01

    Single crystals of magnesium aluminate spinel (MgAl2O4) with (1 0 0) or (1 1 0) orientations and cerium dioxide or ceria (CeO2) were irradiated by 1.0 MeV and 2.5 MeV electrons in a high-fluence range. Point-defect production was studied by off-line UV-visible optical spectroscopy after irradiation. For spinel, regardless of both crystal orientation and electron energy, two characteristic broad bands centered at photon energies of 5.4 eV and 4.9 eV were assigned to F and F+ centers (neutral and singly ionized oxygen vacancies), respectively, on the basis of available literature data. No clear differences in color-center formation were observed for the two crystal orientations. Using calculations from displacement cross sections by elastic collisions, these results are consistent with a very large threshold displacement energy (200 eV) for oxygen atoms at room temperature. A third very broad band centered at 3.7 eV might be attributed either to an oxygen hole center (V-type center) or an F2 dimer center (oxygen di-vacancy). The onset of recovery of these color centers took place at 200 °C with almost full bleaching at 600 °C. Activation energies (~0.3-0.4 eV) for defect recovery were deduced from the isochronal annealing data by using a first-order kinetics analysis. For ceria, a sub-band-gap absorption feature, which peaked at ~3.1 eV, was recorded for 2.5 MeV electron irradiation only. Assuming a ballistic process, we suggest that the latter defect might result from cerium atom displacement on the basis of computed cross sections.

  4. Cytotoxicity and Genotoxicity of Ceria Nanoparticles on Different Cell Lines in Vitro

    PubMed Central

    De Marzi, Laura; Monaco, Antonina; De Lapuente, Joaquin; Ramos, David; Borras, Miquel; Di Gioacchino, Mario; Santucci, Sandro; Poma, Anna

    2013-01-01

    Owing to their radical scavenging and UV-filtering properties, ceria nanoparticles (CeO2-NPs) are currently used for various applications, including as catalysts in diesel particulate filters. Because of their ability to filter UV light, CeO2-NPs have garnered significant interest in the medical field and, consequently, are poised for use in various applications. The aim of this work was to investigate the effects of short-term (24 h) and long-term (10 days) CeO2-NP exposure to A549, CaCo2 and HepG2 cell lines. Cytotoxicity assays tested CeO2-NPs over a concentration range of 0.5 μg/mL to 5000 μg/mL, whereas genotoxicity assays tested CeO2-NPs over a concentration range of 0.5 μg/mL to 5000 μg/mL. In vitro assays showed almost no short-term exposure toxicity on any of the tested cell lines. Conversely, long-term CeO2-NP exposure proved toxic for all tested cell lines. NP genotoxicity was detectable even at 24-h exposure. HepG2 was the most sensitive cell line overall; however, the A549 line was most sensitive to the lowest concentration tested. Moreover, the results confirmed the ceria nanoparticles’ capacity to protect cells when they are exposed to well-known oxidants such as H2O2. A Comet assay was performed in the presence of both H2O2 and CeO2-NPs. When hydrogen peroxide was maintained at 25 μM, NPs at 0.5 μg/mL, 50 μg/mL, and 500 μg/mL protected the cells from oxidative damage. Thus, the NPs prevented H2O2-induced genotoxic damage. PMID:23377016

  5. Color-Center Production and Formation in Electron-Irradiated Magnesium Aluminate Spinel and Ceria

    DOE PAGES

    Costantini, Jean-Marc; Lelong, Gerald; Guillaumet, Maxime; Weber, William J.; Takaki, Seiya; Yasuda, Kazuhiro

    2016-06-20

    Single crystals of magnesium aluminate spinel (MgAl2O4) with (100) or (110) orientations and cerium dioxide or ceria (CeO2) were irradiated by 1.0-MeV and 2.5-MeV electrons in a high fluence range. Point-defect production was studied by off-line UV-visible optical spectroscopy after irradiation. For spinel, regardless of both crystal orientation and electron energy, two characteristic broad bands centered at photon energies of 5.4 eV and 4.9 eV were assigned to F and F+ centers (neutral and singly-ionized oxygen vacancies), respectively, on the basis of available literature data. No clear differences in colour-centre formation were observed for the two crystal orientations. Using calculationsmore » of displacement cross sections by elastic collisions, these results are consistent with a very large threshold displacement energy (200 eV) for oxygen atoms at RT. A third very broad band centered at 3.7 eV might be attributed either to an oxygen hole center (V-type center) or an F2 dimer center (oxygen di-vacancy). The onset of recovery of these color centers took place at 200°C with almost full bleaching at 600°C. Activation energies (~0.3-0.4 eV) for defect recovery were deduced from the isochronal annealing data by using a first-order kinetics analysis. For ceria, a sub band-gap absorption feature peaked at ~3.1 eV was recorded for 2.5-MeV electron irradiation only. Assuming a ballistic process, we suggest that the latter defect might result from cerium atom displacement on the basis of computed cross sections.« less

  6. Mechanical properties of ceria nanorods and nanochains; the effect of dislocations, grain-boundaries and oriented attachment

    NASA Astrophysics Data System (ADS)

    Sayle, Thi X. T.; Inkson, Beverley J.; Karakoti, Ajay; Kumar, Amit; Molinari, Marco; Möbus, Günter; Parker, Stephen C.; Seal, Sudipta; Sayle, Dean C.

    2011-04-01

    We predict that the presence of extended defects can reduce the mechanical strength of a ceria nanorod by 70%. Conversely, the pristine material can deform near its theoretical strength limit. Specifically, atomistic models of ceria nanorods have been generated with full microstructure, including: growth direction, morphology, surface roughening (steps, edges, corners), point defects, dislocations and grain-boundaries. The models were then used to calculate the mechanical strength as a function of microstructure. Our simulations reveal that the compressive yield strengths of ceria nanorods, ca. 10 nm in diameter and without extended defects, are 46 and 36 GPa for rods oriented along [211] and [110] respectively, which represents almost 10% of the bulk elastic modulus and are associated with yield strains of about 0.09. Tensile yield strengths were calculated to be about 50% lower with associated yield strains of about 0.06. For both nanorods, plastic deformation was found to proceed via slip in the {001} plane with direction 〈110〉 - a primary slip system for crystals with the fluorite structure. Dislocation evolution for the nanorod oriented along [110] was nucleated via a cerium vacancy present at the surface. A nanorod oriented along [321] and comprising twin-grain boundaries with {111} interfacial planes was calculated to have a yield strength of about 10 GPa (compression and tension) with the grain boundary providing the vehicle for plastic deformation, which slipped in the plane of the grain boundary, with an associated 〈110〉 slip direction. We also predict, using a combination of atomistic simulation and DFT, that rutile-structured ceria is feasible when the crystal is placed under tension. The mechanical properties of nanochains, comprising individual ceria nanoparticles with oriented attachment and generated using simulated self-assembly, were found to be similar to those of the nanorod with grain-boundary. Images of the atom positions

  7. Lanthanide(III) complexation with an amide derived pyridinophane.

    PubMed

    Castro, Goretti; Bastida, Rufina; Macías, Alejandro; Pérez-Lourido, Paulo; Platas-Iglesias, Carlos; Valencia, Laura

    2015-02-16

    Herein we report a detailed investigation of the solid state and solution structures of lanthanide(III) complexes with the 18-membered pyridinophane ligand containing acetamide pendant arms TPPTAM (TPPTAM = 2,2',2″-(3,7,11-triaza-1,5,9(2,6)-tripyridinacyclododecaphane-3,7,11-triyl)triacetamide). The ligand crystallizes in the form of a clathrated hydrate, where the clathrated water molecule establishes hydrogen-bonding interactions with the amide NH groups and two N atoms of the macrocycle. The X-ray structures of 13 different Ln(3+) complexes obtained as the nitrate salts (Ln(3+) = La(3+)-Yb(3+), except Pm(3+)) have been determined. Additionally, the X-ray structure of the La(3+) complex obtained as the triflate salt was also obtained. In all cases the ligand provides 9-fold coordination to the Ln(3+) ion, ten coordination being completed by an oxygen atom of a coordinated water molecule or a nitrate or triflate anion. The bond distances of the metal coordination environment show a quadratic change along the lanthanide series, as expected for isostructural series of Ln(3+) complexes. Luminescence lifetime measurements obtained from solutions of the Eu(3+) and Tb(3+) complexes in H2O and D2O point to the presence of a water molecule coordinated to the metal ion in aqueous solutions. The analysis of the Ln(3+)-induced paramagnetic shifts indicates that the complexes are ten-coordinated throughout the lanthanide series from Ce(3+) to Yb(3+), and that the solution structure is very similar to the structures observed in the solid state. The complexes of the light Ln(3+) ions are fluxional due to a fast Δ(λλλλλλ) ↔ Λ(δδδδδδ) interconversion that involves the inversion of the macrocyclic ligand and the rotation of the acetamide pendant arms. The complexes of the small Ln(3+) ions are considerably more rigid, the activation free energy determined from VT (1)H NMR for the Lu(3+) complex being ΔG(⧧)298 = 72.4 ± 5.1 kJ mol(-1).

  8. From antenna to assay: lessons learned in lanthanide luminescence.

    PubMed

    Moore, Evan G; Samuel, Amanda P S; Raymond, Kenneth N

    2009-04-21

    Ligand-sensitized, luminescent lanthanide(III) complexes are of considerable importance because their unique photophysical properties (microsecond to millisecond lifetimes, characteristic and narrow emission bands, and large Stokes shifts) make them well suited as labels in fluorescence-based bioassays. The long-lived emission of lanthanide(III) cations can be temporally resolved from scattered light and background fluorescence to vastly enhance measurement sensitivity. One challenge in this field is the design of sensitizing ligands that provide highly emissive complexes with sufficient stability and aqueous solubility for practical applications. In this Account, we give an overview of some of the general properties of the trivalent lanthanides and follow with a summary of advances made in our laboratory in the development of highly luminescent Tb(III) and Eu(III) complexes for applications in biotechnology. A focus of our research has been the optimization of these compounds as potential commercial agents for use in homogeneous time-resolved fluorescence (HTRF) technology. Our approach involves developing high-stability octadentate Tb(III) and Eu(III) complexes that rely on all-oxygen donor atoms and using multichromophore chelates to increase molar absorptivity; earlier examples utilized a single pendant chromophore (that is, a single "antenna"). Ligands based on 2-hydroxyisophthalamide (IAM) provide exceptionally emissive Tb(III) complexes with quantum yield values up to approximately 60% that are stable at the nanomolar concentrations required for commercial assays. Through synthetic modification of the IAM chromophore and time-dependent density functional theory (TD-DFT) calculations, we have developed a method to predict absorption and emission properties of these chromophores as a tool to guide ligand design. Additionally, we have investigated chiral IAM ligands that yield Tb(III) complexes possessing both high quantum yield values and strong circularly

  9. Magneto-photoluminescence in lanthanide-bearing endohedral metallofullerenes with various cage symmetries

    NASA Astrophysics Data System (ADS)

    Merritt, Travis; Dorn, Harry; Khodaparast, Giti A.; McGill, Steve

    2012-02-01

    Taken as a family, endohedral metallofullerenes (EMF) nanomaterials provide opportunities for exquisite functional tunability at the nanoscale, enabling a wide range of synthetic nanoparticles with diverse sizes, symmetries, electronic, optical and, especially, magnetic properties. In particular, metallofullerenes incarcerating lanthanide ions will permit endohedral luminescence due to the 4f optically-active electrons being uninvolved in the stabilizing charge transfer between the endohedral guest and cage. In addition, if those lanthanide ions possess optical transitions beyond the absorption onset of the cage, a well-defined optical spectrum may be observed for the metallofullerene system. In this talk, several magneto-optical and time-resolved studies at high magnetic fields on lanthanide-based EMFs with different cage symmetries will be presented, where the residual magnetic degeneracies in the lanthanide ion energy levels are lifted and observed in the optical spectrum with magnetic field strengths in excess of 10 T.

  10. The interactions between the sterically demanding trimesitylphosphine oxide and trimesityphosphine with scandium and selected lanthanide ions

    NASA Astrophysics Data System (ADS)

    Platt, Andrew W. G.; Singh, Kuldip

    2016-05-01

    The reactions between lanthanide nitrates, Ln(NO3)3 and scandium and lanthanide trifluoromethane sulfonates, Ln(Tf)3 with trimesitylphosphine oxide, Mes3PO show that coordination to the metal ions does not lead to crystalline complexes. Investigation of the reactions by 31-P NMR spectroscopy shows that weak complexes are formed in solution. The crystal structures of Mes3PO·0.5CH3CN (1) and [Mes3PO]3H3O·2CH3CN·Tf (2), formed in the reaction between ScTf3 and Mes3PO, are reported. Trimesitylphosphine, Mes3P, is protonated by scandium and lanthanide trifluoromethane sulfonates and lanthanide nitrates in CD3CN and the structure of [Mes3PH]Cl·HCl·2H2O (3) is reported.

  11. Patterns in the stability of the lower oxidation states of the actinides and lanthanides

    SciTech Connect

    Mikheev, N.B.; Auerman, L.N.; Ionova, G.V.; Korshunov, B.G.; Spitsyn, V.I.

    1986-09-01

    The authors compare the first half of the lanthanides and the second half of the actinides by considering the specifics of the electronic structure of the valence atoms of the f-, d-, and s-orbitals, consisting of he following: The lanthanides from praseodymium to europium and from dysprosium to ytterbium, as well as the actinides from californium to nobelium, have the same electronic configuration f /SUP n/ s/sub 2/ in the state of free neutral atoms, which corresponds to their divalent state. On the basis of a consideration of the energy characteristics of the valence orbitals of the elements of the lanthanide and actinide famililies and as a result of an experimental determination of the standard oxidation potential of these elements, the authors consider the profound similarity between the elements of the first half of the lanthanide family and the second half of the actinide family to be established.

  12. Pentavalent Lanthanide Compounds: Formation and Characterization of Praseodymium(V) Oxides.

    PubMed

    Zhang, Qingnan; Hu, Shu-Xian; Qu, Hui; Su, Jing; Wang, Guanjun; Lu, Jun-Bo; Chen, Mohua; Zhou, Mingfei; Li, Jun

    2016-06-01

    The chemistry of lanthanides (Ln=La-Lu) is dominated by the low-valent +3 or +2 oxidation state because of the chemical inertness of the valence 4f electrons. The highest known oxidation state of the whole lanthanide series is +4 for Ce, Pr, Nd, Tb, and Dy. We report the formation of the lanthanide oxide species PrO4 and PrO2 (+) complexes in the gas phase and in a solid noble-gas matrix. Combined infrared spectroscopic and advanced quantum chemistry studies show that these species have the unprecedented Pr(V) oxidation state, thus demonstrating that the pentavalent state is viable for lanthanide elements in a suitable coordination environment.

  13. Lanthanide salts solutions: representation of osmotic coefficients within the binding mean spherical approximation.

    PubMed

    Ruas, Alexandre; Moisy, Philippe; Simonin, Jean-Pierre; Bernard, Olivier; Dufrêche, Jean-François; Turq, Pierre

    2005-03-24

    Osmotic coefficients of aqueous solutions of lanthanide salts are described using the binding mean spherical approximation (BIMSA) model based on the Wertheim formalism for association. The lanthanide(III) cation and the co-ion are allowed to form a 1-1 ion pair. Hydration is taken into account by introducing concentration-dependent cation size and solution permittivity. An expression for the osmotic coefficient, derived within the BIMSA, is used to fit data for a wide variety of lanthanide pure salt aqueous solutions at 25 degrees C. A total of 38 lanthanide salts have been treated, including perchlorates, nitrates, and chlorides. For most solutions, good fits could be obtained up to high ionic strengths. The relevance of the fitted parameters has been discussed, and a comparison with literature values has been made (especially the association constants) when available.

  14. The TRUSPEAK Concept: Combining CMPO and HDEHP for Separating Trivalent Lanthanides from the Transuranic Elements

    SciTech Connect

    Lumetta, Gregg J.; Gelis, Artem V.; Braley, Jenifer C.; Carter, Jennifer C.; Pittman, Jonathan W.; Warner, Marvin G.; Vandegrift, George F.

    2013-04-08

    Combining octyl(phenyl)-N,N-diisobutyl-carbamoylmethyl-phosphine oxide (CMPO) and bis-(2-ethylhexyl) phosphoric acid (HDEHP) into a single process solvent for separating transuranic elements from liquid high-level waste is explored. Co-extraction of americium and the lanthanide elements from nitric acid solution is possible with a solvent mixture consisting of 0.1-M CMPO plus 1-M HDEHP in n-dodecane. Switching the aqueous-phase chemistry to a citrate-buffered solution of diethylene triamine pentaacetic acid (DTPA) allows for selective stripping of americium, separating it from the lanthanide elements. Potential strategies for managing molybdenum and zirconium (both of which co-extract with americium and the lanthanides) have been developed. The work presented here demonstrates the feasibility of combining CMPO and HDEHP into a single extraction solvent for recovering americium from high-level waste and its separation from the lanthanides.

  15. Trivalent actinide and lanthanide separations using tetraalkyldiglycolamides (TCnDGA) in molecular and ionic liquid diluents

    SciTech Connect

    Bruce J. Mincher; Robert V. Fox; Mary E. Mincher; Chien M. Wai

    2014-09-01

    The use of the diglycolamide, tetrabutyldiglycolamide was investigated for intergroup separations of the lanthanides, focusing especially on those lanthanides (Y, Ce, Eu, Tb, Dy, Er, and Yb) found in lighting phosphors. Tetrabutyldiglycolamide extraction efficiency for the lanthanides varied depending on whether the diluent was the conventional molecular diluent 1-octanol, the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)-imide, or a mixture of the two. This was attributed to extraction of either neutral, cationic or anionic lanthanide metal complexes with nitrate ion. Based on the batch contact solvent extraction results measured here, a series of extractions providing product streams containing separated Y, Ce, Eu, Tb/Dy, and Er/Yb are proposed.

  16. Pentavalent Lanthanide Compounds: Formation and Characterization of Praseodymium(V) Oxides.

    PubMed

    Zhang, Qingnan; Hu, Shu-Xian; Qu, Hui; Su, Jing; Wang, Guanjun; Lu, Jun-Bo; Chen, Mohua; Zhou, Mingfei; Li, Jun

    2016-06-01

    The chemistry of lanthanides (Ln=La-Lu) is dominated by the low-valent +3 or +2 oxidation state because of the chemical inertness of the valence 4f electrons. The highest known oxidation state of the whole lanthanide series is +4 for Ce, Pr, Nd, Tb, and Dy. We report the formation of the lanthanide oxide species PrO4 and PrO2 (+) complexes in the gas phase and in a solid noble-gas matrix. Combined infrared spectroscopic and advanced quantum chemistry studies show that these species have the unprecedented Pr(V) oxidation state, thus demonstrating that the pentavalent state is viable for lanthanide elements in a suitable coordination environment. PMID:27100273

  17. Luminescent properties of Ln3+ doped tellurite glasses containing AlF3

    NASA Astrophysics Data System (ADS)

    Walas, Michalina; Pastwa, Agata; Lewandowski, Tomasz; Synak, Anna; Gryczyński, Ignacy; Sadowski, Wojciech; Kościelska, Barbara

    2016-09-01

    The low-phonon energy tellurite glasses TeO2-BaO-Bi2O3 and TeO2-BaO-Bi2O3-AlF3 triply doped with Eu3+, Tb3+, Tm3+ ions in two different molar ratios were synthesized using melt-quenching technique. Their structure and luminescence properties were widely investigated by X-ray Diffraction (XRD), Differential Scanning Calorimetry (DSC), Fourier Transform Infrared Spectroscopy (FTIR) and Photoluminescence Spectroscopy (PL). The luminescence spectra of Eu3+, Tb3+, Tm3+ co-doped glasses show apart of the bands corresponding to the 4f-4f transitions of lanthanide ions also band corresponding to glass matrix. AlF3 doping increases emission intensity, although to improve overall emission color further studies on molar composition of samples and the molar ratio of the components should be carried out.

  18. Surface electrochemistry of CO2 reduction and CO oxidation on Sm-doped CeO(2-x): coupling between Ce(3+) and carbonate adsorbates.

    PubMed

    Feng, Zhuoluo A; Machala, Michael L; Chueh, William C

    2015-05-14

    The efficient electro-reduction of CO2 to chemical fuels and the electro-oxidation of hydrocarbons for generating electricity are critical toward a carbon-neutral energy cycle. The simplest reactions involving carbon species in solid-oxide fuel cells and electrolyzer cells are CO oxidation and CO2 reduction, respectively. In catalyzing these reactions, doped ceria exhibits a mixed valence of Ce(3+) and Ce(4+), and has been employed as a highly active and coking-resistant electrode. Here we report an operando investigation of the surface reaction mechanism on a ceria-based electrochemical cell using ambient pressure X-ray photoelectron spectroscopy. We show that the reaction proceeds via a stable carbonate intermediate, the coverage of which is coupled to the surface Ce(3+) concentration. Under CO oxidation polarization, both the carbonate and surface Ce(3+) concentration decrease with overpotential. Under CO2 reduction polarization, on the other hand, the carbonate coverage saturates whereas the surface Ce(3+) concentration increases with overpotential. The evolution of these reaction intermediates was analyzed using a simplified two-electron reaction scheme. We propose that the strong adsorbate-adsorbate interaction explains the coverage-dependent reaction mechanism. These new insights into the surface electrochemistry of ceria shed light on the optimization strategies for better fuel cell electrocatalysts.

  19. In Vivo Inflammatory Effects of Ceria Nanoparticles on CD-1 Mouse: Evaluation by Hematological, Histological, and TEM Analysis

    PubMed Central

    Poma, Anna; Ragnelli, Anna Maria; de Lapuente, Joaquin; Ramos, David; Borras, Miquel; Di Gioacchino, Mario; Santucci, Sandro; De Marzi, Laura

    2014-01-01

    The attention on CeO2-NPs environmental and in vivo effects is due to their presence in diesel exhaust and in diesel filters that release a more water-soluble form of ceria NPs, as well as to their use for medical applications. In this work, acute and subacute in vivo toxicity assays demonstrate no lethal effect of these NPs. Anyhow, performing in vivo evaluations on CD-1 mouse systems, we demonstrate that it is even not correct to assert that ceria NPs are harmless for living systems as they can induce status of inflammation, revealed by hematological-chemical-clinical assays as well as histological and TEM microscope observations. TEM analysis showed the presence of NPs in alveolar macrophages. Histological evaluation demonstrated the NPs presence in lungs tissues and this can be explained by assuming their ability to go into the blood stream and lately into the organs (generating inflammation). PMID:25032226

  20. SEPARATION OF EUROPIUM FROM OTHER LANTHANIDE RAE EARTHS BY SOLVENT EXTRACTION

    DOEpatents

    Peppard, D.F.; Horwitz, E.P.; Mason, G.W.

    1963-02-12

    This patent deals with a process of separating europium from other lanthanides present in aqueous hydrochloric or sulfuric acid solutions. The europium is selectively reduced to the divalent state with a divalent chromium salt formed in situ from chromium(III) salt plus zinc amalgam. The other trivalent lanthanides are then extracted away from the divalent europium with a nitrogen-flushed phosphoric acid ester or a phosphonic acid ester. (AEC)

  1. Novel materials based on DNA-CTMA and lanthanide (Ce(3+) , Pr(3+) ).

    PubMed

    Lazar, Cosmina Andreea; Kajzar, François; Mihaly, Maria; Rogozea, Adina Elena; Petcu, Adina Roxana; Olteanu, Nicoleta Liliana; Rau, Ileana

    2016-09-01

    New, deoxyribonucleic acid (DNA) based compounds, functionalized with hexadecyltrimethylammonium chloride (CTMA) and lanthanide hydroxide nanoparticles were synthesized. The spectral measurements suggest that between the DNA-CTMA complex and the lanthanide (III) ions a chemical interaction takes place. The obtained materials exhibit an improved fluorescence efficiency, showing a potential interest for application in photonics, and more particularly, in light emitting devices. © 2016 Wiley Periodicals, Inc. Biopolymers 105: 613-617, 2016. PMID:27120012

  2. Flame made ceria supported noble metal catalysts for efficient H2 production via the water gas shift reaction

    NASA Astrophysics Data System (ADS)

    Cavusoglu, G.; Lichtenberg, H.; Gaur, A.; Goldbach, A.; Grunwaldt, J.-D.

    2016-05-01

    Rh/ceria catalysts were synthesized by flame spray pyrolysis for high temperature water gas shift (WGS) reactions. These catalysts show a high specific surface area due to a high degree of nanocrystallinity. X-ray absorption spectroscopy (XAS) unraveled the formation of small Rh particles under WGS reaction conditions. The catalytic activity was examined at atmospheric pressure by measuring CO conversion as a function of temperature. Some methane formation was observed above 310°C.

  3. Gold Coated Lanthanide Phosphate Nanoparticles for Targeted Alpha Generator Radiotherapy

    SciTech Connect

    McLaughlin, Mark F; Woodward, Jonathan; Boll, Rose Ann; Wall, Jonathan; Rondinone, Adam Justin; Kennel, Steve J; Mirzadeh, Saed; Robertson, David J.

    2013-01-01

    Targeted radiotherapies maximize cytotoxicty to cancer cells. In vivo generators such as 225Ac, which emits four particles in its decay chain, can significantly amplify the radiation dose delivered to the target site. However, renal dose from unbound 213Bi escaping during the decay process limits the dose of 225Ac that can be administered. Traditional chelating moieties are unable to sequester the radioactive daughters because of the high recoil energy from alpha particle emission. To counter this, we demonstrate that an engineered multilayered nanoparticle-antibody conjugate can both deliver radiation and contain the decay daughters of the in vivo -generator 225Ac while targeting biologically relevant receptors. These multi-shell nanoparticles combine the radiation resistance of crystalline lanthanide phosphate to encapsulate and contain 225Ac and its radioactive decay daughters, the magnetic properties of gadolinium phosphate for easy separation, and established surface chemistry of gold for attachment of nanoparticles to targeting antibodies.

  4. Multimodal cancer imaging using lanthanide-based upconversion nanoparticles.

    PubMed

    Yang, Dongmei; Li, Chunxia; Lin, Jun

    2015-01-01

    Multimodal nanoprobes that integrate different imaging modalities in one nano-system could offer synergistic effect over any modality alone to satisfy the higher requirements on the efficiency and accuracy for clinical diagnosis and medical research. Upconversion nanoparticles (UCNPs), particularly lanthanide (Ln)-based NPs have been regarded as an ideal building block for constructing multimodal bioprobes due to their fascinating properties. In this review, we first summarize recent advances in the optimizations of existing UCNPs. In particular, we highlight the applications of Ln-based UCNPs for multimodal cancer imaging in vitro and in vivo. The explorations of UCNPs-based multimodal nanoprobes for targeting diagnosis and imaging-guided therapeutics are also presented. Finally, the challenges and perspectives of Ln-based UCNPs in this rapid growing field are discussed. PMID:26293416

  5. Stabilization of molecular lanthanide polysulfides by bulky scorpionate ligands.

    PubMed

    Kühling, Marcel; McDonald, Robert; Liebing, Phil; Hilfert, Liane; Ferguson, Michael J; Takats, Josef; Edelmann, Frank T

    2016-07-01

    Well-defined lanthanide polysulfide complexes containing S4(2-) and S5(2-) ligands, the samarium(iii) pentasulfide complex Sm(Tp(iPr2))(κ(1)-3,5-(i)Pr2Hpz)(S5) and the tetrasulfide-bridged binuclear ytterbium(iii) complex (μ-S4)[Yb(Tp(iPr2))(κ(1)-3,5-(i)Pr2Hpz)(κ(2)-3,5-(i)Pr2pz)]2 (Tp(iPr2) = hydro-tris(3,5-diisopropylpyrazolyl)borate), have been synthesized and structurally characterized by single-crystal X-ray diffraction. PMID:27151931

  6. Selectivity enhancement of Arsenazo(III) reagent towards heavier lanthanides using polyaminocarboxylic acids: A spectrophotometric study

    NASA Astrophysics Data System (ADS)

    Matharu, Komal; Mittal, Susheel K.; Ashok Kumar, S. K.; Sahoo, Suban K.

    2015-06-01

    A new study has been conducted to quantify lanthanide(III) ions using Arsenazo III-polyaminocarboxylic acid (PACA) system. The study disclosed two different analytically important information: (i) λmax of lanthanide-Arsenazo III complexes for lighter lanthanides like Ce(III) and Nd(III) did not shift from its original position on addition of PACA and (ii) for heavier lanthanides like Dy(III), Tm(III) and Lu(III) a new λmax at 538 nm was observed, while wavelengths at 610 nm and 654 nm were disappeared in presence of ethylenediaminetertracetic acid (EDTA) and trans-1,2-Diaminocyclohexane-N,N,N‧,N‧-tetraacetic acid (DCTA), further the intensity of peak decreased with increase in lanthanide(III) ion concentration. Effect of ethylene glycol-bis(2-aminoethylether)-N,N,N‧,N‧-tetraacetic acid (EGTA) and N-(2-hydroxyethyl) ethylenediamine-N,N‧,N‧-triacetic acid (EDTA-OH) on Arsenzo(III)-Ln(III) complex is very weak and there is no analytically importance of such interaction. Moreover, this work confirms that Nd(III) and heavy lanthanides can be successfully determined with high accuracy in the working range of concentration of these metal ions.

  7. Lanthanide transport in stabilized zirconias: interrelation between ionic radius and diffusion coefficient.

    PubMed

    Kilo, Martin; Taylor, Marcela A; Argirusis, Christos; Borchardt, Günter; Weber, Sylvain; Scherrer, Hubert; Jackson, Robert A

    2004-09-15

    The diffusion of all stable lanthanides was measured both in calcia stabilized zirconia (CSZ) and in yttria stabilized zirconia (YSZ) in the temperature range between 1,286 and 1,600 degrees C. The lanthanide diffusion coefficients obtained increase with increasing ionic radius. The experimental activation enthalpy of diffusion is near 6 eV for CSZ and between 4 and 5 eV for YSZ and is not strongly affected by the type of lanthanide. The results were correlated with defect energy calculations of the lanthanide diffusion enthalpy using the Mott-Littleton approach. An association enthalpy of cation vacancies with oxygen vacancies of about 1 eV (96 kJ/mol) was deduced in the case of CSZ, while there is no association in the case of YSZ. Furthermore, the change in diffusion coefficients can be correlated to the interaction parameter for the interaction between the lanthanide oxide with zirconia: The higher the interaction parameter, the higher the lanthanide diffusion coefficient.

  8. Lanthanide transport in stabilized zirconias: Interrelation between ionic radius and diffusion coefficient

    NASA Astrophysics Data System (ADS)

    Kilo, Martin; Taylor, Marcela A.; Argirusis, Christos; Borchardt, Günter; Weber, Sylvain; Scherrer, Hubert; Jackson, Robert A.

    2004-09-01

    The diffusion of all stable lanthanides was measured both in calcia stabilized zirconia (CSZ) and in yttria stabilized zirconia (YSZ) in the temperature range between 1286 and 1600 °C. The lanthanide diffusion coefficients obtained increase with increasing ionic radius. The experimental activation enthalpy of diffusion is near 6 eV for CSZ and between 4 and 5 eV for YSZ and is not strongly affected by the type of lanthanide. The results were correlated with defect energy calculations of the lanthanide diffusion enthalpy using the Mott-Littleton approach. An association enthalpy of cation vacancies with oxygen vacancies of about 1 eV (96 kJ/mol) was deduced in the case of CSZ, while there is no association in the case of YSZ. Furthermore, the change in diffusion coefficients can be correlated to the interaction parameter for the interaction between the lanthanide oxide with zirconia: The higher the interaction parameter, the higher the lanthanide diffusion coefficient.

  9. Lanthanide-based laser-induced phosphorescence for spray diagnostics

    NASA Astrophysics Data System (ADS)

    van der Voort, D. D.; Maes, N. C. J.; Lamberts, T.; Sweep, A. M.; van de Water, W.; Kunnen, R. P. J.; Clercx, H. J. H.; van Heijst, G. J. F.; Dam, N. J.

    2016-03-01

    Laser-induced phosphorescence (LIP) is a relatively recent and versatile development for studying flow dynamics. This work investigates certain lanthanide-based molecular complexes for their use in LIP for high-speed sprays. Lanthanide complexes in solutions have been shown to possess long phosphorescence lifetimes (˜1-2 ms) and to emit light in the visible wavelength range. In particular, europium and terbium complexes are investigated using fluorescence/phosphorescence spectrometry, showing that europium-thenoyltrifluoracetone-trioctylphosphineoxide (Eu-TTA-TOPO) can be easily and efficiently excited using a standard frequency-tripled Nd:YAG laser. The emitted spectrum, with maximum intensity at a wavelength of 614 nm, is shown not to vary strongly with temperature (293-383 K). The decay constant of the phosphorescence, while independent of ambient pressure, decreases by approximately 12 μs/K between 323 and 373 K, with the base level of the decay constant dependent on the used solvent. The complex does not luminesce in the gas or solid state, meaning only the liquid phase is visualized, even in an evaporating spray. By using an internally excited spray containing the phosphorescent complex, the effect of vaporization is shown through the decrease in measured intensity over the length of the spray, together with droplet size measurements using interferometric particle imaging. This study shows that LIP, using the Eu-TTA-TOPO complex, can be used with different solvents, including diesel surrogates. Furthermore, it can be easily handled and used in sprays to investigate spray breakup and evaporation.

  10. Interaction between lanthanide ions and Saccharomyces cerevisiae cells.

    PubMed

    Ene, Cristian D; Ruta, Lavinia L; Nicolau, Ioana; Popa, Claudia V; Iordache, Virgil; Neagoe, Aurora D; Farcasanu, Ileana C

    2015-10-01

    Lanthanides are a group of non-essential elements with important imaging and therapeutic applications. Although trivalent lanthanide ions (Ln³⁺) are used as potent blockers of Ca²⁺ channels, the systematic studies correlating Ln³⁺ accumulation and toxicity to Ca²⁺ channel blocking activity are scarce. In this study, we made use of the eukaryotic model Saccharomyces cerevisiae to investigate the correlation between Ln³⁺ accumulation, their toxicity and their capacity to block the exogenous stress-induced Ca²⁺ influx into the cytosol. It was found that the Ln³⁺ blocked the Ca²⁺ entry into the yeast cells only when present at concentration high enough to allow rapid binding to cell surface. At lower concentrations, Ln³⁺ were taken up by the cell, but Ca²⁺ blockage was no longer achieved. At 1 mM concentration, all ions from the Ln³⁺ series could block Ca²⁺ entry into cytosol with the exception of La³⁺, and to a lesser extent, Pr³⁺ and Nd³⁺. The plasma membrane Ca²⁺-channel Cch1/Mid1 contributed to La³⁺ and Gd³⁺ entry into the cells, with a significant preference for La³⁺. The results open the possibility to obtain cells loaded with controlled amounts and ratios of Ln³⁺.

  11. Lanthanide-based laser-induced phosphorescence for spray diagnostics.

    PubMed

    van der Voort, D D; Maes, N C J; Lamberts, T; Sweep, A M; van de Water, W; Kunnen, R P J; Clercx, H J H; van Heijst, G J F; Dam, N J

    2016-03-01

    Laser-induced phosphorescence (LIP) is a relatively recent and versatile development for studying flow dynamics. This work investigates certain lanthanide-based molecular complexes for their use in LIP for high-speed sprays. Lanthanide complexes in solutions have been shown to possess long phosphorescence lifetimes (∼1-2 ms) and to emit light in the visible wavelength range. In particular, europium and terbium complexes are investigated using fluorescence/phosphorescence spectrometry, showing that europium-thenoyltrifluoracetone-trioctylphosphineoxide (Eu-TTA-TOPO) can be easily and efficiently excited using a standard frequency-tripled Nd:YAG laser. The emitted spectrum, with maximum intensity at a wavelength of 614 nm, is shown not to vary strongly with temperature (293-383 K). The decay constant of the phosphorescence, while independent of ambient pressure, decreases by approximately 12 μs/K between 323 and 373 K, with the base level of the decay constant dependent on the used solvent. The complex does not luminesce in the gas or solid state, meaning only the liquid phase is visualized, even in an evaporating spray. By using an internally excited spray containing the phosphorescent complex, the effect of vaporization is shown through the decrease in measured intensity over the length of the spray, together with droplet size measurements using interferometric particle imaging. This study shows that LIP, using the Eu-TTA-TOPO complex, can be used with different solvents, including diesel surrogates. Furthermore, it can be easily handled and used in sprays to investigate spray breakup and evaporation. PMID:27036779

  12. X-ray spectral diagnostics of synthetic lanthanide silicates

    NASA Astrophysics Data System (ADS)

    Kravtsova, A. N.; Guda, A. A.; Soldatov, A. V.; Goettlicher, J.; Taroev, V. K.; Kashaev, A. A.; Suvorova, L. F.; Tauson, V. L.

    2015-12-01

    Potassium and rare-earth (Eu, Sm, Yb, Ce) silicate and aluminosilicate crystals are hydrothermally synthesized under isothermal conditions at 500°C and a pressure of 100 MPa. The chemical and structural formulas of the synthesized compounds HK6Eu[Si10O25], K7Sm3[Si12O32], K2Sm[AlSi4O12] · 0.375H2O, K4Yb2[Si8O21], and K4Ce2[Al2Si8O24] are determined. In addition, a synthesis product with Eu, in which the dominant phase is assumed to be K3Eu3+[Si6O15] · 2H2O, is studied. The oxidation state of lanthanides in the silicates under study is determined based on X-ray absorption near-edge structure spectroscopy. The Eu L 3-, Sm L 3-, Yb L 3-, and Ce L 3-edge X-ray absorption spectra of the studied silicates and reference samples are recorded using a Rigaku R-XAS laboratory spectrometer. As reference samples, Eu2+S, Eu3+F3, Eu 2 3+ O3, Sm 2 3+ O3, Yb 2 3+ O3, Yb3+F3, Yb3+Cl3, Ce 2 3+ O3, and Ce4+O2 are used. Comparison of the absorption edge energies of lanthanide silicates and reference samples shows that Eu, Sm, Yb, and Ce in all the samples studied are in the oxidation state 3+. The synthesized silicates will supplement our knowledge of possible rare-earth minerals existing in hydrothermal systems, which is important for analyzing the distribution spectra of rare elements, which are widely used for diagnostics of geochemical processes and determination of sources of ore materials.

  13. Transient heat and mass transfer analysis in a porous ceria structure of a novel solar redox reactor

    SciTech Connect

    Chandran, RB; Bader, R; Lipinski, W

    2015-06-01

    Thermal transport processes are numerically analyzed for a porous ceria structure undergoing reduction in a novel redox reactor for solar thermochemical fuel production. The cylindrical reactor cavity is formed by an array of annular reactive elements comprising the porous ceria monolith integrated with gas inlet and outlet channels. Two configurations are considered, with the reactor cavity consisting of 10 and 20 reactive elements, respectively. Temperature dependent boundary heat fluxes are obtained on the irradiated cavity wall by solving for the surface radiative exchange using the net radiation method coupled to the heat and mass transfer model of the reactive element. Predicted oxygen production rates are in the range 40-60 mu mol s(-1) for the geometries considered. After an initial rise, the average temperature of the reactive element levels off at 1660 and 1680 K for the two geometries, respectively. For the chosen reduction reaction rate model, oxygen release continues after the temperature has leveled off which indicates that the oxygen release reaction is limited by chemical kinetics and/or mass transfer rather than by the heating rate. For a fixed total mass of ceria, the peak oxygen release rate is doubled for the cavity with 20 reactive elements due to lower local oxygen partial pressure. (C) 2015 Elsevier Masson SAS. All rights reserved.

  14. Synthesis and characterization of fluorescence-labelled silica core-shell and noble metal-decorated ceria nanoparticles

    PubMed Central

    Rennhak, Markus; Reller, Armin

    2014-01-01

    Summary The present review article covers work done in the cluster NPBIOMEM in the DFG priority programme SPP 1313 and focuses on synthesis and characterization of fluorescent silica and ceria nanoparticles. Synthetic methods for labelling of silica and polyorganosiloxane/silica core–shell nanoparticles with perylenediimide derivatives are described, as well as the modification of the shell with thiol groups. Photometric methods for the determination of the number of thiol groups and an estimate for the number of fluorescent molecules per nanoparticles, including a scattering correction, have been developed. Ceria nanoparticles decorated with noble metals (Pt, Pd, Rh) are models for the decomposition products of automobile catalytic converters which appear in the exhaust gases and finally interact with biological systems including humans. The control of the degree of agglomeration of small ceria nanoparticles is the basis for their synthesis. Almost monodisperse agglomerates (40 ± 4–260 ± 40 nm diameter) can be prepared and decorated with noble metal nanoparticles (2–5 nm diameter). Fluorescence labelling with ATTO 647N gave the model particles which are now under biophysical investigation. PMID:25671137

  15. Shape-Dependent Activity of Ceria for Hydrogen Electro-Oxidation in Reduced-Temperature Solid Oxide Fuel Cells.

    PubMed

    Tong, Xiaofeng; Luo, Ting; Meng, Xie; Wu, Hao; Li, Junliang; Liu, Xuejiao; Ji, Xiaona; Wang, Jianqiang; Chen, Chusheng; Zhan, Zhongliang

    2015-11-01

    Single crystalline ceria nanooctahedra, nanocubes, and nanorods are hydrothermally synthesized, colloidally impregnated into the porous La0.9Sr0.1Ga0.8Mg0.2O3-δ (LSGM) scaffolds, and electrochemically evaluated as the anode catalysts for reduced temperature solid oxide fuel cells (SOFCs). Well-defined surface terminations are confirmed by the high-resolution transmission electron microscopy--(111) for nanooctahedra, (100) for nanocubes, and both (110) and (100) for nanorods. Temperature-programmed reduction in H2 shows the highest reducibility for nanorods, followed sequentially by nanocubes and nanooctahedra. Measurements of the anode polarization resistances and the fuel cell power densities reveal different orders of activity of ceria nanocrystals at high and low temperatures for hydrogen electro-oxidation, i.e., nanorods > nanocubes > nanooctahedra at T ≤ 450 °C and nanooctahedra > nanorods > nanocubes at T ≥ 500 °C. Such shape-dependent activities of these ceria nanocrystals have been correlated to their difference in the local structure distortions and thus in the reducibility. These findings will open up a new strategy for design of advanced catalysts for reduced-temperature SOFCs by elaborately engineering the shape of nanocrystals and thus selectively exposing the crystal facets.

  16. Ceria-Zirconia Particles Wrapped in a 2D Carbon Envelope: Improved Low-Temperature Oxygen Transfer and Oxidation Activity.

    PubMed

    Aneggi, Eleonora; Rico-Perez, Veronica; de Leitenburg, Carla; Maschio, Stefano; Soler, Lluís; Llorca, Jordi; Trovarelli, Alessandro

    2015-11-16

    Engineering the interface between different components of heterogeneous catalysts at nanometer level can radically alter their performances. This is particularly true for ceria-based catalysts where the interactions are critical for obtaining materials with enhanced properties. Here we show that mechanical contact achieved by high-energy milling of CeO2-ZrO2 powders and carbon soot results in the formation of a core of oxide particles wrapped in a thin carbon envelope. This 2D nanoscale carbon arrangement greatly increases the number and quality of contact points between the oxide and carbon. Consequently, the temperatures of activation and transfer of the oxygen in ceria are shifted to exceptionally low temperatures and the soot combustion rate is boosted. The study confirms the importance of the redox behavior of ceria-zirconia particles in the mechanism of soot oxidation and shows that the organization of contact points at the nanoscale can significantly modify the reactivity resulting in unexpected properties and functionalities. PMID:26448053

  17. Hydrogen and methoxy coadsorption in the computation of the catalytic conversion of methanol on the ceria (111) surface

    NASA Astrophysics Data System (ADS)

    Beste, Ariana; Overbury, Steven H.

    2016-06-01

    Methanol decomposition to formaldehyde catalyzed by the ceria (111) surface was investigated using the DFT + U method. Our results rationalize experimental temperature programmed desorption experiments on the fully oxidized surface. Particular attention was paid to the effect of coadsorption of methoxy and hydrogen on various aspects of the conversion process. This issue had been raised by the experimental observation of water desorption at low temperature removing hydrogen from the system. Within this context, we also investigated hydrogen diffusion on the ceria surface. The hydrogen/methoxy interaction on ceria was shown to be ionic regardless of separation distance. The barrier for dehydrogenation of methoxy using the ionic model system, where hydrogen is coadsorbed, is above 1 eV. This barrier becomes negligible if an incorrect neutral model without coadsorbed hydrogen is employed. While water formation from isolated surface hydrogen is unlikely at low temperature, the presence of coadsorbed methoxy reduces the reaction energy for water formation considerably. For the dehydrated surface, we observed that the preference of the electron to locate at the methoxy oxygen instead of the cerium atom results in a surface that does not contain Ce3 + ions, despite the existence of a vacancy.

  18. Ceria-Zirconia Particles Wrapped in a 2D Carbon Envelope: Improved Low-Temperature Oxygen Transfer and Oxidation Activity.

    PubMed

    Aneggi, Eleonora; Rico-Perez, Veronica; de Leitenburg, Carla; Maschio, Stefano; Soler, Lluís; Llorca, Jordi; Trovarelli, Alessandro

    2015-11-16

    Engineering the interface between different components of heterogeneous catalysts at nanometer level can radically alter their performances. This is particularly true for ceria-based catalysts where the interactions are critical for obtaining materials with enhanced properties. Here we show that mechanical contact achieved by high-energy milling of CeO2-ZrO2 powders and carbon soot results in the formation of a core of oxide particles wrapped in a thin carbon envelope. This 2D nanoscale carbon arrangement greatly increases the number and quality of contact points between the oxide and carbon. Consequently, the temperatures of activation and transfer of the oxygen in ceria are shifted to exceptionally low temperatures and the soot combustion rate is boosted. The study confirms the importance of the redox behavior of ceria-zirconia particles in the mechanism of soot oxidation and shows that the organization of contact points at the nanoscale can significantly modify the reactivity resulting in unexpected properties and functionalities.

  19. Syntheses, structures and tunable luminescence of lanthanide metal-organic frameworks based on azole-containing carboxylic acid ligand

    NASA Astrophysics Data System (ADS)

    Zhao, Dian; Rao, Xingtang; Yu, Jiancan; Cui, Yuanjing; Yang, Yu; Qian, Guodong

    2015-10-01

    Design and synthesis of a series of isostructural lanthanide metal-organic frameworks (LnMOFs) serving as phosphors by coordinate the H2TIPA (5-(1H-tetrazol-5-yl)isophthalic acid) ligands and lanthanide ions is reported. The color of the luminescence can be tuned by adjusting the relative concentration of the lanthanide ions in the host framework GdTIPA, and near-pure-white light emission can be achieved.

  20. Impact of dynamic specimen shape evolution on the atom probe tomography results of doped epitaxial oxide multilayers: Comparison of experiment and simulation

    SciTech Connect

    Madaan, Nitesh; Nandasiri, Manjula; Devaraj, Arun; Bao, Jie; Xu, Zhijie; Thevuthasan, Suntharampillai

    2015-08-31

    The experimental atom probe tomography (APT) results from two different specimen orientations (top-down and sideways) of a high oxygen ion conducting Samaria-doped-ceria/Scandia-stabilized-zirconia multilayer thin film solid oxide fuel cell electrolyte was compared with level-set method based field evaporation simulations for the same specimen orientations. This experiment-simulation comparison explains the dynamic specimen shape evolution and ion trajectory aberrations that can induce density artifacts in final reconstruction, leading to inaccurate estimation of interfacial intermixing. This study highlights the importance of comparing experimental results with field evaporation simulations when using APT to study oxide heterostructure interfaces.