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Sample records for gd2o3-doped ceo2 thin

  1. A facile synthesis of high quality nanostructured CeO2 and Gd2O3-doped CeO2 solid electrolytes for improved electrochemical performance.

    PubMed

    Kuo, Yu-Lin; Su, Yu-Ming; Chou, Hung-Lung

    2015-06-01

    This study describes the use of a composite nitrate salt solution as a precursor to synthesize CeO2 and Gd2O3-doped CeO2 (GDC) nanoparticles (NPs) using an atmospheric pressure plasma jet (APPJ). The microstructures of CeO2 and GDC NPs were found to be cubical and spherical shaped nanocrystallites with average particle sizes of 10.5 and 6.7 nm, respectively. Reactive oxygen species, detected by optical emission spectroscopy (OES), are believed to be the major oxidative agents for the formation of oxide materials in the APPJ process. Based on the material characterization and OES observations, the study effectively demonstrated the feasibility of preparing well-crystallized GDC NPs by the APPJ system as well as the gas-to-particle mechanism. Notably, the Bader charge of CeO2 and Ce0.9Gd0.1O2 characterized by density function theory (DFT) simulation and AC impedance measurements shows that Gd helps in increasing the charge on Ce0.9Gd0.1O2 NPs, thus improving their conductivity and making them candidate materials for electrolytes in solid oxide fuel cells.

  2. A facile synthesis of high quality nanostructured CeO2 and Gd2O3-doped CeO2 solid electrolytes for improved electrochemical performance.

    PubMed

    Kuo, Yu-Lin; Su, Yu-Ming; Chou, Hung-Lung

    2015-06-01

    This study describes the use of a composite nitrate salt solution as a precursor to synthesize CeO2 and Gd2O3-doped CeO2 (GDC) nanoparticles (NPs) using an atmospheric pressure plasma jet (APPJ). The microstructures of CeO2 and GDC NPs were found to be cubical and spherical shaped nanocrystallites with average particle sizes of 10.5 and 6.7 nm, respectively. Reactive oxygen species, detected by optical emission spectroscopy (OES), are believed to be the major oxidative agents for the formation of oxide materials in the APPJ process. Based on the material characterization and OES observations, the study effectively demonstrated the feasibility of preparing well-crystallized GDC NPs by the APPJ system as well as the gas-to-particle mechanism. Notably, the Bader charge of CeO2 and Ce0.9Gd0.1O2 characterized by density function theory (DFT) simulation and AC impedance measurements shows that Gd helps in increasing the charge on Ce0.9Gd0.1O2 NPs, thus improving their conductivity and making them candidate materials for electrolytes in solid oxide fuel cells. PMID:25959436

  3. Structural and compositional characterization of laser ablated CeO 2 thin films

    NASA Astrophysics Data System (ADS)

    Sánchez, F.; Varela, M.; Ferrater, C.; García-Cuenca, M. V.; Aguiar, R.; Morenza, J. L.

    1993-06-01

    CeO 2 thin films have been deposited on Si(100) substrates by laser ablation in ultrahigh vacuum. The structural and compositional properties of the films were studied by XRD, TEM, XPS and SIMS. All the films deposited in the temperature range 400-850°C have a preferential orientation ( hhh). The deposition in an oxygen environment (10 -4 mbar) results in a great reduction of the film crystallinity. The existance of a 5 nm thick amorphous layer between the CeO 2 film and the Si(100) substrate has been observed by TEM. XPS and SIMS results seem to indicate that this layer is a cerium silicade. SIMS profiles show that Ce diffuses toward the substrate, whereas O and Si do not diffuse.

  4. Structural, morphological and optical properties of CeO2 thin films deposited by RF sputtering

    NASA Astrophysics Data System (ADS)

    Murugan, R.; Vijayaprasath, G.; Sakthivel, P.; Mahalingam, T.; Ravi, G.

    2016-05-01

    Cerium oxide (CeO2) thin films were deposited on glass substrates by sputtering at various substrate temperatures. CeO2 films were characterized by X-ray diffraction, FESEM, PL and Raman analyses. X-ray diffraction patterns of films reveal fcc cubic structure with preferential orientation along (2 2 0) crystallographic plane. SEM images show that the particles are uniformly distributed on the film surface. The films were found to be well adheared to the substrates and pin holes are not observed on the surface of the films. PL spectra exhibits a strong near band-gap-edge emission and a broad blue, green luminescence, which can be assigned to the presence of Ce and O vacancies, amorphous phases, deep level impurities and structural defects. The relative intensity between the different peaks of the bands related to defects or impurities was studied as a tool for quality control of the films. Moreover, vibrational measurements through Raman analysis were carried out and the results are discussed.

  5. Surface potentials of (111), (110) and (100) oriented CeO2-x thin films

    NASA Astrophysics Data System (ADS)

    Wardenga, Hans F.; Klein, Andreas

    2016-07-01

    Differently oriented CeO2 thin films were prepared by radio frequency magnetron sputter deposition from a nominally undoped CeO2 target. (111), (110) and (100) oriented films were achieved by deposition onto Al2O3(0001)/Pt(111), MgO(110)/Pt(110) and SrTiO3:Nb(100) substrates, respectively. Epitaxial growth is verified using X-ray diffraction analysis. The films were analyzed by in situ photoelectron spectroscopy to determine the ionization potential, work function, Fermi level position and Ce3+ concentration at the surface in dependence of crystal orientation, deposition conditions and post-deposition treatment in reducing and oxidizing atmosphere. We observed a very high variation of the work function and ionization potential of more than 2 eV for all surface orientations, while the Fermi level varies by only 0.3 eV within the energy gap. The work function generally decreases with increasing Ce3+ surface concentration but comparatively high Ce3+ concentrations remain even after strongly oxidizing treatments. This is related to the presence of subsurface oxygen vacancies.

  6. Ultra-thin solid oxide fuel cells: Materials and devices

    NASA Astrophysics Data System (ADS)

    Kerman, Kian

    Solid oxide fuel cells are electrochemical energy conversion devices utilizing solid electrolytes transporting O2- that typically operate in the 800 -- 1000 °C temperature range due to the large activation barrier for ionic transport. Reducing electrolyte thickness or increasing ionic conductivity can enable lower temperature operation for both stationary and portable applications. This thesis is focused on the fabrication of free standing ultrathin (<100 nm) oxide membranes of prototypical O 2- conducting electrolytes, namely Y2O3-doped ZrO2 and Gd2O3-doped CeO2. Fabrication of such membranes requires an understanding of thin plate mechanics coupled with controllable thin film deposition processes. Integration of free standing membranes into proof-of-concept fuel cell devices necessitates ideal electrode assemblies as well as creative processing schemes to experimentally test devices in a high temperature dual environment chamber. We present a simple elastic model to determine stable buckling configurations for free standing oxide membranes. This guides the experimental methodology for Y 2O3-doped ZrO2 film processing, which enables tunable internal stress in the films. Using these criteria, we fabricate robust Y2O3-doped ZrO2 membranes on Si and composite polymeric substrates by semiconductor and micro-machining processes, respectively. Fuel cell devices integrating these membranes with metallic electrodes are demonstrated to operate in the 300 -- 500 °C range, exhibiting record performance at such temperatures. A model combining physical transport of electronic carriers in an insulating film and electrochemical aspects of transport is developed to determine the limits of performance enhancement expected via electrolyte thickness reduction. Free standing oxide heterostructures, i.e. electrolyte membrane and oxide electrodes, are demonstrated. Lastly, using Y2O3-doped ZrO2 and Gd2O 3-doped CeO2, novel electrolyte fabrication schemes are explored to develop oxide

  7. Water Dissociation on CeO2(100) and CeO2(111) Thin Films

    SciTech Connect

    Mullins, David R; Albrecht, Peter M; Chen, Tsung-Liang; Calaza, Florencia C; Biegalski, Micahel; Christen, Hans; Overbury, Steven {Steve} H

    2012-01-01

    This study reports and compares the adsorption and dissociation of water on oxidized and reduced CeO{sub 2}(100) and CeO{sub 2}(111) thin films. Water adsorbs dissociatively on both surfaces. On fully oxidized CeO{sub 2}(100) the resulting surface hydroxyls are relatively stable and recombine and desorb as water over a range from 200 to 600 K. The hydroxyls are much less stable on oxidized CeO{sub 2}(111), recombining and desorbing between 200 and 300 K. Water produces 30% more hydroxyls on reduced CeO{sub 1.7}(100) than on oxidized CeO{sub 2}(100). The hydroxyl concentration increases by 160% on reduced CeO{sub 1.7}(111) compared to oxidized CeO{sub 2}(111). On reduced CeO{sub 1.7}(100) most of the hydroxyls still recombine and desorb as water between 200 and 750 K. Most of the hydroxyls on reduced CeO{sub 1.7}(111) react to produce H{sub 2} at 560 K, leaving O on the surface. A relatively small amount of H{sub 2} is produced from reduced CeO{sub 1.7}(100) between 450 and 730 K. The differences in the adsorption and reaction of water on CeO{sub X}(100) and CeO{sub X}(111) are attributed to different adsorption sites on the two surfaces. The adsorption site on CeO{sub 2}(100) is a bridging site between two Ce cations. This adsorption site does not change when the ceria is reduced. The adsorption site on CeO{sub 2}(111) is atop a single Ce cation, and the proton is transferred to a surface O in a site between three Ce cations. When the CeO{sub X}(111) is reduced, vacancy sites are produced which allows the water to adsorb and dissociate on the 3-fold Ce cation sites.

  8. Effect of annealing temperature on the structural and optical properties of CeO2:Ni thin films

    NASA Astrophysics Data System (ADS)

    Murugan, R.; Vijayaprasath, G.; Sakthivel, P.; Mahalingam, T.; Ravi, G.

    2016-05-01

    High quality Ni-doped CeO2 (CeO2:Ni) thin films were deposited on glass substrates at room temperature by using radio frequency magnetron sputtering. The effect of annealing temperature on structural and optical properties of the CeO2:Ni films was investigated. The structural, optical and vibrational properties of the films were determined using X-ray diffraction (XRD), photoluminescence spectrometer (PL) and Raman spectrometer. It was found that the as-deposited film has a fluorite cubic structure. By increasing annealing temperature from 100°C to 300°C, the crystalline quality of the thin films could be improved. The UV and visible band emissions were observed in the photoluminescence spectra, due to exciton, defect related emissions respectively. The micro-Raman results show the characteristic peak of CeO2 F2g at 465 cm-1 and 2L0 at 1142 cm-1. Defect peaks like D and 0 bands were observed at 641 cm-1 and 548 cm-1 respectively. It is found from the spectra that the peak intensity of the films increased with increase of annealing temperature.

  9. YBCO thin films on CeO2 buffered silver substrates

    NASA Astrophysics Data System (ADS)

    Gallistl, B.; Gritzner, G.

    2008-02-01

    CeO2 was deposited on silver substrates by the chemical solution deposition method. Silver was dipped into a 0.05 M Ce(NO3)3 solution, dried in air and then annealed in air at 900 °C for 30 minutes. The CeO2 buffer layer was characterized by X-ray diffraction and scanning electron microscopy. YBCO was deposited onto the buffered substrate via screen printing. The YBCO films where sintered at temperatures of 880 °C and 890 °C. Dense and crack free YBCO layers were obtained with transition temperatures (Tc0) up to 83 K. Characterization of the superconducting film was performed by X-ray diffraction and SEM.

  10. Electrode engineering for improving resistive switching performance in single crystalline CeO2 thin films

    NASA Astrophysics Data System (ADS)

    Liao, Zhaoliang; Gao, Peng; Meng, Yang; Fu, Wangyang; Bai, Xuedong; Zhao, Hongwu; Chen, Dongmin

    2012-06-01

    We have studied the electrode effect on the resistive switching behavior in the single crystalline films of CeO2 grown on Nb-SrTiO3. The fabricated devices with the top electrode made of non-reactive metals (Ag, Au, Pt) show bipolar resistive switching but are volatile. In contrast, the devices with top electrodes made of reactive metals (Al, Ta, Ti) present different bipolar resistive switching direction and are non-volatile, with Ta one having the best in OFF/ON switching ratio. The devices with these kinds of electrodes also exhibit remarkably different rectification behavior because of the difference of electrode/CeO2 interface formation. These results demonstrate that it is possible to improve the performance of resistive switching by electrode engineering.

  11. Effect of Doping on Surface Reactivity and Conduction Mechanism in Sm-doped CeO2 Thin Films

    DOE PAGESBeta

    Yang, Nan; Belianinov, Alex; Strelcov, Evgheni; Tebano, Antonello; Daniele, Di Castro; Schlueter, Christoph; Lee, Tien-Lin; Baddorf, Arthur P.; Wisinger, Nina; Jesse, Stephen; et al

    2014-11-21

    Scanning probe microscopy measurements show irreversible surface electrochemistry in Sm-doped CeO2 thin films, which depends on humidity, temperature and doping concentration. A systematic study by electrochemical strain microscopy (ESM) in samples with two different Sm content and in several working conditions allows disclosing the microscopic mechanism underlying the difference in water adsorption and splitting with subsequent proton liberation. We measure the behavior of the hysteresis loops by changing temperature and humidity, both in standard ESM configuration and using the first order reversal curve (FORC) method. Complementing our study with spectroscopic measurements by hard x-ray photoemission spectroscopy we find that watermore » incorporation is favored until the doping with Sm is too high to allow the presence of Ce3+. The influence of doping on the surface reactivity and conduction mechanism clearly emerges from all of our experimental results. We find that at lower Sm concentration proton conduction is prevalent, featured by lower activation energy and higher mobility. Defect concentrations determine the type of the prevalent charge carrier in a doping dependent manner.« less

  12. Effect of Doping on Surface Reactivity and Conduction Mechanism in Sm-doped CeO2 Thin Films

    SciTech Connect

    Yang, Nan; Belianinov, Alex; Strelcov, Evgheni; Tebano, Antonello; Daniele, Di Castro; Schlueter, Christoph; Lee, Tien-Lin; Baddorf, Arthur P.; Wisinger, Nina; Jesse, Stephen; Kalinin, Sergei V; Balestrino, Giuseppe; Aruta, Carmela

    2014-11-21

    Scanning probe microscopy measurements show irreversible surface electrochemistry in Sm-doped CeO2 thin films, which depends on humidity, temperature and doping concentration. A systematic study by electrochemical strain microscopy (ESM) in samples with two different Sm content and in several working conditions allows disclosing the microscopic mechanism underlying the difference in water adsorption and splitting with subsequent proton liberation. We measure the behavior of the hysteresis loops by changing temperature and humidity, both in standard ESM configuration and using the first order reversal curve (FORC) method. Complementing our study with spectroscopic measurements by hard x-ray photoemission spectroscopy we find that water incorporation is favored until the doping with Sm is too high to allow the presence of Ce3+. The influence of doping on the surface reactivity and conduction mechanism clearly emerges from all of our experimental results. We find that at lower Sm concentration proton conduction is prevalent, featured by lower activation energy and higher mobility. Defect concentrations determine the type of the prevalent charge carrier in a doping dependent manner.

  13. THE OXYGEN PERMEATION PROPERTIES OF NANO CRYSTALLINE CEO2 THIN FILMS

    SciTech Connect

    Brinkman, K.

    2010-09-27

    The measurement of oxygen flux across nanocrystalline CeO{sub 2} cerium oxide thin films at intermediate temperature (650 to 800 C) is presented. Porous ceria support substrates were fabricated by sintering with carbon additions. The final dense film was deposited from an optimized sol-gel solution resulting in a mean grain size of 50 nm which displayed oxygen flux values of up to 0.014 {micro}mol/cm{sup 2}s over the oxygen partial pressure range from air to helium gas used in the measurement at 800 C. The oxygen flux characteristics confirm mixed ionic and electronic conductivity in nanocrystalline ceria films and demonstrate the role of size dependent materials properties as a design parameter in functional membranes for oxygen separation.

  14. Ultrafast pump-probe spectroscopy studies of CeO2 thin film deposited on Ni-W substrate by RF magnetron sputtering

    NASA Astrophysics Data System (ADS)

    Singh, Preetam; Srivatsa, K. M. K.; Jewariya, Mukesh

    2016-08-01

    This study presents the first investigation of rapid dynamical processes that occur in pure CeO2 thin film, using ultra fast pump-probe spectroscopy at room temperature. For this purpose we have used a single (200) oriented CeO2 film deposited on biaxially textured Ni-W substrate by RF magnetron sputtering technique. The ultrafast transient spectra show initial sharp rise transition followed by an exponential photon decay. This rise time is about 10 ps irrespective of the probe wavelengths range 500-800 nm. The initial decay constant (τ) at 500 nm probe wavelength is found to be 171 ps, while at 800 nm probe wavelength it is 107.5 ps. The ultrafast absorption spectra show two absorption peaks at 745 and 800 nm, and are attributed to the electronic transitions from 2F7/2-2F5/2 and 1S0-1F3 respectively. The relatively high intensity absorption peak at 745 nm indicates dominant f-f electronic transition. Further, the absorption peak at 745 nm splits into two distinct peaks with respect to delay time, and is attributed to the charge transfer in between Ce4+ and Ce3+ ions. These results indicate that CeO2 itself is a potential candidate and can be used for optical applications.

  15. 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.

  16. Synthesis and characterization of Gd2O3 doped UO2 nanoparticles

    NASA Astrophysics Data System (ADS)

    Soldati, A. L.; Gana Watkins, I.; Fernández Zuvich, A.; Napolitano, F.; Troiani, H.; Caneiro, A.; Prado, M.

    2016-10-01

    UO2 nanoparticles doped with 4, 8, 10 and 15 wt% Gd2O3were synthesized by a reverse strike method. Crystal structure and chemical homogeneity were evaluated using a combination of X-ray diffraction and microscopy tools. An exhaustive study of the composition and its homogeneity at the micro and at the nanometer level was carried out in this nuclear fuel material. Field Emission Gun Scanning and Transmission Electron Microscopy images revealed the presence of micrometer scale agglomerates of nanoparticles, with rounded morphology and an average crystallite size of 100 nm. Rietveld refinements of high-statistic X-ray Diffraction data determined the crystal structure and composition. Furthermore, Energy Dispersive Spectroscopy using a 2 nm2 spot on the sample surface determined a Gd concentration variation around the average of ±5% in different spots of a single crystallite and of ±10% between different crystallites. However, when measuring large amounts of nanoparticles the concentration averages, producing a homogeneous composition distribution at the micrometer scale.

  17. Structural and flux-pinning properties of laser ablated YBa 2Cu 3O 7-δ thin films: Effects of self-assembled CeO 2 nanodots on LaAlO 3 substrates

    NASA Astrophysics Data System (ADS)

    Haywood, Talisha; Oh, Sang Ho; Kebede, Abebe; Pai, Devdas M.; Sankar, Jag; Christen, David K.; Pennycook, Stephen J.; Kumar, Dhananjay

    2008-12-01

    Self-assembled nanodots of CeO 2 on (1 0 0) LaAlO 3 substrates, generated in situ by means of a pulsed laser deposition method prior to the deposition of YBa 2Cu 3O 7-δ (YBCO) films, have been used to modify the superconducting properties of resulting YBCO films. Structural characterization has indicated that CeO 2 layers grow via van der Merwe three-dimensional mode and the islands eventually acquire a pancake type of structure with lateral dimension several times larger than vertical dimension. The three-dimensional growth of CeO 2 islands with (1 0 0) preferred orientation is believed to be associated with its surface energy anisotropy. The magnetization versus temperature and magnetization versus field measurements and analysis have suggested that CeO 2 can affect the superconducting properties of YBCO films favorably or adversely depending on the density of CeO 2 nanodots on the substrate surfaces prior to the deposition of YBCO films.

  18. Comparison of superconducting properties between FeSe0.5Te0.5/CeO2/SrTiO3 and FeSe0.5Te0.5/SrTiO3 thin films

    NASA Astrophysics Data System (ADS)

    Chen, S. H.; Han, Y. Y.; Liu, J. Z.; Wang, T.; Tian, M. L.; Wen, H. H.; Xing, Z. W.

    2016-09-01

    The electrical resistance behaviors under angle-dependent magnetic fields up to 16 T are investigated in superconducting FeSe0.5Te0.5 (FST) thin films grown on SrTiO3 (STO) substrates without or with a CeO2 buffer layer. It is found that the FST/CeO2/STO films have an enhanced superconducting transition temperature Tc and slightly increased superconducting anisotropy in comparison with the FST/STO films. The enhancement of Tc in the presence of the CeO2 buffer is closely related to the changes in both the out-of-plane lattice constant and Se-Fe-Se (Te-Fe-Te) bond angle.

  19. Collective magnetic response of CeO2 nanoparticles

    NASA Astrophysics Data System (ADS)

    Coey, Michael; Ackland, Karl; Venkatesan, Munuswamy; Sen, Siddhartha

    2016-07-01

    The magnetism of nanoparticles and thin films of wide-bandgap oxides that include no magnetic cations is an unsolved puzzle. Progress has been hampered by both the irreproducibility of much of the experimental data, and the lack of any generally accepted theoretical explanation. The characteristic signature is a virtually anhysteretic, temperature-independent magnetization curve that saturates in an applied field that is several orders of magnitude greater than the magnetization. It would seem as if a tiny volume fraction, <~0.1%, of the samples is magnetic and that the energy scale is unusually high for spin magnetism. Here we investigate the effect of dispersing 4 nm CeO2 nanoparticles with powders of γAl2O3, sugar or latex microspheres. The saturation magnetization, Ms ≍ 60 A m-1 for compact samples, is maximized by 1 wt% lanthanum doping. Dispersing the CeO2 nanopowder reduces its magnetic moment by up to an order of magnitude, and there is a characteristic length scale of order 100 nm for the magnetism to appear in CeO2 nanoparticle clusters. The phenomenon is explained in terms of a giant orbital paramagnetism that appears in coherent mesoscopic domains due to resonant interaction with zero-point fluctuations of the vacuum electromagnetic field. The theory explains the observed temperature-independent magnetization curve and its doping and dispersion dependence, based on a length scale of 300 nm that corresponds to the wavelength of a maximum in the ultraviolet absorption spectrum of the magnetic CeO2 nanoparticles. The coherent domains occupy roughly 10% of the sample volume.

  20. Polarity driven morphology of CeO2(1 0 0) islands on Cu(1 1 1)

    NASA Astrophysics Data System (ADS)

    Stetsovych, O.; Beran, J.; Dvořák, F.; Mašek, K.; Mysliveček, J.; Matolín, V.

    2013-11-01

    Thin ceria films supported by metal substrates represent important model systems for reactivity studies in heterogeneous catalysis. Here we report the growth study of the polar CeO2(1 0 0) phase as part of a mixed CeO2(1 1 1)-CeO2(1 0 0) thin film supported by Cu(1 1 1). The two ceria phases grow on different areas of the substrate, what allows a reliable growth characterization of the CeO2(1 0 0) islands on Cu(1 1 1). Scanning tunneling microscopy measurements reveal CeO2(1 0 0) to grow in the form of highly dispersed three dimensional (3D) islands on a CeO2(1 0 0) interfacial layer. The CeO2(1 0 0) islands exhibit a 2 × 2 surface reconstruction. The presence of the surface reconstruction together with the highly dispersed growth of CeO2(1 0 0) islands corresponds to the requirement for compensation of the surface dipole moment on the CeO2(1 0 0). CeO2(1 0 0) islands are further characterized by reflection high energy electron diffraction yielding their epitaxial relations with respect to the Cu(1 1 1) substrate. The growth of well characterized CeO2(1 0 0) islands supported by Cu(1 1 1) represents a starting point for developing a novel template for structure-related reactivity studies of ceria based model catalysts.

  1. Fundamental Understanding of the Interaction of Acid Gases with CeO2 : From Surface Science to Practical Catalysis

    DOE PAGESBeta

    Tumuluri, Uma; Rother, Gernot; Wu, Zili

    2016-03-21

    Acid gases including CO2, SO2, and NOx are ubiquitous in large-scale energy applications including heterogeneous catalysis. The adverse environmental and health effects of these acid gases have resulted in high interest in the research and development of technologies to remove or convert these acid gases. The main challenge for the development of these technologies is to develop catalysts that are highly efficient, stable, and cost-effective, and many catalysts have been reported in this regard. CeO2 and CeO2-based catalysts have gained prominence in the removal and conversion of CO2, SO2, and NOx because of their structural robustness and redox and acid–basemore » properties. In this article, we provide a brief overview of the application of CeO2 and CeO2-based catalysts for the removal of CO2, SO2, and NOx gases with an emphasis on the fundamental understanding of the interactions of these acid gases with CeO2. The studies summarized in this review range from surface science using single crystals and thin films with precise crystallographic planes to practical catalysis applications of nanocrystalline and polycrystalline CeO2 materials with defects and dopants. After an introduction to the properties of CeO2 surfaces, their catalytic properties for conversions of different acid gases are reviewed and discussed. Lastly, we find that the surface atomic structure, oxygen vacancies, and surface acid–base properties of CeO2 play vital roles in the surface chemistry and structure evolution during the interactions of acid gases with CeO2 and CeO2-based catalysts.« less

  2. High Curie temperature for La(0.7)Sr(0.3)MnO(3) thin films deposited on CeO(2) /YSZ-based buffered silicon substrates.

    PubMed

    Perna, P; Méchin, L; Chauvat, M P; Ruterana, P; Simon, Ch; Scotti di Uccio, U

    2009-07-29

    Two kinds of epitaxial structures were grown by standard pulsed laser deposition on (001) Si, namely La(0.7)Sr(0.3)MnO(3)/Bi(4)Ti(3)O(12)/CeO(2) /YSZ/Si (BTO-based), and La(0.7)Sr(0.3)MnO(3)/SrTiO(3)/CeO(2) /YSZ/Si (STO-based) multilayers. The samples were investigated by means of x-ray diffraction, transmission electron microscopy, magnetic and transport measurements. The Curie temperature T(C) of the BTO-based samples was found to be higher (360 K) than for the typical reference epitaxial LSMO film grown on (001) SrTiO(3) single crystal (345 K), due to high compressive in-plane strain. The STO-based samples show high structural quality, low roughness and high T(C) (350 K), making them interesting candidates for use in innovative LSMO-based bolometers or spintronic devices operating at room temperature.

  3. Investigation of trimethylacetic acid adsorption on stoichiometric and oxygen-deficient CeO2(111) surfaces.

    PubMed

    Sanghavi, Shail; Wang, Weina; Nandasiri, Manjula I; Karakoti, Ajay S; Wang, Wenliang; Yang, Ping; Thevuthasan, S

    2016-06-21

    We studied the interactions between the carboxylate anchoring group from trimethylacetic acid (TMAA) and CeO2(111) surfaces as a function of oxygen stoichiometry using in situ X-ray photoelectron spectroscopy (XPS). The stoichiometric CeO2(111) surface was obtained by annealing the thin film under 2.0 × 10(-5) Torr of oxygen at ∼550 °C for 30 min. In order to reduce the CeO2(111) surface, the thin film was annealed under ∼5.0 × 10(-10) Torr vacuum conditions at 550 °C, 650 °C, 750 °C and 850 °C for 30 min to progressively increase the oxygen defect concentration on the surface. The saturated TMAA coverage on the CeO2(111) surface determined from XPS elemental composition is found to increase with increasing oxygen defect concentration. This is attributed to the increase of under-coordinated cerium sites on the surface with the increase in the oxygen defect concentrations. XPS results were in agreement with periodic density functional theory (DFT) calculations and indicate a stronger binding between the carboxylate group from TMAA and the oxygen deficient CeO2-δ(111) surface through dissociative adsorption.

  4. Investigation of trimethylacetic acid adsorption on stoichiometric and oxygen-deficient CeO2 (111) surfaces

    DOE PAGESBeta

    Sanghavi, Shail; Wang, Weina; Nandasiri, Manjula I.; Karakoti, Ajay S.; Wang, Wenliang; Yang, Ping; Thevuthasan, S.

    2016-05-12

    We studied the interactions between the carboxylate anchoring group from trimethylacetic acid (TMAA) and CeO2(111) surfaces as a function of oxygen stoichiometry using in situ X-ray photoelectron spectroscopy (XPS). The stoichiometric CeO2(111) surface was obtained by annealing the thin film under 2.0 × 10–5 Torr of oxygen at ~550 °C for 30 min. In order to reduce the CeO2(111) surface, the thin film was annealed under ~5.0 × 10–10 Torr vacuum conditions at 550 °C, 650 °C, 750 °C and 850 °C for 30 min to progressively increase the oxygen defect concentration on the surface. The saturated TMAA coverage onmore » the CeO2(111) surface determined from XPS elemental composition is found to increase with increasing oxygen defect concentration. This is attributed to the increase of under-coordinated cerium sites on the surface with the increase in the oxygen defect concentrations. Furthermore, XPS results were in agreement with periodic density functional theory (DFT) calculations and indicate a stronger binding between the carboxylate group from TMAA and the oxygen deficient CeO2–δ(111) surface through dissociative adsorption.« less

  5. CeO2 nanorods and gold nanocrystals supported on CeO2 nanorods as catalyst.

    PubMed

    Huang, P X; Wu, F; Zhu, B L; Gao, X P; Zhu, H Y; Yan, T Y; Huang, W P; Wu, S H; Song, D Y

    2005-10-20

    The formation mechanism of uniform CeO2 structure at the nanometer scale via a wet-chemical reaction is of great interest in fundamental study as well as a variety of applications. In this work, large-scale well-crystallized CeO2 nanorods with uniform diameters in the range of 20-30 nm and lengths up to tens of micrometers are first synthesized through a hydrothermal synthetic route in 5 M KOH solution at 180 degrees C for 45 h without any templates and surfactants. The nanorod formation involves dehydration of CeO2 nanoparticles and orientation growth along the 110 direction in KOH solution. Subsequently, gold nanoparticles with crystallite sizes between 10 and 20 nm are loaded on the surface of CeO2 nanorods using HAuCl4 solution as the gold source and NaBH4 solution as a reducing agent. The synthesized Au/CeO2 nanorods demonstrate a higher catalytic activity in CO oxidation than the pure CeO2 nanorods. PMID:16853472

  6. Electrodeposited Biaxially Textured CeO2 and CeO2:Sm Buffer Layer for YBCO Superconductor Oxide Films

    NASA Astrophysics Data System (ADS)

    Bhattacharya, Raghu; Phok, Sovannary; Spagnol, Priscila; Chaudhuri, Tapas

    2006-03-01

    Nonvacuum electrodeposition was used to prepare biaxially textured CeO2 and Sm-doped CeO2 coatings on Ni-W substrates. The samples were characterized by X-ray diffraction (including θ/2θ, pole figures, omega scans, and phi scans), atomic force microscopy (AFM), Auger electron spectroscopy (AES), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Full-width at half-maximum values of the ω scan and φ scan of the electrodeposited layers were better than those of the Ni-W base substrates, indicating improved biaxial texturing of the electrodeposited layers.

  7. 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

  8. Photocatalytic degradation of methyl orange by CeO2 and Fe-doped CeO2 films under visible light irradiation.

    PubMed

    Channei, D; Inceesungvorn, B; Wetchakun, N; Ukritnukun, S; Nattestad, A; Chen, J; Phanichphant, S

    2014-01-01

    Undoped CeO2 and 0.50-5.00 mol% Fe-doped CeO2 nanoparticles were prepared by a homogeneous precipitation combined with homogeneous/impreganation method, and applied as photocatalyst films prepared by a doctor blade technique. The superior photocatalytic performances of the Fe-doped CeO2 films, compared with undoped CeO2 films, was ascribed mainly to a decrease in band gap energy and an increase in specific surface area of the material. The presence of Fe(3+) as found from XPS analysis, may act as electron acceptor and/or hole donor, facilitating longer lived charge carrier separation in Fe-doped CeO2 films as confirmed by photoluminescence spectroscopy. The 1.50 mol% Fe-doped CeO2 film was found to be the optimal iron doping concentration for MO degradation in this study.

  9. Redox Pathways for HCOOH Decomposition over CeO2 Surfaces

    SciTech Connect

    Senanayake,S.; Mullins, D.

    2008-01-01

    The reaction of HCOOH, the simplest C-1 carboxylic acid, has been studied on oxidized (CeO2) and reduced cerium oxide (CeOX) thin films. HCOOH has been proposed as an important C1 precursor to the formation of CO2 and H2 in the water-gas-shift (WGS) reaction, in which ceria is also used as a stable support rich in oxygen. The HCOOH is observed to adsorb by way of a formate intermediate species (HCOO-) through the dissociation of the acidic H over both CeO2 (Ce4+) and CeOX (Ce4+/Ce3+) surfaces. On the fully oxidized CeO2 surface, this H species reacts with surface O and desorbs as H2O when the temperature is <300 K. In addition to water, temperature programmed desorption spectra indicate the evolution of CO2 and H2 between 350 and 400 K followed by CO desorption in two regimes at 450 and 525 K. On reduced ceria, only CO and H2 were produced between 450 and 600 K. The reaction of HCOOH with ceria therefore leads to both the reduction of the oxide, through the formation of H2O and CO2, and oxidation of the oxide, through decomposition to H2 and CO, depending on the initial state of the ceria. C K-edge near-edge X-ray absorption fine structure and soft X-ray photoelectron spectroscopy indicate that formate and -OH were the only surface intermediates.

  10. Unusual Compression Behavior of Nanocrystalline CeO2

    PubMed Central

    Wang, Qiming; He, Duanwei; Peng, Fang; Lei, Li; Liu, Pingping; Yin, Shuai; Wang, Pei; Xu, Chao; Liu, Jing

    2014-01-01

    The x-ray diffraction study of 12 nm CeO2 was carried out up to ~40 GPa using an angle dispersive synchrotron-radiation in a diamond-anvil cell with different pressure transmitting medium (PTM) (4:1 methanol: ethanol mixture, silicone oil and none) at room temperature. While the cubic fluorite-type structure CeO2 was retained to the highest pressure, there is progressive broadening and intensity reduction of the reflections with increasing pressure. At pressures above 12 GPa, an unusual change in the compression curve was detected in all experiments. Significantly, apparent negative volume compressibility was observed at P = 18–27 GPa with silicone oil as PTM, however it was not detected in other circumstances. The expansion of the unit cell volume of cubic CeO2 was about 1% at pressures of 15–27 GPa. To explain this abnormal phenomenon, a dual structure model (hard amorphous shell and relatively soft crystalline core) has been proposed. PMID:24658049

  11. Synthesis of supported CeO2 nanofibers via electrospinning

    NASA Astrophysics Data System (ADS)

    Starbova, K.; Nihtianova, D.; Petrov, D.; Starbov, N.; Lovchinov, V.

    2012-12-01

    Fibrous CeO2 non-woven mats are synthesized via electrospinning. Homogeneous and stable aqueous polymer/cerium acetate blend spinning solutions are used. It is shown how the parameters of the solution, electrospinning, thermal post-processing can be successfully combined thus providing the synthesis of fibrous webs with mean diameters in the nanosized range. The morphologies of the samples are recorded under SEM and HRTEM while SAED is applied for studying their phase composition. The results obtained pave the way for the development of functional immobilized and self-supporting electrospun ceria ceramic materials.

  12. Origin of enhanced photocatalytic activity of F-doped CeO2 nanocubes

    NASA Astrophysics Data System (ADS)

    Miao, Hui; Huang, Gui-Fang; Liu, Jin-Hua; Zhou, Bing-Xin; Pan, Anlian; Huang, Wei-Qing; Huang, Guo-Fang

    2016-05-01

    CeO2 nanoparticles are synthesized using a low-temperature solution combustion method and subsequent heat treatment in air. It is found that F-doping leads to smaller particle size and the formation of CeO2 nanocubes with higher percentage of reactive facets exposed. The band gap is estimated to be 3.16 eV and 2.88 eV, for pure CeO2 and fluorine doped CeO2 (F-doped CeO2) nanocubes, respectively. The synthesized F-doped CeO2 nanocubes exhibit much higher photocatalytic activities than commercial TiO2 and spherical CeO2 for the degradation of MB dye under UV and visible light irradiation. The apparent reaction rate constant k of MB decomposition over the optimized F-doped CeO2 nanocubes is 9.5 times higher than that of pure CeO2 and 2.2 times higher than that of commercial TiO2. The enhanced photocatalytic activity of F-doped CeO2 nanocubes originates from the fact that F-doping induces the small size, the highly reactive facets exposed, the intense absorption in the UV-vis range and the narrowing of the band gap. This research provides some new insights for the synthesis of the doping of the foreign atoms into photocatalyst with controlled morphology and enhanced photocatalytic activity.

  13. Materials and electrical characterization of molecular beam deposited CeO2 and CeO2/HfO2 bilayers on germanium

    NASA Astrophysics Data System (ADS)

    Brunco, D. P.; Dimoulas, A.; Boukos, N.; Houssa, M.; Conard, T.; Martens, K.; Zhao, C.; Bellenger, F.; Caymax, M.; Meuris, M.; Heyns, M. M.

    2007-07-01

    Properties of CeO2 and CeO2/HfO2 bilayers grown by molecular beam deposition on in situ prepared, oxide-free Ge(100) surfaces are reported here. Deposition is achieved by a simultaneous flux of electron-beam evaporated metal (Ce or Hf) and of remote plasma generated atomic oxygen. These conditions result in an interfacial layer (IL) between the cubic CeO2 and Ge substrate. Electron energy loss spectroscopy shows that this IL is comprised of Ge and O and a small amount of Ce, and x-ray photoelectron spectroscopy suggests that the Ge is in a mix of 2+ and 3+ oxidation states. A comparison of capacitance, conductance, and leakage data shows a higher quality dielectric for 225 °C deposition than for room temperature. However, CeO2-only deposition results in an unacceptably high leakage current due to the small CeO2 band gap, which is remedied by the use of CeO2/HfO2 bilayers. Using the Nicollian-Goetzberger method, interface trap densities in the mid 1011 eV-1 cm-2 are obtained for CeO2/HfO2 gate stacks on both n- and p-Ge.

  14. Structural, dielectric, ferroelectric, and electrocaloric properties of 2% Gd2O3 doping (Na0.5Bi0.5)0.94Ba0.06TiO3 ceramics

    NASA Astrophysics Data System (ADS)

    Turki, O.; Slimani, A.; Seveyrat, L.; Sebald, G.; Perrin, V.; Sassi, Z.; Khemakhem, H.; Lebrun, L.

    2016-08-01

    Structural, dielectric, and ferroelectric properties, and electrocaloric effects of pure and Gd doped ( Na0.5 Bi 0.5 ) 0.94 Ba 0.06 TiO 3 ceramics prepared by the conventional solid-solid method have been carried out. The X-ray diffraction analysis confirms a pure perovskite structure with the coexistence of tetragonal and rhombohedra structures in both powders. The thermal and frequency dependences of the dielectric constants of both ceramics revealed relaxor behavior. The two compounds exhibited two phase transitions: ferroelectric/antiferroelectric (FE/AFE) transition followed by an antiferroelectric/paraelectric (AFE/PE) transition at higher temperatures. Remarkably, we noticed that the small amount of Gd doping (2%) highly enhanced the dielectric properties of the parent compound by about 71%. The phase diagram was as well influenced by the Gd doping, where the FE/AFE transition temperature rose from 90 in the parent compound to 115 °C in the doped one whereas the AFE/PE transition temperature was decreased from 320 to 270 °C, respectively. The direct electrocaloric measurements performed on both compounds showed that the ferroelectric/antiferroelectric phase transition was accompanied by a significant electrocaloric effect. The Gd3+ doping improved the electrocaloric properties of the parent compound, where a remarkable temperature variation of 1.4 K was obtained in the doped ceramic. The results of the direct electrocaloric measurements will be compared and discussed with those derived from the indirect method.

  15. Redox enzyme-mimicking activities of CeO2 nanostructures: Intrinsic influence of exposed facets

    PubMed Central

    Yang, Yushi; Mao, Zhou; Huang, Wenjie; Liu, Lihua; Li, Junli; Li, Jialiang; Wu, Qingzhi

    2016-01-01

    CeO2 nanoparticles (NPs) have been well demonstrated as an antioxidant in protecting against oxidative stress-induced cellular damages and a potential therapeutic agent for various diseases thanks to their redox enzyme-mimicking activities. The Ce3+/Ce4+ ratio and oxygen vacancies on the surface have been considered as the major originations responsible for the redox enzyme-mimicking activities of CeO2 NPs. Herein, CeO2 nanostructures (nanocubes and nanorods) exposed different facets were synthesized via a facile hydrothermal method. The characterizations by X-ray photoelectron spectroscopy, Raman spectroscopy, and UV-Vis spectroscopy show that the Ce3+/Ce4+ ratio and oxygen vacancy content on the surfaces of as-synthesized CeO2 nanostructures are nearly at the same levels. Meanwhile, the enzymatic activity measurements indicate that the redox enzyme-mimicking activities of as-synthesized CeO2 nanostructures are greatly dependent on their exposed facets. CeO2 nanocubes with exposed {100} facets exhibit a higher peroxidase but lower superoxide dismutase activity than those of the CeO2 nanorods with exposed {110} facets. Our results provide new insights into the redox enzyme-mimicking activities of CeO2 nanostructures, as well as the design and synthesis of inorganic nanomaterials-based artificial enzymes. PMID:27748403

  16. Redox enzyme-mimicking activities of CeO2 nanostructures: Intrinsic influence of exposed facets

    NASA Astrophysics Data System (ADS)

    Yang, Yushi; Mao, Zhou; Huang, Wenjie; Liu, Lihua; Li, Junli; Li, Jialiang; Wu, Qingzhi

    2016-10-01

    CeO2 nanoparticles (NPs) have been well demonstrated as an antioxidant in protecting against oxidative stress-induced cellular damages and a potential therapeutic agent for various diseases thanks to their redox enzyme-mimicking activities. The Ce3+/Ce4+ ratio and oxygen vacancies on the surface have been considered as the major originations responsible for the redox enzyme-mimicking activities of CeO2 NPs. Herein, CeO2 nanostructures (nanocubes and nanorods) exposed different facets were synthesized via a facile hydrothermal method. The characterizations by X-ray photoelectron spectroscopy, Raman spectroscopy, and UV-Vis spectroscopy show that the Ce3+/Ce4+ ratio and oxygen vacancy content on the surfaces of as-synthesized CeO2 nanostructures are nearly at the same levels. Meanwhile, the enzymatic activity measurements indicate that the redox enzyme-mimicking activities of as-synthesized CeO2 nanostructures are greatly dependent on their exposed facets. CeO2 nanocubes with exposed {100} facets exhibit a higher peroxidase but lower superoxide dismutase activity than those of the CeO2 nanorods with exposed {110} facets. Our results provide new insights into the redox enzyme-mimicking activities of CeO2 nanostructures, as well as the design and synthesis of inorganic nanomaterials-based artificial enzymes.

  17. Photon management properties of rare-earth (Nd,Yb,Sm)-doped CeO2 films prepared by pulsed laser deposition.

    PubMed

    Balestrieri, Matteo; Colis, Silviu; Gallart, Mathieu; Schmerber, Guy; Bazylewski, Paul; Chang, Gap Soo; Ziegler, Marc; Gilliot, Pierre; Slaoui, Abdelilah; Dinia, Aziz

    2016-01-28

    CeO2 is a promising material for applications in optoelectronics and photovoltaics due to its large band gap and values of the refractive index and lattice parameters, which are suitable for silicon-based devices. In this study, we show that trivalent Sm, Nd and Yb ions can be successfully inserted and optically activated in CeO2 films grown at a relatively low deposition temperature (400 °C), which is compatible with inorganic photovoltaics. CeO2 thin films can therefore be efficiently functionalized with photon-management properties by doping with trivalent rare earth (RE) ions. Structural and optical analyses provide details of the electronic level structure of the films and of their energy transfer mechanisms. In particular, we give evidence of the existence of an absorption band centered at 350 nm from which energy transfer to rare earth ions occurs. The transfer mechanisms can be completely explained only by considering the spontaneous migration of Ce(3+) ions in CeO2 at a short distance from the RE(3+) ions. The strong absorption cross section of the f-d transitions in Ce(3+) ions efficiently intercepts the UV photons of the solar spectrum and therefore strongly increases the potential of these layers as downshifters and downconverters.

  18. Preparation of a novel fluorescent nanocomposite: CeO2 / ANS by a simple method

    NASA Astrophysics Data System (ADS)

    Liu, X.; Lian, X.; Li, Y.; Zhang, N.

    2012-03-01

    For the first time, a novel fluorescent material, composed of CeO2/ANS nanocomposites was successfully synthesized by a simple ultrasonic method, using CeO2 nanoparticles and 8-anilino-1-naphthalenesulfonic acid (ANS) as the raw materials. The samples were characterized by scanning electron microscope (SEM), photoluminescence spectroscopy and Fourier transformation infrared spectroscopy (FTIR). The results showed that the PL intensity of the CeO2/ANS nanocomposites was higher than that of both CeO2 nanoparticles and ANS powders, and the peak wavelength was also different from the peak wavelength typical of each of the used materials, which suggests that the chemical reaction occurs between CeO2 nanoparticles and ANS molecules. In addition, the effect of the ANS concentrations on the photoluminescence of the nanocomposites was also investigated.

  19. Role of vacancies, light elements and rare-earth metals doping in CeO2.

    PubMed

    Shi, H; Hussain, T; Ahuja, R; Kang, T W; Luo, W

    2016-01-01

    The magnetic properties and electronic structures of pure, doped and defective cerium oxide (CeO2) have been studied theoretically by means of ab initio calculations based on the density function theory (DFT) with the hybrid HF/DFT technique named PBE0. Carbon (C), nitrogen (N), phosphorus (P), sulphur (S), lanthanum (La) and praseodymium (Pr) doped in CeO2 and CeO2 containing oxygen vacancies (Ov) were considered. Our spin-polarized calculations show that C, N, Pr dopants and Ov defects magnetize the non-magnetic CeO2 in different degree. The optical band gap related to photocatalysis for pure CeO2, corresponding to the ultraviolet region, is reduced obviously by C, N, S, Pr impurities and oxygen vacancies, shifting to the visible region and even further to the infrared range. Especially, N-, S- and Pr-doped CeO2 could be used to photocatalytic water splitting for hydrogen production. As the concentration of Ov increasing up to 5%, the CeO2 exhibits a half-metallic properties. PMID:27554285

  20. Effect of the Addition of CeO2 to Iron Phosphate Glass for Catalytic Applications.

    PubMed

    Chung, Jae-Yeop; Kim, Jong-Hwan; Choi, Su-Yeon; Ryu, Bong-Ki

    2015-10-01

    We investigated the effect of CeO2 content on the catalytic behavior and chemical properties of the (100 - x)(80P2O5-20Fe2O3)-xCeO2 (x = 0, 4, 8, 12, 16, 20 and 24 wt%) glass system. Using thermogravimetric analysis, we confirmed that the catalytic activity increased until a CeO2 content of 16 wt%, beyond which, it decreased. The reasons for the change in the catalytic properties of the glass samples were determined using Fourier transform infrared (FT-IR) spectroscopy, X-ray photoelectron spectroscopy (XPS), and density analyses. It was confirmed using the FT-IR and XPS-01s spectra that CeO2 acts as a network modifier in iron phosphate glass. When the CeO2 content is above 16 wt%, the number of non-bridging oxygen atoms decreases with increasing CeO2 content. For these reasons, the catalytic properties decrease when the CeO2 content is more than 16 wt%. From the dissolution rate measurements, it can be observed that cerium-iron phosphate has a high water resistance. Also, as we expected, it can be confirmed that the chemical durability is improved with increasing CeO2 content.

  1. CeO2 nanorods-supported transition metal catalysts for CO oxidation.

    PubMed

    Mock, Samantha A; Sharp, Shannon E; Stoner, Thomas R; Radetic, Michael J; Zell, Elizabeth T; Wang, Ruigang

    2016-03-15

    A catalytically active oxide support in combination with metal catalysts is required in order to achieve better low temperature activity and selectivity. Here, we report that CeO2 nanorods with a superior surface oxygen release/storage capability were used as an active support of transition metal (TM) catalysts (Mn, Fe, Co, Ni, Cu) for CO oxidation reaction. The as-prepared CeO2 nanorods supported 10 wt% TM catalysts were highly active for CO oxidation at low temperature, except for the Fe sample. It is found that the 10%Cu-CeO2 catalyst performed best, and it provided a lower light-off temperature with T50 (50% conversion) at 75 °C and T100 (100% conversion) of CO to CO2 at 194 °C. The atomic level surface structure of CeO2 nanorods was investigated in order to understand the improved low temperature catalytic activity. The richness of surface roughness and various defects (voids, lattice distortion, bending, steps, twinning) on CeO2 nanorods could facilitate oxygen release and storage. According to XRD and Raman analysis, copper species migrate into the bulk CeO2 nanorods to a greater degree. Since CO adsorbed over the surface of the catalyst/support is detrimental to its catalytic activity, the surface defects on the CeO2 nanorods and CeO2-TM interactions were critical to the enhanced activity.

  2. Photocatalytic and antibacterial properties of phytosynthesized CeO2 NPs using Moringa oleifera peel extract.

    PubMed

    Surendra, T V; Roopan, Selvaraj Mohana

    2016-08-01

    Biosynthetic methods are alternative approaches which are much safer than the normal techniques (physical and chemical) used for the methods for synthesis of metal nanoparticles. The benefits are sample as it is economic and environment friendly. Herein present investigation, we have reported a microwave mediated eco-friendly synthetic approach for preparing cerium oxide (CeO2) nanoparticles. Here, we used Moringa oleifera peel as the stabilizing and reducing agent towards synthesize of Ce2O NPs via microwave irradiation. The NPs were further characterized using UV-Vis, FT-IR, XRD and HR-TEM techniques. The FTIR analysis confirmed the phytochemical involvement in NPs stabilization. The crystallinity of CeO2 nanoparticles are well demonstrated through X-ray Diffraction and HR-TEM. The TEM images reveal the spherical shape of the CeO2 NPs having an average size of 45nm. Additionally, these CeO2 NPs were used successfully as a catalyst in the degradation of the dye, crystal violet. Also the antibacterial activity of the synthesized CeO2 NPs was evaluated using Staphylococcus aureus (Gram positive bacteria) and Escherichia coli (Gram negative bacteria). CeO2 NPs showed better activity on E. coli than S. aureus. We have demonstrated an eco-friendly preparation of CeO2 nanoparticles, a good photocatalyst and having better antibacterial properties.

  3. Surface passivation of CeO2 catalyst and its ultraviolet screening effect.

    PubMed

    Kang, Joo-Hee; Kim, Yun-Hee; Paek, Seung-Min; Choy, Jin-Ho

    2011-07-01

    A new strategy was attempted to fabricate CeO2 nanoparticles using the surface fluorination technique to control the particle size and suppress the catalytic activity. The fluorinated CeO2 nanoparticles are fully characterized with XRD, XANES, UV-vis spectroscopy, HR-TEM, XPS along with the evaluation of photo and thermal catalytic activities. XRD patterns were not affected by surface fluorination. That is to say, the crystalline structure of CeO2 was not deteriorated upon fluorination. The TEM analysis showed that the fluorinated CeO2 nanoparticles with the primary particle size of 7 nm could be prepared. According to the X-ray absorption near edge structure (XANES) analysis, overall XANES spectrum was not changed upon fluorination, suggesting that the local structure of fluorinated CeO2 resembled that of the starting CeO2 nanoparticles. It was also revealed that both photo and thermal catalytic activities could be almost totally suppressed at the fluorination level of ca. 6.0 wt%. It is suggested that the selective surface fluorination with fluoride could lead to fluorinated CeO2 nanoparticles, which could be applied to new fields such as the cosmetics industries. PMID:22121733

  4. Role of vacancies, light elements and rare-earth metals doping in CeO2

    PubMed Central

    Shi, H.; Hussain, T.; Ahuja, R.; Kang, T. W.; Luo, W.

    2016-01-01

    The magnetic properties and electronic structures of pure, doped and defective cerium oxide (CeO2) have been studied theoretically by means of ab initio calculations based on the density function theory (DFT) with the hybrid HF/DFT technique named PBE0. Carbon (C), nitrogen (N), phosphorus (P), sulphur (S), lanthanum (La) and praseodymium (Pr) doped in CeO2 and CeO2 containing oxygen vacancies (Ov) were considered. Our spin-polarized calculations show that C, N, Pr dopants and Ov defects magnetize the non-magnetic CeO2 in different degree. The optical band gap related to photocatalysis for pure CeO2, corresponding to the ultraviolet region, is reduced obviously by C, N, S, Pr impurities and oxygen vacancies, shifting to the visible region and even further to the infrared range. Especially, N-, S- and Pr-doped CeO2 could be used to photocatalytic water splitting for hydrogen production. As the concentration of Ov increasing up to 5%, the CeO2 exhibits a half-metallic properties. PMID:27554285

  5. Role of vacancies, light elements and rare-earth metals doping in CeO2.

    PubMed

    Shi, H; Hussain, T; Ahuja, R; Kang, T W; Luo, W

    2016-08-24

    The magnetic properties and electronic structures of pure, doped and defective cerium oxide (CeO2) have been studied theoretically by means of ab initio calculations based on the density function theory (DFT) with the hybrid HF/DFT technique named PBE0. Carbon (C), nitrogen (N), phosphorus (P), sulphur (S), lanthanum (La) and praseodymium (Pr) doped in CeO2 and CeO2 containing oxygen vacancies (Ov) were considered. Our spin-polarized calculations show that C, N, Pr dopants and Ov defects magnetize the non-magnetic CeO2 in different degree. The optical band gap related to photocatalysis for pure CeO2, corresponding to the ultraviolet region, is reduced obviously by C, N, S, Pr impurities and oxygen vacancies, shifting to the visible region and even further to the infrared range. Especially, N-, S- and Pr-doped CeO2 could be used to photocatalytic water splitting for hydrogen production. As the concentration of Ov increasing up to 5%, the CeO2 exhibits a half-metallic properties.

  6. Role of vacancies, light elements and rare-earth metals doping in CeO2

    NASA Astrophysics Data System (ADS)

    Shi, H.; Hussain, T.; Ahuja, R.; Kang, T. W.; Luo, W.

    2016-08-01

    The magnetic properties and electronic structures of pure, doped and defective cerium oxide (CeO2) have been studied theoretically by means of ab initio calculations based on the density function theory (DFT) with the hybrid HF/DFT technique named PBE0. Carbon (C), nitrogen (N), phosphorus (P), sulphur (S), lanthanum (La) and praseodymium (Pr) doped in CeO2 and CeO2 containing oxygen vacancies (Ov) were considered. Our spin-polarized calculations show that C, N, Pr dopants and Ov defects magnetize the non-magnetic CeO2 in different degree. The optical band gap related to photocatalysis for pure CeO2, corresponding to the ultraviolet region, is reduced obviously by C, N, S, Pr impurities and oxygen vacancies, shifting to the visible region and even further to the infrared range. Especially, N-, S- and Pr-doped CeO2 could be used to photocatalytic water splitting for hydrogen production. As the concentration of Ov increasing up to 5%, the CeO2 exhibits a half-metallic properties.

  7. Photocatalytic and antibacterial properties of phytosynthesized CeO2 NPs using Moringa oleifera peel extract.

    PubMed

    Surendra, T V; Roopan, Selvaraj Mohana

    2016-08-01

    Biosynthetic methods are alternative approaches which are much safer than the normal techniques (physical and chemical) used for the methods for synthesis of metal nanoparticles. The benefits are sample as it is economic and environment friendly. Herein present investigation, we have reported a microwave mediated eco-friendly synthetic approach for preparing cerium oxide (CeO2) nanoparticles. Here, we used Moringa oleifera peel as the stabilizing and reducing agent towards synthesize of Ce2O NPs via microwave irradiation. The NPs were further characterized using UV-Vis, FT-IR, XRD and HR-TEM techniques. The FTIR analysis confirmed the phytochemical involvement in NPs stabilization. The crystallinity of CeO2 nanoparticles are well demonstrated through X-ray Diffraction and HR-TEM. The TEM images reveal the spherical shape of the CeO2 NPs having an average size of 45nm. Additionally, these CeO2 NPs were used successfully as a catalyst in the degradation of the dye, crystal violet. Also the antibacterial activity of the synthesized CeO2 NPs was evaluated using Staphylococcus aureus (Gram positive bacteria) and Escherichia coli (Gram negative bacteria). CeO2 NPs showed better activity on E. coli than S. aureus. We have demonstrated an eco-friendly preparation of CeO2 nanoparticles, a good photocatalyst and having better antibacterial properties. PMID:27236047

  8. CeO2 nanorods-supported transition metal catalysts for CO oxidation.

    PubMed

    Mock, Samantha A; Sharp, Shannon E; Stoner, Thomas R; Radetic, Michael J; Zell, Elizabeth T; Wang, Ruigang

    2016-03-15

    A catalytically active oxide support in combination with metal catalysts is required in order to achieve better low temperature activity and selectivity. Here, we report that CeO2 nanorods with a superior surface oxygen release/storage capability were used as an active support of transition metal (TM) catalysts (Mn, Fe, Co, Ni, Cu) for CO oxidation reaction. The as-prepared CeO2 nanorods supported 10 wt% TM catalysts were highly active for CO oxidation at low temperature, except for the Fe sample. It is found that the 10%Cu-CeO2 catalyst performed best, and it provided a lower light-off temperature with T50 (50% conversion) at 75 °C and T100 (100% conversion) of CO to CO2 at 194 °C. The atomic level surface structure of CeO2 nanorods was investigated in order to understand the improved low temperature catalytic activity. The richness of surface roughness and various defects (voids, lattice distortion, bending, steps, twinning) on CeO2 nanorods could facilitate oxygen release and storage. According to XRD and Raman analysis, copper species migrate into the bulk CeO2 nanorods to a greater degree. Since CO adsorbed over the surface of the catalyst/support is detrimental to its catalytic activity, the surface defects on the CeO2 nanorods and CeO2-TM interactions were critical to the enhanced activity. PMID:26745742

  9. Preparation for CeO2/Nanographite Composite Materials and Electrochemical Degradation of Phenol by CeO2/Nanographite Cathodes.

    PubMed

    Yu, Li; Yu, Xiujuan; Sun, Tianyi; Wang, Na

    2015-07-01

    CeO2/nanographite (CeO2/nano-G) composite materials were got by chemical precipitation method with nanographite (nano-G) and cerous nitrate hexahydrate as raw materials. The microstructures of CeO2/nano-G composite materials were characterized by means of SEM, XRD, XPS and Raman. The cathodes were made by nano-G and CeO2/nano-G composite materials, respectively. The electrolysis phenol was conducted by the diaphragm cell prepared cathode and the Ti/RuO2 anode. The results indicated that the Cerium oxide is mainly in nanoscale spherical state, uniformly dispersed in the nanographite sheet surface, and there are two different oxidation states for elemental Ce, namely, Ce(III) and Ce(IV). In the diaphragm electrolysis system with the aeration conditions, the degradation rate of phenol reached 93.9% under 120 min's electrolysis. Ceria in the cathode materials might lead to an increase in the local oxygen concentration, which accelerated the two-electron reduction of O2 to hydrogen peroxide (H2O2). The removal efficiency of phenol by using the CeO2/nano-G composite cathode was better than that of the nano-G cathode.

  10. Fruit juice extract mediated synthesis of CeO2 nanoparticles for antibacterial and photocatalytic activities

    NASA Astrophysics Data System (ADS)

    Reddy Yadav, L. S.; Manjunath, K.; Archana, B.; Madhu, C.; Raja Naika, H.; Nagabhushana, H.; Kavitha, C.; Nagaraju, G.

    2016-05-01

    Ceria ( CeO2 is a technologically important rare-earth material because of its unique properties and various engineering/biological applications. In the present work, cerium oxide nanoparticles have been prepared by a simple solution combustion method using watermelon juice as a novel combustible fuel. The structure and morphology of the synthesized CeO2 nanoparticles were analyzed using various analytical tools such as PXRD, FTIR, Raman, UV-Visible and SEM. PXRD pattern confirms that the prepared material is composed of cubic-phase cerium oxide nanoparticles. Photocatalytic degradation of Methylene blue dye using CeO2 nanoparticles shows 98% of degradation in UV irradiations. Furthermore the antibacterial properties of CeO2 nanoparticles were investigated by their bacterial activity against two bacterial strains using the agar well diffusion method.

  11. Leucas aspera mediated multifunctional CeO2 nanoparticles: Structural, photoluminescent, photocatalytic and antibacterial properties.

    PubMed

    Malleshappa, J; Nagabhushana, H; Sharma, S C; Vidya, Y S; Anantharaju, K S; Prashantha, S C; Daruka Prasad, B; Raja Naika, H; Lingaraju, K; Surendra, B S

    2015-01-01

    Spherical shaped cerium dioxide (CeO2) nanoparticles (NPs) were synthesized via bio mediated route using Leucas aspera (LA) leaf extract. The NPs were characterized by PXRD, SEM, UV-Visible techniques. Photoluminescence (PL), photocatalysis and antibacterial properties of NPs were studied. PXRD patterns and Rietveld analysis confirm cubic fluorite structure with space group Fm-3m. SEM results evident that morphology of the NPs was greatly influenced by the concentration of LA leaf extract in the reaction mixture. The band gap energy of the NPs was found to be in the range of 2.98-3.4 eV. The photocatalytic activity of NPs was evaluated by decolorization of Rhodamine-B (RhB) under UVA and Sun light irradiation. CeO2 NPs show intense blue emission with CIE coordinates (0.14, 0.22) and average color coordinated temperature value ∼148,953 K. Therefore the present NPs quite useful for cool LEDs. The superior photocatalytic activity was observed for CeO2 NPs with 20 ml LA under both UVA and Sunlight irradiation. The enhanced photocatalytic activity and photoluminescent properties were attributed to defect induced band gap engineered CeO2 NPs. Further, CeO2 with 20 ml LA exhibit significant antibacterial activity against Escherichia coli (EC) and Staphylococcus aureus (SA). These findings show great promise of CeO2 NPs as multifunctional material for various applications.

  12. Hexagonal CeO2 nanostructures: an efficient electrode material for supercapacitors.

    PubMed

    Maheswari, Nallappan; Muralidharan, Gopalan

    2016-09-28

    Cerium oxide (CeO2) has emerged as a new and promising pseudocapacitive material due to its prominent valance states and extensive applications in various fields. In the present study, hexagonal CeO2 nanostructures have been prepared via the hydrothermal method employing cationic surfactant cetyl trimethyl ammonium bromide (CTAB). CTAB ensures a slow rate of hydrolysis to form small sized CeO2 nanostructures. The role of calcination temperature on the morphological, structural, electrochemical properties and cyclic stability has been assessed for supercapacitor applications. The mesoscopic hexagonal architecture endows the CeO2 with not only a higher specific capacity, but also with an excellent rate capability and cyclability. When the charge/discharge current density is increased from 2 to 10 A g(-1) the reversible charge capacity decreased from 927 F g(-1) to 475 F g(-1) while 100% capacity retention at a high current density of 20 A g(-1) even after 1500 cycles could be achieved. Furthermore, the asymmetric supercapacitor based on CeO2 exhibited a significantly higher energy density of 45.6 W h kg(-1) at a power density of 187.5 W kg(-1) with good cyclic stability. The electrochemical richness of the CeO2 nanostructure makes it a suitable electrode material for supercapacitor applications.

  13. Toxicity of CeO2 nanoparticles - the effect of nanoparticle properties.

    PubMed

    Leung, Yu Hang; Yung, Mana M N; Ng, Alan M C; Ma, Angel P Y; Wong, Stella W Y; Chan, Charis M N; Ng, Yip Hang; Djurišić, Aleksandra B; Guo, Muyao; Wong, Mabel Ting; Leung, Frederick C C; Chan, Wai Kin; Leung, Kenneth M Y; Lee, Hung Kay

    2015-04-01

    Conflicting reports on the toxicity of CeO2 nanomaterials have been published in recent years, with some studies finding CeO2 nanoparticles to be toxic, while others found it to have protective effects against oxidative stress. To investigate the possible reasons for this, we have performed a comprehensive study on the physical and chemical properties of nanosized CeO2 from three different suppliers as well as CeO2 synthesized by us, and tested their toxicity. For toxicity tests, we have studied the effects of CeO2 nanoparticles on a Gram-negative bacterium Escherichia coli in the dark, under ambient and UV illuminations. We have also performed toxicity tests on the marine diatom Skeletonema costatum under ambient and UV illuminations. We found that the CeO2 nanoparticle samples exhibited significantly different toxicity, which could likely be attributed to the differences in interactions with cells, and possibly to differences in nanoparticle compositions. Our results also suggest that toxicity tests on bacteria may not be suitable for predicting the ecotoxicity of nanomaterials. The relationship between the toxicity and physicochemical properties of the nanoparticles is explicitly discussed in the light of the current results. PMID:25768267

  14. Toxicity of CeO2 nanoparticles - the effect of nanoparticle properties.

    PubMed

    Leung, Yu Hang; Yung, Mana M N; Ng, Alan M C; Ma, Angel P Y; Wong, Stella W Y; Chan, Charis M N; Ng, Yip Hang; Djurišić, Aleksandra B; Guo, Muyao; Wong, Mabel Ting; Leung, Frederick C C; Chan, Wai Kin; Leung, Kenneth M Y; Lee, Hung Kay

    2015-04-01

    Conflicting reports on the toxicity of CeO2 nanomaterials have been published in recent years, with some studies finding CeO2 nanoparticles to be toxic, while others found it to have protective effects against oxidative stress. To investigate the possible reasons for this, we have performed a comprehensive study on the physical and chemical properties of nanosized CeO2 from three different suppliers as well as CeO2 synthesized by us, and tested their toxicity. For toxicity tests, we have studied the effects of CeO2 nanoparticles on a Gram-negative bacterium Escherichia coli in the dark, under ambient and UV illuminations. We have also performed toxicity tests on the marine diatom Skeletonema costatum under ambient and UV illuminations. We found that the CeO2 nanoparticle samples exhibited significantly different toxicity, which could likely be attributed to the differences in interactions with cells, and possibly to differences in nanoparticle compositions. Our results also suggest that toxicity tests on bacteria may not be suitable for predicting the ecotoxicity of nanomaterials. The relationship between the toxicity and physicochemical properties of the nanoparticles is explicitly discussed in the light of the current results.

  15. Influence of CeO2 nanoparticles on growth and physiology of sorghum

    NASA Astrophysics Data System (ADS)

    Mu, Linlin; Liang, Wei-zhen; Kinsey, Erin; Rauh, Bradley; Kresovich, Stephen; Darnault, Christophe

    2016-04-01

    Cerium oxide nanoparticles (CeO2 NPs) are commonly used as polishing agents for industry and fuel additives to decrease the particulate matter emissions. CeO2 NPs may be encountered in the soil and water environment through their life cycle or accidental releases, and have potential phytotoxicity effects. Therefore, it is critical to assess the potential effects of CeO2 NPs in soil on plant growth and physiology. The objective of this research is to determine the physiological responses of three sorghums (Grassl, BtX623 and Rio) to the effect of CeO2 nanoparticles in potting soil environment. Sorghums were germinated and grown in potting soil in the greenhouse for three weeks cultivation with treatments of 0, 100, 500, 1000 mg CeO2 NPs per kg soil. Plant parameters, such as length, weight, and biomass of root and leaves were measured in each treatment with 12 replications. After three weeks germination, the sorghum plants were dig out and the roots were examined and scanned by the Silverfast SE Plus scanner to compare and analyze their dimensions and shapes. To further study the growth and physiological changes in plants due to the presence of CeO2 NPs in soil, one selected type of sorghum (Grassl) was grown under the four different CeO2 NPs concentration treatments for six months until plant maturity, and was also cut and harvested three times to study CeO2 NPs effect on plant re-growth. At the end of each growing period, above ground vegetative tissues were air-dried, grounded to 2mm particle size and compositional traits were estimated by using near-infrared spectroscopy. The influence of nanoparticles was observed on some of the plant traits. Preliminary results showed the influence of CeO2 NPs on the roots growth, as Grassl and Btx623 in 100 mgkg-1 treatment grew significantly faster than other concentrations; however no significant difference between control and 100 mgkg-1 treatment in Rio. CeO2 NPs concentration of 100 mgkg-1 had no impact on sorghum growth, compared to the control treatment. Results of the six months growth and repetitive cutting experiments indicated that the different treatments, including the presence and/or concentrations of the nanoparticles, impacted some of the compositional traits of sorghum.

  16. Influence of CeO2 nanoparticles on growth and physiology of sorghum

    NASA Astrophysics Data System (ADS)

    Mu, Linlin; Liang, Wei-zhen; Kinsey, Erin; Rauh, Bradley; Kresovich, Stephen; Darnault, Christophe

    2016-04-01

    Cerium oxide nanoparticles (CeO2 NPs) are commonly used as polishing agents for industry and fuel additives to decrease the particulate matter emissions. CeO2 NPs may be encountered in the soil and water environment through their life cycle or accidental releases, and have potential phytotoxicity effects. Therefore, it is critical to assess the potential effects of CeO2 NPs in soil on plant growth and physiology. The objective of this research is to determine the physiological responses of three sorghums (Grassl, BtX623 and Rio) to the effect of CeO2 nanoparticles in potting soil environment. Sorghums were germinated and grown in potting soil in the greenhouse for three weeks cultivation with treatments of 0, 100, 500, 1000 mg CeO2 NPs per kg soil. Plant parameters, such as length, weight, and biomass of root and leaves were measured in each treatment with 12 replications. After three weeks germination, the sorghum plants were dig out and the roots were examined and scanned by the Silverfast SE Plus scanner to compare and analyze their dimensions and shapes. To further study the growth and physiological changes in plants due to the presence of CeO2 NPs in soil, one selected type of sorghum (Grassl) was grown under the four different CeO2 NPs concentration treatments for six months until plant maturity, and was also cut and harvested three times to study CeO2 NPs effect on plant re-growth. At the end of each growing period, above ground vegetative tissues were air-dried, grounded to 2mm particle size and compositional traits were estimated by using near-infrared spectroscopy. The influence of nanoparticles was observed on some of the plant traits. Preliminary results showed the influence of CeO2 NPs on the roots growth, as Grassl and Btx623 in 100 mgkg‑1 treatment grew significantly faster than other concentrations; however no significant difference between control and 100 mgkg‑1 treatment in Rio. CeO2 NPs concentration of 100 mgkg‑1 had no impact on sorghum growth, compared to the control treatment. Results of the six months growth and repetitive cutting experiments indicated that the different treatments, including the presence and/or concentrations of the nanoparticles, impacted some of the compositional traits of sorghum.

  17. CeO2-covered nanofiber for highly efficient removal of phosphorus from aqueous solution.

    PubMed

    Ko, Young Gun; Do, Taegu; Chun, Youngsang; Kim, Choong Hyun; Choi, Ung Su; Kim, Jae-Yong

    2016-04-15

    The lowering phosphorus concentration of lakes or rivers using adsorbents has been considered to be the most effective way to prevent water eutrophication. However, the development of an adsorbent is still challenging because conventional adsorbents have not shown a sufficient phosphorus adsorption capacity (0.3-2.0mmol/g) to treat industrial, agricultural or domestic wastewater at a large scale. Herein, a novel and effective strategy to remove phosphorus efficiently with a CeO2-covered nanofiber is shown. The CeO2-covered nanofiber was synthesized through (1) amine group immobilization onto an electrospun polyacrylonitrile nanofiber and (2) adsorption of Ce(3+) on it. The CeO2-covered nanofiber played a role in catching phosphate ions in an aqueous solution by the oxidation, reduction, and ion-exchange of adsorbed Ce(3+) on the nanofiber from CeO2 to CePO4, and enabled remarkable phosphate adsorption capacity of the nanofiber (ca. 17.0mmol/g) at the range of ca. pH 2-6. Our strategy might be the most feasible method to efficiently lower the phosphorus concentration in lakes or rivers owing to the easy and inexpensive preparation of CeO2-covered nanofiber at an industrial scale, with a high phosphate adsorption capacity.

  18. Facet-Controlled CeO2 Nanocrystals for Oxidative Coupling of Methane.

    PubMed

    Sun, Yongnan; Shen, Yue; Song, Jianjun; Ba, Rongbin; Huang, Shuangshuang; Zhao, Yonghui; Zhang, Jun; Sun, Yuhan; Zhu, Yan

    2016-05-01

    Whether the catalysts of the high temperature reaction such methane oxidation coupling has a structure-sensitive catalytic behavior or not, it is discussed and confirmed the shape-specific impact on methane activity by designing the catalysts with different crystal facets exposed. CeO2 nanowires enclosed by {110} and {100} planes show the higher CH4 conversion and higher C2 hydrocarbons (C2H4 and C2H6) selectivity, compared with particle CeO2 rounded by {111} and {100} planes, suggesting that CeO2 (110) surface favors the activation of CH4. Encouraged by the result, to control facet-controlled synthesis of catalysts for tailoring the catalytic properties at high temperature, the CeO2 (110) surface is chosen as doped sites to form the doped catalyst such as Ca doped CeO2 nanowires for OCM reaction, enhancing C2 hydrocarbons selectivity dramatically and suppressing the deep oxidation product (CO and CO2) selectivity.

  19. Facet-Controlled CeO2 Nanocrystals for Oxidative Coupling of Methane.

    PubMed

    Sun, Yongnan; Shen, Yue; Song, Jianjun; Ba, Rongbin; Huang, Shuangshuang; Zhao, Yonghui; Zhang, Jun; Sun, Yuhan; Zhu, Yan

    2016-05-01

    Whether the catalysts of the high temperature reaction such methane oxidation coupling has a structure-sensitive catalytic behavior or not, it is discussed and confirmed the shape-specific impact on methane activity by designing the catalysts with different crystal facets exposed. CeO2 nanowires enclosed by {110} and {100} planes show the higher CH4 conversion and higher C2 hydrocarbons (C2H4 and C2H6) selectivity, compared with particle CeO2 rounded by {111} and {100} planes, suggesting that CeO2 (110) surface favors the activation of CH4. Encouraged by the result, to control facet-controlled synthesis of catalysts for tailoring the catalytic properties at high temperature, the CeO2 (110) surface is chosen as doped sites to form the doped catalyst such as Ca doped CeO2 nanowires for OCM reaction, enhancing C2 hydrocarbons selectivity dramatically and suppressing the deep oxidation product (CO and CO2) selectivity. PMID:27483809

  20. CeO2-covered nanofiber for highly efficient removal of phosphorus from aqueous solution.

    PubMed

    Ko, Young Gun; Do, Taegu; Chun, Youngsang; Kim, Choong Hyun; Choi, Ung Su; Kim, Jae-Yong

    2016-04-15

    The lowering phosphorus concentration of lakes or rivers using adsorbents has been considered to be the most effective way to prevent water eutrophication. However, the development of an adsorbent is still challenging because conventional adsorbents have not shown a sufficient phosphorus adsorption capacity (0.3-2.0mmol/g) to treat industrial, agricultural or domestic wastewater at a large scale. Herein, a novel and effective strategy to remove phosphorus efficiently with a CeO2-covered nanofiber is shown. The CeO2-covered nanofiber was synthesized through (1) amine group immobilization onto an electrospun polyacrylonitrile nanofiber and (2) adsorption of Ce(3+) on it. The CeO2-covered nanofiber played a role in catching phosphate ions in an aqueous solution by the oxidation, reduction, and ion-exchange of adsorbed Ce(3+) on the nanofiber from CeO2 to CePO4, and enabled remarkable phosphate adsorption capacity of the nanofiber (ca. 17.0mmol/g) at the range of ca. pH 2-6. Our strategy might be the most feasible method to efficiently lower the phosphorus concentration in lakes or rivers owing to the easy and inexpensive preparation of CeO2-covered nanofiber at an industrial scale, with a high phosphate adsorption capacity. PMID:26795705

  1. Imaging the atomic surface structures of CeO2 nanoparticles

    SciTech Connect

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

    2014-01-01

    Atomic surface structures of CeO2 nanoparticles are under debate owing to the lack of clear experimental determination of the positions of the surface oxygen atoms. Particularly controversial is the (100) surface structure of this material. In this study, with oxygen atoms clearly observed using aberration corrected high resolution electron microscopy, we determined the atomic structures of the (100), (110) and (111) surfaces of CeO2 nanocubes. The predominantly exposed (100) surface has a mixture of Ce, O, and reduced CeO terminations, underscoring the complex structures of this polar surface that previously was often oversimplified. The (110) surface shows saw-like (111) nanofacets and flat CeO2-x terminations with oxygen vacancies. The (111) surface has an O termination. As these three low index surfaces are the most often exposed facets in the majority of CeO2 nanoparticles, these findings can be extended to the surfaces of differently shaped CeO2 nanoparticles as well as provide insight about face-selective catalysis.

  2. Dielectrical Properties of CeO2 Nanoparticles at Different Temperatures

    PubMed Central

    Zamiri, Reza; Abbastabar Ahangar, Hossein; Kaushal, Ajay; Zakaria, Azmi; Zamiri, Golnoosh; Tobaldi, David; Ferreira, J. M. F.

    2015-01-01

    A template-free precipitation method was used as a simple and low cost method for preparation of CeO2 nanoparticles. The structure and morphology of the prepared nanoparticle samples were studied in detail using X-ray diffraction, Raman spectroscopy and Scanning Electron Microscopy (SEM) measurements. The whole powder pattern modelling (WPPM) method was applied on XRD data to accurately measure the crystalline domain size and their size distribution. The average crystalline domain diameter was found to be 5.2 nm, with a very narrow size distribution. UV-visible absorbance spectrum was used to calculate the optical energy band gap of the prepared CeO2 nanoparticles. The FT-IR spectrum of prepared CeO2 nanoparticles showed absorption bands at 400 cm-1 to 450 cm-1 regime, which correspond to CeO2 stretching vibration. The dielectric constant (εr) and dielectric loss (tan δ) values of sintered CeO2 compact consolidated from prepared nanoparticles were measured at different temperatures in the range from 298 K (room temperature) to 623 K, and at different frequencies from 1 kHz to 1 MHz. PMID:25910071

  3. Influence of CeO2 morphology on the catalytic activity of CeO2-Pt hybrids for CO oxidation.

    PubMed

    Singhania, Nisha; Anumol, E A; Ravishankar, N; Madras, Giridhar

    2013-11-21

    Ceria, because of its excellent redox behavior and oxygen storage capacity, is used as a catalyst for several technologically important reactions. In the present study, different morphologies of nano-CeO2 (rods, cubes, octahedra) were synthesized using the hydrothermal route. An ultrafast microwave-assisted method was used to efficiently attach Pt particles to the CeO2 polyhedra. These nanohybrids were tested as catalysts for the CO oxidation reaction. The CeO2/Pt catalyst with nanorods as the support was found to be the most active catalyst. XPS and IR spectroscopy measurements were carried out in order to obtain a mechanistic understanding and it was observed that the adsorbed carbonates with lower stability on the reactive planes of nanorods and cubes are the major contributor to this enhanced catalytic activity.

  4. Surface structure and catalytic properties of MoO3/CeO2 and CuO/MoO3/CeO2.

    PubMed

    Yu, Wujiang; Zhu, Jie; Qi, Lei; Sun, Chuanzhi; Gao, Fei; Dong, Lin; Chen, Yi

    2011-12-15

    XRD, LRS, TPR and in situ NH(3) adsorption FT-IR were used to investigate the dispersion state of the copper oxide and molybdena species of MoO(3)/CeO(2) and CuO/MoO(3)/CeO(2) catalysts as well as their surface acidity. The results showed that the molybdena monolayer modification promoted the dispersion of CuO due to the formation of new tetrahedral vacancies. Meanwhile, CuO changed the structure of molybdenum species and then influenced the surface acidity of the samples. A detail discussion about the possible model of the surface structure of the catalyst was presented. In addition, combining with the in situ NH(3) adsorption FT-IR, the relationships between the activities for ''NO + NH(3) + O(2)'' reaction and surface acid properties (Brønsted and Lewis acid sites) of the catalysts were discussed. PMID:21930282

  5. Structural, morphological, Raman, optical, magnetic, and antibacterial characteristics of CeO2 nanostructures

    NASA Astrophysics Data System (ADS)

    Abbas, Fazal; Iqbal, Javed; Jan, Tariq; Badshah, Noor; Mansoor, Qaisar; Ismail, Muhammad

    2016-01-01

    In this study, CeO2 nanostructures were synthesized by a soft chemical method. A hydrothermal treatment was observed to lead to an interesting morphological transformation of the nanoparticles into homogeneous microspheres composed of nanosheets with an average thickness of 40 nm. Structural analysis revealed the formation of a single-phase cubic fluorite structure of CeO2 for both samples. A Raman spectroscopic study confirmed the XRD results and furthermore indicated the presence of a large number of oxygen vacancies in the nanosheets. These oxygen vacancies led to room-temperature ferromagnetism (RTFM) of the CeO2 nanosheets with enhanced magnetic characteristics. Amazingly, the nanosheets exhibited substantially greater antibacterial activity than the nanoparticles. This greater antibacterial activity was attributed to greater exposure of high-surface-energy polar surfaces and to the presence of oxygen vacancies.

  6. Upconversion emission properties of CeO2: Tm3+, Yb3+ inverse opal photonic crystals

    NASA Astrophysics Data System (ADS)

    Cheng, Gong; Wu, Hangjun; Yang, Zhengwen; Liao, Jiayan; Lai, Shenfeng; Qiu, Jianbei; Song, Zhiguo

    2014-10-01

    The ordered and disordered templates were assembled by vertical deposition of polystyrene microspheres. The CeO2: Tm3+, Yb3+ precursor solution was used to infiltrate into the voids of the ordered and disordered templates, respectively. Then the ordered and disordered templates were calcined at 950°C in an air furnace, and the CeO2: Tm3+, Yb3+ inverse opals were obtained. The upconversion emissions from CeO2: Tm3+, Yb3+ inverse opals were suppressed due to the photon trapping caused by Bragg reflection of lattice planes when the upconversion emission band was in the range of the photonic band gaps in the inverse opals.

  7. First-principles characterization of formate and carboxyl adsorption on the stoichiometric CeO2(111) and CeO2(110) surfaces

    SciTech Connect

    Mei, Donghai

    2013-05-20

    Molecular adsorption of formate and carboxyl on the stoichiometric CeO2(111) and CeO2(110) surfaces was studied using periodic density functional theory (DFT+U) calculations. Two distinguishable adsorption modes (strong and weak) of formate are identified. The bidentate configuration is more stable than the monodentate adsorption configuration. Both formate and carboxyl bind at the more open CeO2(110) surface are stronger. The calculated vibrational frequencies of two adsorbed species are consistent with experimental measurements. Finally, the effects of U parameters on the adsorption of formate and carboxyl over both CeO2 surfaces were investigated. We found that the geometrical configurations of two adsorbed species are not affected by using different U parameters (U=0, 5, and 7). However, the calculated adsorption energy of carboxyl pronouncedly increases with the U value while the adsorption energy of formate only slightly changes (<0.2 eV). The Bader charge analysis shows the opposite charge transfer occurs for formate and carboxyl adsorption where the adsorbed formate is negatively charge whiled the adsorbed carboxyl is positively charged. Interestingly, with the increasing U parameter, the amount of charge is also increased. This work was supported by the Laboratory Directed Research and Development (LDRD) project of the Pacific Northwest National Laboratory (PNNL) and by a Cooperative Research and Development Agreement (CRADA) with General Motors. The computations were performed using the Molecular Science Computing Facility in the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL), which is a U.S. Department of Energy national scientific user facility located at PNNL in Richland, Washington. Part of the computing time was also granted by the National Energy Research Scientific Computing Center (NERSC)

  8. Effects of pH and phosphate on CeO2 nanoparticle dissolution.

    PubMed

    Dahle, Jessica T; Livi, Ken; Arai, Yuji

    2015-01-01

    As the result of rapidly grown nanotechnology industries, release of engineered nanoparticles (ENPs) to environment has increased, posing in a serious risk to environmental and human health. To better understand the chemical fate of ENPs in aquatic environments, solubility of CeO2 NPs was investigated using batch dissolution experiments as a function of pH (1.65-12.5), [phosphate] and particle size (33 and 78 nm). It was found that CeO2 dissolution was only significant at pH<5 and inversely proportional to surface area. After 120 h, the release of Ce was ∼3 times greater in large NPs than that in small NPs that is likely contributed by the difference in exchangeable Ce(III) impurity (small: 0.3 mM kg(-1), large: 1.56 mM kg(-1)). When 100 μM of phosphate was added, the dissolution rate of CeO2 NPs was decreased in small NPs by 15% at pH 1.65 and 75% at pH 4.5 and in large NPs by 56% at pH 1.65 and 63% at pH 4.5. The inner-sphere surface complexation of P that is revealed by the zeta potential measurements is effectively suppressing the CeO2 NP dissolution. Predicting the fate and transport of CeO2 NPs in aquatic environment, pH and P ligands might play important roles in controlling the solubility of CeO2 NPs.

  9. Structural and dielectric properties of Cu doped CeO2

    NASA Astrophysics Data System (ADS)

    Kumar, Pawan; Chand, F.; Kumar, Parmod; Meena, R. C.; Kumar, Ashish; Asokan, K.

    2016-05-01

    In the present work, we report the structural and dielectric properties of Cu doped CeO2 compounds synthesized by solid state reaction method. X-ray diffraction study confirms the formation of cubic phase with Fm-3m space group corresponding to fluorite CeO2 structure. The crystallite size was found to decrease with Cu concentration. Furthermore, the dielectric measurements were carried out by varying frequency in the temperature range of 120 to 380 K. It has been found that the increase in Cu concentration in the host lattice leads to an enhancement in dielectric constant.

  10. Transmission Electron Microscopy Investigation of Krypton Bubbles in Polycrystalline CeO2

    SciTech Connect

    Lingfeng He; Clarissa Yablinsky; Mahima Gupta; Jian Gan; Marquis A. Kirk; Todd R. Allen

    2013-05-01

    To gain an understanding of gas bubble transport in oxide nuclear fuel, this paper uses polycrystalline CeO2, composed of both nanograins and micrograins, as a surrogate material for UO2. The CeO2 was implanted with 150-keV Kr ions up to a dose of 1 x 1016 ions/cm2 at 600 degrees C. Transmission electron microscopy characterizations of small Kr bubbles in nanograin and micrograin regions were compared. The grain boundary acted as an efficient defect sink, as evidenced by smaller bubbles and a lower bubble density in the nanograin region as compared to the micrograin region.

  11. Conversion of Acetic Acid from the Catalytic Pyrolysis of Xylan Over CeO2.

    PubMed

    Lee, Heejin; Ko, Jeong Huy; Kwon, Woo Hyun; Park, Young-Kwon

    2016-05-01

    CeO2 was synthesized hydrothermally in supercritical water and applied to the catalytic pyrolysis of xylan. Acetic acid, which is the main component in bio-oil produced from the non-catalytic pyrolysis of xylan, deteriorates the fuel quality of the oil. Catalysis over CeO2 effectively converted the acetic acid to ketone species, such as acetone, thereby reducing the acidity of the oil considerably. The content of aromatics in bio-oil was also increased substantially by catalysis. PMID:27483777

  12. Formation of CeO 2 buffer layer using multi-plume PLD

    NASA Astrophysics Data System (ADS)

    Sutoh, Y.; Nakaoka, K.; Miura, M.; Matsuda, J.; Nakanishi, T.; Nakai, A.; Yoshizumi, M.; Izumi, T.; Miyata, S.; Iijima, Y.; Yamada, Y.; Shiohara, Y.; Saitoh, T.

    2008-09-01

    The CeO 2 buffer layer was fabricated using the multi-plume pulsed laser deposition (PLD) method with different deposition rates controlled by the excimer laser energy and frequency on the Gd 2Zr 2O 7 template tape formed by the ion-beam assisted deposition (IBAD) with 14° of Δ φ (full width at half maximum (FWHM) value of X-ray diffraction φ-scan for Gd 2Zr 2O 7 (2 2 2) pole). The laser conditions with high pulse energy and low frequency resulted in a highly textured in-plane grain alignment (Δ φ). The surface roughness and Δ φ values were improved by increasing the thickness of the CeO 2 buffer layer. YBCO films with the thickness of 1 μm and 1.6 μm were further deposited by the advanced trifluoroacetates-metal organic deposition (TFA-MOD) on the CeO 2 buffered substrates with the deposition rate of 0.15 and 0.5 μm/min. The Jc values of 2.5 MA/cm 2 and 2 MA/cm 2 were obtained, respectively. High Jc films could be deposited on the CeO 2 buffer layer even at high deposition rate by the multi-plume deposition.

  13. Fundamentals and Catalytic Applications of CeO2-Based Materials.

    PubMed

    Montini, Tiziano; Melchionna, Michele; Monai, Matteo; Fornasiero, Paolo

    2016-05-25

    Cerium dioxide (CeO2, ceria) is becoming an ubiquitous constituent in catalytic systems for a variety of applications. 2016 sees the 40(th) anniversary since ceria was first employed by Ford Motor Company as an oxygen storage component in car converters, to become in the years since its inception an irreplaceable component in three-way catalysts (TWCs). Apart from this well-established use, ceria is looming as a catalyst component for a wide range of catalytic applications. For some of these, such as fuel cells, CeO2-based materials have almost reached the market stage, while for some other catalytic reactions, such as reforming processes, photocatalysis, water-gas shift reaction, thermochemical water splitting, and organic reactions, ceria is emerging as a unique material, holding great promise for future market breakthroughs. While much knowledge about the fundamental characteristics of CeO2-based materials has already been acquired, new characterization techniques and powerful theoretical methods are deepening our understanding of these materials, helping us to predict their behavior and application potential. This review has a wide view on all those aspects related to ceria which promise to produce an important impact on our life, encompassing fundamental knowledge of CeO2 and its properties, characterization toolbox, emerging features, theoretical studies, and all the catalytic applications, organized by their degree of establishment on the market.

  14. Facile synthesis of ferromagnetic Ni doped CeO2 nanoparticles with enhanced anticancer activity

    NASA Astrophysics Data System (ADS)

    Abbas, Fazal; Jan, Tariq; Iqbal, Javed; Ahmad, Ishaq; Naqvi, M. Sajjad H.; Malik, Maaza

    2015-12-01

    NixCe1-xO2 (where x = 0, 0.01, 0.03, 0.05 and 0.07) nanoparticles were synthesized by soft chemical method and were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), Raman, UV-vis absorption spectroscopy and vibrating sample magnetometer (VSM). XRD and Raman results indicated the formation of single phase cubic fluorite structure for the synthesized nanoparticles. Ni dopant induced excessive structural changes such as decrease in crystallite size as well as lattice constants and enhancement in oxygen vacancies in CeO2 crystal structure. These structural variations significantly influenced the optical and magnetic properties of CeO2 nanoparticles. The synthesized NixCe1-xO2 nanoparticles exhibited room temperature ferromagnetic behavior. Ni doping induced effects on the cytotoxicity of CeO2 nanoparticles were examined against HEK-293 healthy cell line and SH-SY5Y neuroblastoma cancer cell line. The prepared NixCe1-xO2 nanoparticles demonstrated differential cytotoxicity. Furthermore, anticancer activity of CeO2 nanoparticles observed to be significantly enhanced with Ni doping which was found to be strongly correlated with the level of reactive oxygen species (ROS) production. The prepared ferromagnetic NixCe1-xO2 nanoparticles with differential cytotoxic nature may be potential for future targeted cancer therapy.

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

    PubMed Central

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

    2016-01-01

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

  16. Hierarchically mesostructured doped CeO2 with potential for solar-cell use

    NASA Astrophysics Data System (ADS)

    Corma, Avelino; Atienzar, Pedro; García, Hermenegildo; Chane-Ching, Jean-Yves

    2004-06-01

    Many properties provided by supramolecular chemistry, nanotechnology and catalysis only appear in solids exhibiting large surface areas and regular porosity at the nanometre scale. In nanometre-sized particles, the ratio of the number of atoms in the surface to the number in the bulk is much larger than for micrometre-sized materials, and this can lead to novel properties. Here we report the preparation of a hierarchically structured mesoporous material from nanoparticles of CeO2 of strictly uniform size. The synthesis involves self-assembly of these 5-nm CeO2 pre-treated nanoparticles in the presence of a structure directing agent (poly(alkylene oxide) block polymer). The walls of this hexagonal structured CeO2 material are formed from the primary nanoparticles. The material possesses large pore volumes, high surface areas, and marked thermal stability, allowing it to be easily doped after synthesis whilst maintaining textural and mechanical integrity. It also exhibits a photovoltaic response, which is directly derived from the nanometric particle size-normal CeO2 does not show this response. We have constructed operational organic-dye-free solar cells using nanometric ceria particles (in both mesostructured or amorphous forms) as the active component, and find efficiencies that depend on the illuminating power.

  17. Ionic liquid-assisted sonochemical preparation of CeO2 nanoparticles for CO oxidation

    DOE PAGESBeta

    Alammar, Tarek; Noei, Heshmat; Wang, Yuemin; Grünert, Wolfgang; Mudring, Anja -Verena

    2014-10-10

    CeO2 nanoparticles were synthesized via a one-step ultrasound synthesis in different kinds of ionic liquids based on bis(trifluoromethanesulfonylamide, [Tf2N]–, in combination with various cations including 1-butyl-3-methylimidazolium ([C4mim]+), 1-ethyl-2,3-dimethylimidazolium ([Edimim]+), butyl-pyridinium([Py4]+), 1-butyl-1-methyl-pyrrolidinium ([Pyrr14]+), and 2-hydroxyethyl-trimethylammonium ([N1112OH]+). Depending on synthetic parameters, such as ionic liquid, Ce(IV) precursor, heating method, and precipitator, formed ceria exhibits different morphologies, varying from nanospheres, nanorods, nanoribbons, and nanoflowers. The morphology, crystallinity, and chemical composition of the obtained materials were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray spectroscopy (EDX), Raman spectroscopy, and N2 adsorption. The structural and electronic propertiesmore » of the as-prepared CeO2 samples were probed by CO adsorption using IR spectroscopy under ultrahigh vacuum conditions. The catalytic activities of CeO2 nanoparticles were investigated in the oxidation of CO. CeO2 nanospheres obtained sonochemically in [C4mim][Tf2N] exhibit the best performance for low-temperature CO oxidation. As a result, the superior catalytic performance of this material can be related to its mesoporous structure, small particle size, large surface area, and high number of surface oxygen vacancy sites.« less

  18. Fate of cerium dioxide (CeO2) nanoparticles in municipal wastewater during activated sludge treatment.

    PubMed

    Gómez-Rivera, Francisco; Field, James A; Brown, Dustin; Sierra-Alvarez, Reyes

    2012-03-01

    This study investigated the fate of nano-CeO(2) during municipal wastewater treatment using a laboratory-scale activated sludge (A/S) system fed with primarily-treated municipal wastewater and nano-CeO(2) (55.0 mg Ce/L). Nano-CeO(2) was highly removed during A/S treatment (96.6% total Ce). Extensive removal of CeO(2) <200 nm was also attained and the concentration escaping treatment was only 0.11 mg Ce/L. Elimination occurred mainly by aggregation and settling of CeO(2) particles, promoted by circumneutral pH values and by nanoparticle interactions with organic and/or inorganic wastewater constituents. Biosorption also contributed to CeO(2) removal as shown by sludge analysis and batch adsorption studies. Batch bioassays demonstrated that nano-CeO(2) only exerted inhibition of O(2) uptake by A/S at concentrations exceeding those in the bioreactor feed (50% inhibition at 950 mg CeO(2)/L). These findings indicate that A/S treatment is expected to provide extensive removal of nano-CeO(2) in municipal wastewaters.

  19. Sensor properties of the nanostructured In2O3-CeO2 system in detection of reducing gases

    NASA Astrophysics Data System (ADS)

    Gerasimov, G. N.; Gromov, V. F.; Trakhtenberg, L. I.; Belysheva, T. V.; Spiridonova, E. Yu.; Rozenbaum, V. M.

    2014-03-01

    The sensor properties of nanostructured In2O3-CeO2 composite films with different compositions in hydrogen and carbon monoxide detection in air in the temperature range 280-500°C were studied. The temperature curves of the sensor effect S have a shape typical for metal oxide sensors with maxima S max at definite temperatures Tmax. The maxima characterize the sensor properties of the films and increased considerably when small amounts of CeO2 were added to In2O3. The highest sensitivity was found in composite films with 3-10 wt % CeO2. When the composite was further enriched with ceric oxide, the sensitivity decreased; at 40 wt % CeO2 it was considerably lower than that of pure In2O3. The introduction of CeO2 in In2O3 also caused a shift of Tmax toward lower temperatures. The mechanism of the sensitivity of the In2O3-CeO2 composite was considered; it includes the promotion of sensor reactions by small CeO2 nanoclusters lying on the surface of In2O3 crystals and an electron transfer from In2O3 to CeO2.

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

    EPA Science Inventory

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

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

    PubMed

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

    2015-05-01

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

  2. On the mechanism of nanoparticulate CeO2 toxicity to freshwater algae.

    PubMed

    Angel, Brad M; Vallotton, Pascal; Apte, Simon C

    2015-11-01

    The factors affecting the chronic (72-h) toxicity of three nanoparticulate (10-34nm) and one micron-sized form of CeO2 to the green alga, Pseudokirchneriella subcapitata were investigated. To characterise transformations in solution, hydrodynamic diameters (HDD) were measured by dynamic light scatter, zeta potential values by electrophoretic mobility, and dissolution by equilibrium dialysis. The protective effects of humic and fulvic dissolved organic carbon (DOC) on toxicity were also assessed. To investigate the mechanisms of algal toxicity, the CytoViva hyperspectral imaging system was used to visualise algal-CeO2 interactions in the presence and absence of DOC, and the role of reactive oxygen species (ROS) was investigated by 'switching off' ROS production using UV-filtered lighting conditions. The nanoparticulate CeO2 immediately aggregated in solution to HDDs measured in the range 113-193nm, whereas the HDD and zeta potential values were significantly lower in the presence of DOC. Negligible CeO2 dissolution over the time course of the bioassay ruled out potential toxicity from dissolved cerium. The nanoparticulate CeO2 concentration that caused 50% inhibition of algal growth rate (IC50) was in the range 7.6-28mg/L compared with 59mg/L for micron-sized ceria, indicating that smaller particles were more toxic. The presence of DOC mitigated toxicity, with IC50s increasing to greater than 100mg/L. Significant ROS were generated in the nanoparticulate CeO2 bioassays under normal light conditions. However, 'switching off' ROS under UV-filtered light conditions resulted in a similar IC50, indicating that ROS generation was not the toxic mechanism. The CytoViva imaging showed negligible sorption of nanoparticulate CeO2 to algal cells in the presence of DOC, and strong sorption in its absence, suggesting that this was the toxic mechanism. The results suggest that DOC in natural waters will coat CeO2 particles and mitigate toxicity to algal cells.

  3. Growth-Rate Induced Epitaxial Orientation of CeO2 on Al2O3(0001)

    SciTech Connect

    Kuchibhatla, Satyanarayana V N T; Nachimuthu, Ponnusamy; Gao, Fei; Jiang, Weilin; Shutthanandan, V.; Engelhard, Mark H.; Seal, Sudipta; Thevuthasan, Suntharampillai

    2009-05-19

    High-quality ceria (CeO2) films were grown on sapphire (Al2O3) (0001) substrates using oxygen plasma-assisted molecular beam epitaxy. The epitaxial orientation of the ceria films has been found to be (100) and (111) at low (< 8 Å/min) and higher growth rates (up to ~30 Å/min), respectively. Evidence shows that CeO2 (100) film grows as three-dimensional islands, while CeO2 (111) proceeds with layered growth. Three in-plane domains at 30° to each other are observed in the CeO2 (100), which is attributed to the close match of the oxygen sub-lattices in the film and substrate that has a three-fold symmetry. Molecular dynamic simulations have further confirmed that the CeO2 film retains (100) orientation on the Al2O3 (0001) substrate.

  4. Synthesis of novel CeO2-BiVO4/FAC composites with enhanced visible-light photocatalytic properties.

    PubMed

    Zhang, Jin; Wang, Bing; Li, Chuang; Cui, Hao; Zhai, Jianping; Li, Qin

    2014-09-01

    To utilize visible light more effectively in photocatalytic reactions, a fly ash cenosphere (FAC)-supported CeO2-BiVO4 (CeO2-BiVO4/FAC) composite photocatalyst was prepared by modified metalorganic decomposition and impregnation methods. The physical and photophysical properties of the composite have been characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), and UV-Visible diffuse reflectance spectra. The XRD patterns exhibited characteristic diffraction peaks of both BiVO4 and CeO2 crystalline phases. The XPS results showed that Ce was present as both Ce(4+) and Ce(3+) oxidation states in CeO2 and dispersed on the surface of BiVO4 to constitute a p-n heterojunction composite. The absorption threshold of the CeO2-BiVO4/FAC composite shifted to a longer wavelength in the UV-Vis absorption spectrum compared to the pure CeO2 and pure BiVO4. The composites exhibited enhanced photocatalytic activity for Methylene Blue (MB) degradation under visible light irradiation. It was found that the 7.5wt.% CeO2-BiVO4/FAC composite showed the highest photocatalytic activity for MB dye wastewater treatment.

  5. Morphology-dependent interplay of reduction behaviors, oxygen vacancies and hydroxyl reactivity of CeO2 nanocrystals.

    PubMed

    Gao, Yuxian; Li, Rongtan; Chen, Shilong; Luo, Liangfeng; Cao, Tian; Huang, Weixin

    2015-12-21

    Reduction behaviors, oxygen vacancies and hydroxyl groups play decisive roles in the surface chemistry and catalysis of oxides. Employing isothermal H2 reduction we simultaneously reduced CeO2 nanocrystals with different morphologies, created oxygen vacancies and produced hydroxyl groups. The morphology of CeO2 nanocrystals was observed to strongly affect the reduction process and the resultant oxygen vacancy structure. The resultant oxygen vacancies are mainly located on the surfaces of CeO2 cubes and rods but in the subsurface/bulk of CeO2 octahedra. The reactivity of isolated bridging hydroxyl groups on CeO2 nanocrystals was found to depend on the local oxygen vacancy concentration, in which they reacted to produce water at low local oxygen vacancy concentrations but to produce both water and hydrogen with increasing local oxygen vacancy concentration. These results reveal a morphology-dependent interplay among the reduction behaviors, oxygen vacancies and hydroxyl reactivity of CeO2 nanocrystals, which deepens the fundamental understanding of the surface chemistry and catalysis of CeO2.

  6. Effects of CeO2 nanoparticles on system performance and bacterial community dynamics in a sequencing batch reactor.

    PubMed

    Qiu, Guanglei; Neo, Sin-Yi; Ting, Yen-Peng

    2016-01-01

    The effects of CeO2 nanoparticles (NPs) on the system performance and the bacterial community dynamics in a sequencing batch reactor (SBR) were investigated, along with the fate and removal of CeO2 NPs within the SBR. Significant impact was observed on nitrification; NH4+-N removal efficiency decreased from almost 100% to around 70% after 6 days of continuous exposure to 1.0 mg/L of CeO2 NPs, followed by a gradual recovery until a stable value of around 90% after 20 days. Additionally, CeO2 NPs also led to a significant increase in the protein content in the soluble microbial products, showing the disruptive effects of CeO2 NPs on the extracellular polymeric substance matrix and related activated sludge structure. Denaturing gradient gel electrophoresis analysis showed remarkable changes in the bacterial community structure in the activated sludge after exposure to CeO2 NPs. CeO2 NPs were effectively removed in the SBR mainly via sorption onto the sludge. However, the removal efficiency decreased from 95 to 80% over 30 days. Mass balance evaluation showed that up to 50% of the NPs were accumulated within the activated sludge and were removed with the waste sludge.

  7. Effects of CeO2 nanoparticles on system performance and bacterial community dynamics in a sequencing batch reactor.

    PubMed

    Qiu, Guanglei; Neo, Sin-Yi; Ting, Yen-Peng

    2016-01-01

    The effects of CeO2 nanoparticles (NPs) on the system performance and the bacterial community dynamics in a sequencing batch reactor (SBR) were investigated, along with the fate and removal of CeO2 NPs within the SBR. Significant impact was observed on nitrification; NH4+-N removal efficiency decreased from almost 100% to around 70% after 6 days of continuous exposure to 1.0 mg/L of CeO2 NPs, followed by a gradual recovery until a stable value of around 90% after 20 days. Additionally, CeO2 NPs also led to a significant increase in the protein content in the soluble microbial products, showing the disruptive effects of CeO2 NPs on the extracellular polymeric substance matrix and related activated sludge structure. Denaturing gradient gel electrophoresis analysis showed remarkable changes in the bacterial community structure in the activated sludge after exposure to CeO2 NPs. CeO2 NPs were effectively removed in the SBR mainly via sorption onto the sludge. However, the removal efficiency decreased from 95 to 80% over 30 days. Mass balance evaluation showed that up to 50% of the NPs were accumulated within the activated sludge and were removed with the waste sludge. PMID:26744939

  8. Erosion-Corrosion Property of CeO2-Modified HVOF WC-Co Coating

    NASA Astrophysics Data System (ADS)

    Liu, Yan; Hang, Zongqiu; Chen, Hui; Ceng, Shengbo; Gou, Guoqing; Wang, Xiaomin; Tu, Mingjing; Wu, Xiangyang

    2016-04-01

    Rare-earth elements have been widely used in materials manufacturing to improve hardness and toughness. In this work, conventional, nanostructured, and CeO2-modified WC-12Co powders were sprayed using high-velocity oxygen flame spraying. The erosion-corrosion behavior and interaction of erosion and corrosion of the coatings in 3.5 wt.% NaCl solution were investigated. In situ observation was employed to analyze the failure mechanism. The results showed that the CeO2-modified WC-12Co coating possessed the best erosion-corrosion resistance, while the lowest corrosion resistance was exhibited by the conventional WC-12Co coating. The results also suggested that the erosion-corrosion mechanism in the three coatings was dominated by corrosion-accelerated erosion. However, the extent of acceleration of erosion by corrosion differed.

  9. Long-term aging of a CeO(2) based nanocomposite used for wood protection.

    PubMed

    Auffan, Melanie; Masion, Armand; Labille, Jerome; Diot, Marie-Ange; Liu, Wei; Olivi, Luca; Proux, Olivier; Ziarelli, Fabio; Chaurand, Perrine; Geantet, Christophe; Bottero, Jean-Yves; Rose, Jerome

    2014-05-01

    A multi-scale methodology was used to characterize the long-term behavior and chemical stability of a CeO2-based nanocomposite used as UV filter in wood stains. ATR-FTIR and (13)C NMR demonstrated that the citrate coated chelates with Ce(IV) through its central carboxyl- and its α-hydroxyl- groups at the surface of the unaged nanocomposite. After 42 days under artificial daylight, the citrate completely disappeared and small amount of degradation products remained attached to the surface even after 112 days. Moreover, the release/desorption of the citrate layer led to a surface reorganization of the nano-sized CeO2 core observed by XANES (Ce L3-edge). Such a surface and structural transformation of the commercialized nanocomposite could have implications in term of fate, transport, and potential impacts towards the environment.

  10. Reactivity and reaction intermediates for acetic acid adsorbed on CeO2(111)

    DOE PAGESBeta

    Calaza, Florencia C.; Chen, Tsung -Liang; Mullins, David R.; Xu, Ye; Steven H. Overbury

    2015-05-02

    Adsorption and reaction of acetic acid on a CeO2(1 1 1) surface was studied by a combination of ultra-highvacuum based methods including temperature desorption spectroscopy (TPD), soft X-ray photoelectronspectroscopy (sXPS), near edge X-ray absorption spectroscopy (NEXAFS) and reflection absorption IRspectroscopy (RAIRS), together with density functional theory (DFT) calculations. TPD shows that thedesorption products are strongly dependent upon the initial oxidation state of the CeO2 surface, includingselectivity between acetone and acetaldehyde products. The combination of sXPS and NEXAFS demon-strate that acetate forms upon adsorption at low temperature and is stable to above 500 K, above whichpoint ketene, acetone and acetic acidmore » desorb. Furthermore, DFT and RAIRS show that below 500 K, bridge bondedacetate coexists with a moiety formed by adsorption of an acetate at an oxygen vacancy, formed bywater desorption.« less

  11. Stable Electron Field Emission from CeO2 Nanowires by Hydrothermal Method

    NASA Astrophysics Data System (ADS)

    Fu, Xing-Qiu; Feng, Ping; Wang, Chong; Wang, Tai-Hong

    2007-08-01

    CeO2 nanowires are successful synthesized by hydrothermal method and their field emission (FE) properties are investigated. The turn-on electric field is 5.8 V/μm at an emitter-anode spacing of 700 μm. The FE current is stable and the current fluctuations are less than 3% over 5 h. All the plotted Fowler-Nordheim curves yield straight lines, which are in agreement with the Fowler-Nordheim theory. The relationship between the field enhancement factor β and the emitter-anode spacing d follows a universal equation. Our results imply that the CeO2 nanowires are promising materials for fabricating FE cathodes.

  12. Mn3O4-CeO2 nano-catalysts: Synthesis, characterization and application

    NASA Astrophysics Data System (ADS)

    Anushree, Sharma, C.; Kumar, S.

    2016-05-01

    Nano-sized Mn3O4-CeO2 catalysts were synthesized by a cost effective co-precipitation method, and were studied as a heterogeneous catalyst for wet air oxidation of paper industry wastewater at mild operating conditions of 90 °C and 1 atm. The structural, micro-structural and textural properties of synthesized catalysts were studied through various characterization techniques, i.e. XRD, TEM, N2-sorption and EDS. The catalytic activity of Mn3O4-CeO2 was interestingly found to be higher than the corresponding single-metal oxides, and the Ce50Mn50 nano-catalyst with small crystallite size (4.5 nm), high specific surface area (75 m2g-1) and high porosity (0.24 ccg-1) was found to be most efficient with 69% color, 60% COD, 59% TOC, 48% AOX removal.

  13. Cell uptake, intracellular distribution, fate and reactive oxygen species generation of polymer brush engineered CeO2-x NPs

    NASA Astrophysics Data System (ADS)

    Qiu, Yuan; Rojas, Elena; Murray, Richard A.; Irigoyen, Joseba; Gregurec, Danijela; Castro-Hartmann, Pablo; Fledderman, Jana; Estrela-Lopis, Irina; Donath, Edwin; Moya, Sergio E.

    2015-04-01

    Cerium Oxide nanoparticles (CeO2-x NPs) are modified with polymer brushes of negatively charged poly (3-sulfopropylmethacrylate) (PSPM) and positively charged poly (2-(methacryloyloxy)ethyl-trimethylammonium chloride) (PMETAC) by Atom Transfer Radical Polymerisation (ATRP). CeO2-x NPs are fluorescently labelled by covalently attaching Alexa Fluor® 488/Fluorescein isothiocyanate to the NP surface prior to polymerisation. Cell uptake, intracellular distribution and the impact on the generation of intracellular Reactive Oxygen Species (ROS) with respect to CeO2-x NPs are studied by means of Raman Confocal Microscopy (CRM), Transmission Electron Microscopy (TEM) and Inductively Coupled Plasma Mass Spectroscopy (ICP-MS). PSPM and PMETAC coated CeO2-x NPs show slower and less uptake compared to uncoated Brush modified NPs display a higher degree of co-localisation with cell endosomes and lysosomes after 24 h of incubation. They also show higher co-localisation with lipid bodies when compared to unmodified CeO2-x NPs. The brush coating does not prevent CeO2-x NPs from displaying antioxidant properties.Cerium Oxide nanoparticles (CeO2-x NPs) are modified with polymer brushes of negatively charged poly (3-sulfopropylmethacrylate) (PSPM) and positively charged poly (2-(methacryloyloxy)ethyl-trimethylammonium chloride) (PMETAC) by Atom Transfer Radical Polymerisation (ATRP). CeO2-x NPs are fluorescently labelled by covalently attaching Alexa Fluor® 488/Fluorescein isothiocyanate to the NP surface prior to polymerisation. Cell uptake, intracellular distribution and the impact on the generation of intracellular Reactive Oxygen Species (ROS) with respect to CeO2-x NPs are studied by means of Raman Confocal Microscopy (CRM), Transmission Electron Microscopy (TEM) and Inductively Coupled Plasma Mass Spectroscopy (ICP-MS). PSPM and PMETAC coated CeO2-x NPs show slower and less uptake compared to uncoated Brush modified NPs display a higher degree of co-localisation with cell endosomes and lysosomes after 24 h of incubation. They also show higher co-localisation with lipid bodies when compared to unmodified CeO2-x NPs. The brush coating does not prevent CeO2-x NPs from displaying antioxidant properties. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr00884k

  14. Investigation of oxygen vacancies in CeO2/Pt system with synchrotron light techniques

    NASA Astrophysics Data System (ADS)

    Braglia, L.; Bugaev, A. L.; Lomachenko, K. A.; Soldatov, A. V.; Lamberti, C.; Guda, A. A.

    2016-05-01

    A peculiar property of ceria is the ease to form oxygen vacancies, producing reactive sites or facilitating ionic diffusion. For these reasons ceria promotes catalytic activities for a number of important reactions when it is used as a support for transition metals. In our work we study the temporal evolution of oxygen vacancies formation by time-resolved XANES at Ce K- edge and XRD measurements on CeO2/Pt nanoparticles, successfully monitoring the reaction of CO oxidation.

  15. CO Oxidation mechanism on CeO2-supported Au nanoclusters

    SciTech Connect

    Kim H. Y.; Henkelman, G.

    2013-09-08

    To reveal the richer chemistry of CO oxidation by CeO2 supported Au Nanoclusters(NCs)/Nanoparticles, we design Au13 and Au12 supported on a flat and a stepped-CeO2 model (Au/CeO2) and study various kinds of CO oxidation mechanisms at the Au-CeO2 interface and the Au NC as well.

  16. WO 3/CeO 2/YSZ nanocomposite as a potential catalyst for methanol reforming

    NASA Astrophysics Data System (ADS)

    Natile, Marta Maria; Glisenti, Antonella

    A WO 3/CeO 2/YSZ nanocomposite material [W/Zr nominal atomic ratio = 0.025, Ce/Zr nominal atomic ratio = 0.020] was prepared by wet impregnation and characterized by means of X-ray photoelectron and diffuse reflectance infrared Fourier transform spectroscopic techniques, X-ray diffraction and thermal analysis. Both tungsten and cerium oxides are significantly reduced at the interface with YSZ: Ce(III), in particular, seems to be the prevailing species. The interaction of the WO 3/CeO 2/YSZ nanopowder with pyridine and CO 2 allowed to investigate the acidic/basic sites. Weak contributions at 1602, 1625 and 1647 cm -1 suggest the presence of Lewis and Brønsted acidic sites, whereas basic sites are not evidenced by the interaction with carbon dioxide. The presence of tungsten oxide causes the decrement of the acidic/basic sites, as indicated by the comparison with the results obtained on the CeO 2/YSZ support. Consistently, the interaction with methanol is mainly molecular. The oxidation of methanol was investigated both in the absence and in the presence of water. In the last case carbon dioxide starts forming from room temperature.

  17. Exposure to CeO(2) nanoparticles during flame spray process.

    PubMed

    Leppänen, Maija; Lyyränen, Jussi; Järvelä, Merja; Auvinen, Ari; Jokiniemi, Jorma; Pimenoff, Joe; Tuomi, Timo

    2012-09-01

    The use of nanotechnology in different fields is increasing rapidly. Engineered nanoparticles (ENPs) may have adverse effect on human health, but little is known about the exposure levels of ENPs at occupational settings. In this study, exposure levels of cerium oxide (CeO(2)) ENPs were measured during enclosed flame spray process used for coating and surface modification of materials. Particle number concentration, mass concentration, and morphology and composition of the ENPs were studied. The average particle number concentration varied from 4.7·10(3) to 2.1·10(5) 1/cm(3) inside the enclosure, and from 4.6·10(3) to 1.4·10(4) 1/cm(3) outside the enclosure. The average mass concentrations inside and outside the enclosure were 320 and 66 μg/m(3), respectively. A batch-type process caused significant variation in the concentrations, especially inside the enclosure. CeO(2) ENPs were mainly chainlike aggregates, consisting of spherical 20-40 nm primary particles having crystalline structure. In conclusion, enclosure of the process with efficient ventilation seemed to be an effective means to reduce the exposure to CeO(2) ENPs as expected. PMID:21770722

  18. [Catalytic degradation of naphthalene by CuO (-CeO2)/Al2O3].

    PubMed

    Zha, Jian; Zhou, Hong-Cang; He, Du-Liang; Shan, Long; Zhang, Lu; Xie, Jie

    2014-10-01

    Three catalysts CuO/Al2O3, CeO2/Al2O3 and CuO-CeO2/Al2O3 were prepared by the impregnation method. The textural and structural properties of the synthesized catalysts were characterized by N2 adsorption/desorption, SEM and XRD, and the effect of active ingredients, flow rate and reaction temperature on catalytic degradation of naphthalene (NaP) were investigated in fixed-bed reactor. The experimental results show that the prepared 18% CeO2/Al2O3 has a low catalytic activity of NaP. Nevertheless, both 18% CuO/Al2O3 and 9% CuO-9% CeO2/Al2O3 exhibit high catalytic activity whose removal efficiencies at 300°C can reach 91% and 89%, respectively. Besides, compared with CuO/Al2O3, CuO-CeO2/Al2O3 possesses a higher low-temperature activity. Furthermore, the variation of flow rates has little effect on the performance of two catalysts.

  19. [Catalytic degradation of naphthalene by CuO (-CeO2)/Al2O3].

    PubMed

    Zha, Jian; Zhou, Hong-Cang; He, Du-Liang; Shan, Long; Zhang, Lu; Xie, Jie

    2014-10-01

    Three catalysts CuO/Al2O3, CeO2/Al2O3 and CuO-CeO2/Al2O3 were prepared by the impregnation method. The textural and structural properties of the synthesized catalysts were characterized by N2 adsorption/desorption, SEM and XRD, and the effect of active ingredients, flow rate and reaction temperature on catalytic degradation of naphthalene (NaP) were investigated in fixed-bed reactor. The experimental results show that the prepared 18% CeO2/Al2O3 has a low catalytic activity of NaP. Nevertheless, both 18% CuO/Al2O3 and 9% CuO-9% CeO2/Al2O3 exhibit high catalytic activity whose removal efficiencies at 300°C can reach 91% and 89%, respectively. Besides, compared with CuO/Al2O3, CuO-CeO2/Al2O3 possesses a higher low-temperature activity. Furthermore, the variation of flow rates has little effect on the performance of two catalysts. PMID:25693411

  20. Laser-induced evaporation, reactivity and deposition of ZrO 2, CeO 2, V 2O 5 and mixed Ce-V oxides

    NASA Astrophysics Data System (ADS)

    Flamini, C.; Ciccioli, A.; Traverso, P.; Gnecco, F.; Giardini Guidoni, A.; Mele, A.

    2000-12-01

    It has been found that pulsed laser ablation has good potentiality for the deposition of ZrO2, CeO2, V2O5 and mixed Ce-V oxides which are very important materials for their application in optics and electrochromic devices. Laser induced compositional changes of thin films in the ablation and deposition processes of these materials have been explored. The effect of the oxygen gas pressure on the thin film composition has been examined. The congruency of the process has been treated on the basis of a thermal mechanism of evaporation-decomposition of the compounds. An attempt to model the processes by means of a thermodynamic approach is reported.

  1. Enhancement of photocatalytic activity of combustion-synthesized CeO2/C3N4 nanoparticles

    NASA Astrophysics Data System (ADS)

    Li, Dong-Feng; Yang, Ke; Wang, Xiao-qin; Ma, Ya-Li; Huang, Gui-Fang; Huang, Wei-Qing

    2015-09-01

    Nanocrystalline CeO2/C3N4 was synthesized via a one-step solution combustion method using urea as fuel for the first time. The effects of the molar ratio of urea to cerium chloride on the photocatalytic activity of the synthesized samples were investigated. The synthesized nanocrystalline CeO2/C3N4 shows small size and large surface exposure area. Photocatalytic degradation of methylene blue demonstrates that the synthesized nanocrystalline CeO2/C3N4 possesses enhanced photocatalytic activity. It is proposed that the enhanced photocatalytic activity might be related to the favorable morphology and structure, and the effective charge separation between C3N4 and CeO2 in the photocatalytic process.

  2. A facile method of fabricating mechanical durable anti-icing coatings based on CeO2 microparticles

    NASA Astrophysics Data System (ADS)

    Wang, Pengren; Peng, Chaoyi; Wu, Binrui; Yuan, Zhiqing; Yang, Fubiao; Zeng, Jingcheng

    2015-07-01

    Compromising between hydrophobicity and mechanical durability may be a feasible approach to fabricating usable anti-icing coatings. This work improves the contact angle of current commercial anti-icing coatings applied to wind turbine blades dramatically and keeps relatively high mechanical durability. CeO2 microparticles and diluent were mixed with fluorocarbon resin to fabricate high hydrophobic coatings on the glass fiber reinforced epoxy composite substrates. The proportion of CeO2 microparticles and diluent influences the contact angles significantly. The optimum mass ratio of fluorocarbon resin to CeO2 microparticles to diluent is 1:1.5:1, which leads to the highest contact angle close to 140°. The microscopy analysis shows that the CeO2 microparticles form nano/microscale hierarchical structure on the surface of the coatings.

  3. Mechanisms of enhanced sulfur tolerance on samarium (Sm)-doped cerium oxide (CeO2) from first principles.

    PubMed

    Lim, Dong-Hee; Kim, Hee Su; Yoon, Sung Pil; Han, Jonghee; Yoon, Chang Won; Choi, Sun Hee; Nam, Suk Woo; Ham, Hyung Chul

    2014-06-14

    The role of samarium (Sm) 4f states and Sm-perturbed O 2p states in determining the sulfur tolerance of Sm-doped CeO2 was elucidated by using the density functional theory (DFT) + U calculation. We find that the sulfur tolerance of Sm-doped CeO2 is closely related to the modification of O 2p states by the strong interaction between Sm 4f and O 2p states. In particular, the availability of unoccupied O 2p states near the Fermi level is responsible for enhancing the sulfur tolerance of Sm-doped CeO2 compared to the pure CeO2 by increasing the activity of the surface lattice oxygen toward sulfur adsorption, by weakening the interaction between Sm-O, and by increasing the migration tendency of the subsurface oxygen ion toward the surface.

  4. Photocatalytic activity of the binary composite CeO2/SiO2 for degradation of dye

    NASA Astrophysics Data System (ADS)

    Phanichphant, Sukon; Nakaruk, Auppatham; Channei, Duangdao

    2016-11-01

    In this study, CeO2 photocatalyst was modified by composite with SiO2 to increase efficiency and improve photocatalytic activity. The as-prepared SiO2 particles have been incorporated into the precursor mixture of CeO2 by homogeneous precipitation and subsequent calcination process. The phase compositions of CeO2 before and after compositing with SiO2 were identified by X-ray diffraction (XRD). The morphology and particle size of CeO2/SiO2 composite was analyzed by high resolution transmission electron microscopy (HRTEM) and field emission scanning electron microscopy (FESEM). The results showed SiO2 spheres with the particle size approximately 100-120 nm, and a uniform layer of CeO2 nanoparticles with a diameter of about 5-7 nm that were fully composite to the surfaces of SiO2. The X-ray photoelectron spectroscopy (XPS) technique was carried out in order to characterize the change in valence state and composite characteristic by shifted peaks of binding energies. The photocatalytic activity was studied through the degradation of Rhodamine B in aqueous solution under visible light exposure. The highest photocatalytic efficiency of CeO2/SiO2 composite was also obtained. To explain the high photocatalytic efficiency of CeO2/SiO2 composite, the proposed mechanism involves the high surface properties of the CeO2/SiO2 composite, as measured by Brunauer-Emmett-Teller (BET) method.

  5. Microstructural evolution of CeO2 from porous structures to clusters of nanosheet arrays assisted by gas bubbles via electrodeposition.

    PubMed

    Li, Gao-Ren; Qu, Dun-Lin; Yu, Xiao-Lan; Tong, Ye-Xiang

    2008-04-15

    Here we report the preparation of porous CeO2 and clusters of CeO2 nanosheet arrays via a simple, efficient electrochemical approach. Gas bubbles functioning as a dynamic template were utilized in our research for the synthesis of nanosheet array clusters. The Hc and Mr values of porous CeO2 are almost the same as those of CeO2 nanosheet array clusters at 5 K, and they are about 5916 Oe and 8.83 x 10(-4) emu, respectively. However, the saturation magnetization of CeO2 nanosheet array clusters is much larger than that of porous CeO2 structures. The magnetic property of the prepared CeO2 deposits may be caused by the existence of Ce(III), indicating potential interest in the nanodevices because of their electronic and magnetic properties.

  6. CeO2 nanoparticles induce no changes in phenanthrene toxicity to the soil organisms Porcellionides pruinosus and Folsomia candida.

    PubMed

    Tourinho, Paula S; Waalewijn-Kool, Pauline L; Zantkuijl, Irene; Jurkschat, Kerstin; Svendsen, Claus; Soares, Amadeu M V M; Loureiro, Susana; van Gestel, Cornelis A M

    2015-03-01

    Cerium oxide nanoparticles (CeO2 NPs) are used as diesel fuel additives to catalyze oxidation. Phenanthrene is a major component of diesel exhaust particles and one of the most common pollutants in the environment. This study aimed at determining the effect of CeO2 NPs on the toxicity of phenanthrene in Lufa 2.2 standard soil for the isopod Porcellionides pruinosus and the springtail Folsomia candida. Toxicity tests were performed in the presence of CeO2 concentrations of 10, 100 or 1000mg Ce/kg dry soil and compared with results in the absence of CeO2 NPs. CeO2 NPs had no adverse effects on isopod survival and growth or springtail survival and reproduction. For the isopods, LC50s for the effect of phenanthrene ranged from 110 to 143mg/kg dry soil, and EC50s from 17.6 to 31.6mg/kg dry soil. For the springtails, LC50s ranged between 61.5 and 88.3mg/kg dry soil and EC50s from 52.2 to 76.7mg/kg dry soil. From this study it may be concluded that CeO2 NPs have a low toxicity and do not affect toxicity of phenanthrene to isopods and springtails. PMID:25499053

  7. MnO2/CeO2 for catalytic ultrasonic decolorization of methyl orange: Process parameters and mechanisms.

    PubMed

    Zhao, He; Zhang, Guangming; Chong, Shan; Zhang, Nan; Liu, Yucai

    2015-11-01

    MnO2/CeO2 catalyst was prepared and characterized by means of Brunauer-Emmet-Teller (BET) method, X-ray diffraction (XRD) and scanning electron microscope (SEM). The characterization showed that MnO2/CeO2 had big specific surface area and MnO2 was dispersed homogeneously on the surface of CeO2. Excellent degradation efficiency of methyl orange was achieved by MnO2/CeO2 catalytic ultrasonic process. Operating parameters were studied and optimized. The optimal conditions were 10 min of ultrasonic irradiation, 1.0 g/L of catalyst dose, 2.6 of pH value and 1.3 W/ml of ultrasonic density. Under the optimal conditions, nearly 90% of methyl orange was removed. The mechanism of methyl orange degradation was further studied. The decolorization mechanism in the ultrasound-MnO2/CeO2 system was quite different with that in the ultrasound-MnO2 system. Effects of manganese and cerium in catalytic ultrasonic process were clarified. Manganese ions in solution contributed to generating hydroxyl free radical. MnO2/CeO2 catalyst strengthened the oxidation ability of ultrasound and realized complete decolorization of methyl orange.

  8. Synthesis and Characterization of CeO2 Nanoparticles via Solution Combustion Method for Photocatalytic and Antibacterial Activity Studies.

    PubMed

    Ravishankar, Thammadihalli Nanjundaiah; Ramakrishnappa, Thippeswamy; Nagaraju, Ganganagappa; Rajanaika, Hanumanaika

    2015-04-01

    CeO2 nanoparticles have been proven to be competent photocatalysts for environmental applications because of their strong redox ability, nontoxicity, long-term stability, and low cost. We have synthesized CeO2 nanoparticles via solution combustion method using ceric ammonium nitrate as an oxidizer and ethylenediaminetetraacetic acid (EDTA) as fuel at 450 °C. These nanoparticles exhibit good photocatalytic degradation and antibacterial activity. The obtained product was characterized by various techniques. X-ray diffraction data confirms a cerianite structure: a cubic phase CeO2 having crystallite size of 35 nm. The infrared spectrum shows a strong band below 700 cm(-1) due to the Ce-O-Ce stretching vibrations. The UV/Vis spectrum shows maximum absorption at 302 nm. The photoluminescence spectrum shows characteristic peaks of CeO2 nanoparticles. Scanning electron microscopy (SEM) images clearly show the presence of a porous network with a lot of voids. From transmission electron microscopy (TEM) images, it is clear that the particles are almost spherical, and the average size of the nanoparticles is found to be 42 nm. CeO2 nanoparticles exhibit photocatalytic activity against trypan blue at pH 10 in UV light, and the reaction follows pseudo first-order kinetics. Finally, CeO2 nanoparticles also reduce Cr(VI) to Cr(III) and show antibacterial activity against Pseudomonas aeruginosa.

  9. CeO2 nanoparticles induce no changes in phenanthrene toxicity to the soil organisms Porcellionides pruinosus and Folsomia candida.

    PubMed

    Tourinho, Paula S; Waalewijn-Kool, Pauline L; Zantkuijl, Irene; Jurkschat, Kerstin; Svendsen, Claus; Soares, Amadeu M V M; Loureiro, Susana; van Gestel, Cornelis A M

    2015-03-01

    Cerium oxide nanoparticles (CeO2 NPs) are used as diesel fuel additives to catalyze oxidation. Phenanthrene is a major component of diesel exhaust particles and one of the most common pollutants in the environment. This study aimed at determining the effect of CeO2 NPs on the toxicity of phenanthrene in Lufa 2.2 standard soil for the isopod Porcellionides pruinosus and the springtail Folsomia candida. Toxicity tests were performed in the presence of CeO2 concentrations of 10, 100 or 1000mg Ce/kg dry soil and compared with results in the absence of CeO2 NPs. CeO2 NPs had no adverse effects on isopod survival and growth or springtail survival and reproduction. For the isopods, LC50s for the effect of phenanthrene ranged from 110 to 143mg/kg dry soil, and EC50s from 17.6 to 31.6mg/kg dry soil. For the springtails, LC50s ranged between 61.5 and 88.3mg/kg dry soil and EC50s from 52.2 to 76.7mg/kg dry soil. From this study it may be concluded that CeO2 NPs have a low toxicity and do not affect toxicity of phenanthrene to isopods and springtails.

  10. Synthesis and Characterization of CeO2 Nanoparticles via Solution Combustion Method for Photocatalytic and Antibacterial Activity Studies

    PubMed Central

    Ravishankar, Thammadihalli Nanjundaiah; Ramakrishnappa, Thippeswamy; Nagaraju, Ganganagappa; Rajanaika, Hanumanaika

    2015-01-01

    CeO2 nanoparticles have been proven to be competent photocatalysts for environmental applications because of their strong redox ability, nontoxicity, long-term stability, and low cost. We have synthesized CeO2 nanoparticles via solution combustion method using ceric ammonium nitrate as an oxidizer and ethylenediaminetetraacetic acid (EDTA) as fuel at 450 °C. These nanoparticles exhibit good photocatalytic degradation and antibacterial activity. The obtained product was characterized by various techniques. X-ray diffraction data confirms a cerianite structure: a cubic phase CeO2 having crystallite size of 35 nm. The infrared spectrum shows a strong band below 700 cm−1 due to the Ce−O−Ce stretching vibrations. The UV/Vis spectrum shows maximum absorption at 302 nm. The photoluminescence spectrum shows characteristic peaks of CeO2 nanoparticles. Scanning electron microscopy (SEM) images clearly show the presence of a porous network with a lot of voids. From transmission electron microscopy (TEM) images, it is clear that the particles are almost spherical, and the average size of the nanoparticles is found to be 42 nm. CeO2 nanoparticles exhibit photocatalytic activity against trypan blue at pH 10 in UV light, and the reaction follows pseudo first-order kinetics. Finally, CeO2 nanoparticles also reduce CrVI to CrIII and show antibacterial activity against Pseudomonas aeruginosa. PMID:25969812

  11. Mild activation of CeO2-supported gold nanoclusters and insight into the catalytic behavior in CO oxidation.

    PubMed

    Li, Weili; Ge, Qingjie; Ma, Xiangang; Chen, Yuxiang; Zhu, Manzhou; Xu, Hengyong; Jin, Rongchao

    2016-01-28

    We report a new activation method and insight into the catalytic behavior of a CeO2-supported, atomically precise Au144(SR)60 nanocluster catalyst (where thiolate -SR = -SCH2CH2Ph) for CO oxidation. An important finding is that the activation of the catalyst is closely related to the production of active oxygen species on CeO2, rather than ligand removal of the Au144(SR)60 clusters. A mild O2 pretreatment (at 80 °C) can activate the catalyst, and the addition of reductive gases (CO or H2) can enhance the activation effects of O2 pretreatment via a redox cycle in which CO could reduce the surface of CeO2 to produce oxygen vacancies-which then adsorb and activate O2 to produce more active oxygen species. The CO/O2 pulse experiments confirm that CO is adsorbed on the cluster catalyst even with ligands on, and active oxygen species present on the surface of the pretreated catalyst reacts with CO pulses to generate CO2. The Au144(SR)60/CeO2 exhibits high CO oxidation activity at 80 °C without the removal of thiolate ligands. The surface lattice-oxygen of the support CeO2 possibly participates in the oxidation of CO over the Au144(SR)60/CeO2 catalyst.

  12. Mild activation of CeO2-supported gold nanoclusters and insight into the catalytic behavior in CO oxidation.

    PubMed

    Li, Weili; Ge, Qingjie; Ma, Xiangang; Chen, Yuxiang; Zhu, Manzhou; Xu, Hengyong; Jin, Rongchao

    2016-01-28

    We report a new activation method and insight into the catalytic behavior of a CeO2-supported, atomically precise Au144(SR)60 nanocluster catalyst (where thiolate -SR = -SCH2CH2Ph) for CO oxidation. An important finding is that the activation of the catalyst is closely related to the production of active oxygen species on CeO2, rather than ligand removal of the Au144(SR)60 clusters. A mild O2 pretreatment (at 80 °C) can activate the catalyst, and the addition of reductive gases (CO or H2) can enhance the activation effects of O2 pretreatment via a redox cycle in which CO could reduce the surface of CeO2 to produce oxygen vacancies-which then adsorb and activate O2 to produce more active oxygen species. The CO/O2 pulse experiments confirm that CO is adsorbed on the cluster catalyst even with ligands on, and active oxygen species present on the surface of the pretreated catalyst reacts with CO pulses to generate CO2. The Au144(SR)60/CeO2 exhibits high CO oxidation activity at 80 °C without the removal of thiolate ligands. The surface lattice-oxygen of the support CeO2 possibly participates in the oxidation of CO over the Au144(SR)60/CeO2 catalyst. PMID:26750474

  13. O/W/O double emulsion-assisted synthesis and catalytic properties of CeO 2 hollow microspheres

    NASA Astrophysics Data System (ADS)

    Zhang, DongEn; Xie, Qing; Wang, MingYan; Zhang, XiaoBo; Li, ShanZhong; Han, GuiQuan; Ying, AiLing; Chen, AiMei; Gong, JunYan; Tong, ZhiWei

    2010-09-01

    CeO 2 hollow microspheres have been fabricated through a simple thermal decomposition of precursor approach. The precursor with an average size of 10 μm was prepared in a reverse microemulsions containing Ce(NO 3) 3·6H 2O and CO(NH 2) 2 at 160 °C. The products were characterized by X-ray powder diffraction (XRD), transmission electron microscope (TEM), selected area electron diffraction (SAED) and scanning electron microscopy (SEM). The possible formation mechanism of hollow spheres was discussed. In addition, the CeO 2 hollow microspheres modified glassy carbon electrode exhibit excellent sensing performance towards methyl orange, which provide a new application of CeO 2 hollow spheres. The catalytic activity of CeO 2 hollow spheres on the thermal decomposition of ammonium perchlorate (AP) also was investigated by TGA. The catalytic performance of CeO 2 hollow spheres is superior to that of commercial CeO 2 powder.

  14. Fate and Phytotoxicity of CeO2 Nanoparticles on Lettuce Cultured in the Potting Soil Environment

    PubMed Central

    Gui, Xin; Zhang, Zhiyong; Liu, Shutong; Ma, Yuhui; Zhang, Peng; He, Xiao; Li, Yuanyuan; Zhang, Jing; Li, Huafen; Rui, Yukui; Liu, Liming; Cao, Weidong

    2015-01-01

    Cerium oxide nanoparticles (CeO2 NPs) have been shown to have significant interactions in plants. Previous study reported the specific-species phytotoxicity of CeO2 NPs by lettuce (Lactuca sativa), but their physiological impacts and vivo biotransformation are not yet well understood, especially in relative realistic environment. Butterhead lettuce were germinated and grown in potting soil for 30 days cultivation with treatments of 0, 50, 100, 1000 mg CeO2 NPs per kg soil. Results showed that lettuce in 100 mg·kg-1 treated groups grew significantly faster than others, but significantly increased nitrate content. The lower concentrations treatment had no impact on plant growth, compared with the control. However, the higher concentration treatment significantly deterred plant growth and biomass production. The stress response of lettuce plants, such as Superoxide dismutase (SOD), Peroxidase (POD), Malondialdehyde(MDA) activity was disrupted by 1000 mg·kg-1 CeO2 NPs treatment. In addition, the presence of Ce (III) in the roots of butterhead lettuce explained the reason of CeO2 NPs phytotoxicity. These findings demonstrate CeO2 NPs modification of nutritional quality, antioxidant defense system, the possible transfer into the food chain and biotransformation in vivo. PMID:26317617

  15. Cell uptake, intracellular distribution, fate and reactive oxygen species generation of polymer brush engineered CeO(2-x) NPs.

    PubMed

    Qiu, Yuan; Rojas, Elena; Murray, Richard A; Irigoyen, Joseba; Gregurec, Danijela; Castro-Hartmann, Pablo; Fledderman, Jana; Estrela-Lopis, Irina; Donath, Edwin; Moya, Sergio E

    2015-04-21

    Cerium Oxide nanoparticles (CeO(2-x) NPs) are modified with polymer brushes of negatively charged poly (3-sulfopropylmethacrylate) (PSPM) and positively charged poly (2-(methacryloyloxy)ethyl-trimethylammonium chloride) (PMETAC) by Atom Transfer Radical Polymerisation (ATRP). CeO(2-x) NPs are fluorescently labelled by covalently attaching Alexa Fluor® 488/Fluorescein isothiocyanate to the NP surface prior to polymerisation. Cell uptake, intracellular distribution and the impact on the generation of intracellular Reactive Oxygen Species (ROS) with respect to CeO(2-x) NPs are studied by means of Raman Confocal Microscopy (CRM), Transmission Electron Microscopy (TEM) and Inductively Coupled Plasma Mass Spectroscopy (ICP-MS). PSPM and PMETAC coated CeO(2-x) NPs show slower and less uptake compared to uncoated Brush modified NPs display a higher degree of co-localisation with cell endosomes and lysosomes after 24 h of incubation. They also show higher co-localisation with lipid bodies when compared to unmodified CeO(2-x) NPs. The brush coating does not prevent CeO(2-x) NPs from displaying antioxidant properties.

  16. Fate and Phytotoxicity of CeO2 Nanoparticles on Lettuce Cultured in the Potting Soil Environment.

    PubMed

    Gui, Xin; Zhang, Zhiyong; Liu, Shutong; Ma, Yuhui; Zhang, Peng; He, Xiao; Li, Yuanyuan; Zhang, Jing; Li, Huafen; Rui, Yukui; Liu, Liming; Cao, Weidong

    2015-01-01

    Cerium oxide nanoparticles (CeO2 NPs) have been shown to have significant interactions in plants. Previous study reported the specific-species phytotoxicity of CeO2 NPs by lettuce (Lactuca sativa), but their physiological impacts and vivo biotransformation are not yet well understood, especially in relative realistic environment. Butterhead lettuce were germinated and grown in potting soil for 30 days cultivation with treatments of 0, 50, 100, 1000 mg CeO2 NPs per kg soil. Results showed that lettuce in 100 mg·kg-1 treated groups grew significantly faster than others, but significantly increased nitrate content. The lower concentrations treatment had no impact on plant growth, compared with the control. However, the higher concentration treatment significantly deterred plant growth and biomass production. The stress response of lettuce plants, such as Superoxide dismutase (SOD), Peroxidase (POD), Malondialdehyde(MDA) activity was disrupted by 1000 mg·kg-1 CeO2 NPs treatment. In addition, the presence of Ce (III) in the roots of butterhead lettuce explained the reason of CeO2 NPs phytotoxicity. These findings demonstrate CeO2 NPs modification of nutritional quality, antioxidant defense system, the possible transfer into the food chain and biotransformation in vivo.

  17. Oxygen vacancies versus fluorine at CeO2(111): a case of mistaken identity?

    PubMed

    Kullgren, J; Wolf, M J; Castleton, C W M; Mitev, P; Briels, W J; Hermansson, K

    2014-04-18

    We propose a resolution to the puzzle presented by the surface defects observed with STM at the (111) surface facet of CeO 2 single crystals. In the seminal paper of Esch et al. [Science 309, 752 (2005)] they were identified with oxygen vacancies, but the observed behavior of these defects is inconsistent with the results of density functional theory (DFT) studies of oxygen vacancies in the literature. We resolve these inconsistencies via DFT calculations of the properties of both oxygen vacancies and fluorine impurities at CeO2(111), the latter having recently been shown to exist in high concentrations in single crystals from a widely used commercial source of such samples. We find that the simulated filled-state STM images of surface-layer oxygen vacancies and fluorine impurities are essentially identical, which would render problematic their experimental distinction by such images alone. However, we find that our theoretical results for the most stable location, mobility, and tendency to cluster, of fluorine impurities are consistent with experimental observations, in contrast to those for oxygen vacancies. Based on these results, we propose that the surface defects observed in STM experiments on CeO2 single crystals reported heretofore were not oxygen vacancies, but fluorine impurities. Since the similarity of the simulated STM images of the two defects is due primarily to the relative energies of the 2p states of oxygen and fluorine ions, this confusion might also occur for other oxides which have been either doped or contaminated with fluorine.

  18. Structure, bonding, and catalytic activity of monodisperse, transition-metal-substituted CeO2 nanoparticles.

    PubMed

    Elias, Joseph S; Risch, Marcel; Giordano, Livia; Mansour, Azzam N; Shao-Horn, Yang

    2014-12-10

    We present a simple and generalizable synthetic route toward phase-pure, monodisperse transition-metal-substituted ceria nanoparticles (M0.1Ce0.9O2-x, M = Mn, Fe, Co, Ni, Cu). The solution-based pyrolysis of a series of heterobimetallic Schiff base complexes ensures a rigorous control of the size, morphology and composition of 3 nm M0.1Ce0.9O2-x crystallites for CO oxidation catalysis and other applications. X-ray absorption spectroscopy confirms the dispersion of aliovalent (M(3+) and M(2+)) transition metal ions into the ceria matrix without the formation of any bulk transition metal oxide phases, while steady-state CO oxidation catalysis reveals an order of magnitude increase in catalytic activity with copper substitution. Density functional calculations of model slabs of these compounds confirm the stabilization of M(3+) and M(2+) in the lattice of CeO2. These results highlight the role of the host CeO2 lattice in stabilizing high oxidation states of aliovalent transition metal dopants that ordinarily would be intractable, such as Cu(3+), as well as demonstrating a rational approach to catalyst design. The current work demonstrates, for the first time, a generalizable approach for the preparation of transition-metal-substituted CeO2 for a broad range of transition metals with unparalleled synthetic control and illustrates that Cu(3+) is implicated in the mechanism for CO oxidation on CuO-CeO2 catalysts. PMID:25406101

  19. EPR of Gd3+ ion in mixed CeO2-Y2O3 nanocrystals

    NASA Astrophysics Data System (ADS)

    Aminov, L. K.; Kurkin, I. N.; Rakhmatullin, R. M.; Böttcher, R.; Pöppl, A.; Sen, S.

    2009-11-01

    This paper reports on the results of EPR studies of mixed CeO2-Y2O3 crystals (including nanosized crystals) doped by gadolinium ions. It is revealed that the width of the line corresponding to the allowed transition 1/2 ↔ -1/2 between the Kramers-conjugated states |±1/2> of the Gd3+ ion decreases with a decrease in the powder size from macrosizes to nanosizes. The observed dependence can be due to the increase in the unit cell size during grinding of the samples.

  20. Interplay of structural, optical and magnetic properties in Gd doped CeO2

    NASA Astrophysics Data System (ADS)

    Soni, S.; Kumar, Sudish; Meena, R. S.; Vats, V. S.; Dalela, S.

    2015-06-01

    In this research wok systematic investigation on the synthesis, characterization, optical and magnetic properties of Ce1-xGdxO2 (where x=0.02, 0.04, 0.06, and 0.10) synthesized using the Solid-state method. Structural, Optical and Magnetic properties of the samples were investigated by X-ray diffraction (XRD), UV-VIS-NIR spectroscopy and VSM. Fluorite structure is confirmed from the XRD measurement on Gd doped CeO2 samples. Magnetic studies showed that the Gd doped polycrystalline samples display room temperature ferromagnetism and the ferromagnetic ordering strengthens with the Gd concentration.

  1. Role of Microstructure and Surface Defects on the Dissolution Kinetics of CeO2, a UO2 Fuel Analogue.

    PubMed

    Corkhill, Claire L; Bailey, Daniel J; Tocino, Florent Y; Stennett, Martin C; Miller, James A; Provis, John L; Travis, Karl P; Hyatt, Neil C

    2016-04-27

    The release of radionuclides from spent fuel in a geological disposal facility is controlled by the surface mediated dissolution of UO2 in groundwater. In this study we investigate the influence of reactive surface sites on the dissolution of a synthesized CeO2 analogue for UO2 fuel. Dissolution was performed on the following: CeO2 annealed at high temperature, which eliminated intrinsic surface defects (point defects and dislocations); CeO2-x annealed in inert and reducing atmospheres to induce oxygen vacancy defects and on crushed CeO2 particles of different size fractions. BET surface area measurements were used as an indicator of reactive surface site concentration. Cerium stoichiometry, determined using X-ray Photoelectron Spectroscopy (XPS) and supported by X-ray Diffraction (XRD) analysis, was used to determine oxygen vacancy concentration. Upon dissolution in nitric acid medium at 90 °C, a quantifiable relationship was established between the concentration of high energy surface sites and CeO2 dissolution rate; the greater the proportion of intrinsic defects and oxygen vacancies, the higher the dissolution rate. Dissolution of oxygen vacancy-containing CeO2-x gave rise to rates that were an order of magnitude greater than for CeO2 with fewer oxygen vacancies. While enhanced solubility of Ce(3+) influenced the dissolution, it was shown that replacement of vacancy sites by oxygen significantly affected the dissolution mechanism due to changes in the lattice volume and strain upon dissolution and concurrent grain boundary decohesion. These results highlight the significant influence of defect sites and grain boundaries on the dissolution kinetics of UO2 fuel analogues and reduce uncertainty in the long term performance of spent fuel in geological disposal.

  2. Stability of engineered nanomaterials in complex aqueous matrices: Settling behaviour of CeO2 nanoparticles in natural surface waters.

    PubMed

    Van Koetsem, Frederik; Verstraete, Simon; Van der Meeren, Paul; Du Laing, Gijs

    2015-10-01

    The stability of engineered nanoparticles (ENPs) in complex aqueous matrices is a key determinant of their fate and potential toxicity towards the aquatic environment and human health. Metal oxide nanoparticles, such as CeO2 ENPs, are increasingly being incorporated into a wide range of industrial and commercial applications, which will undoubtedly result in their (unintentional) release into the environment. Hereby, the behaviour and fate of CeO2 ENPs could potentially serve as model for other nanoparticles that possess similar characteristics. The present study examined the stability and settling of CeO2 ENPs (7.3±1.4 nm) as well as Ce(3+) ions in 10 distinct natural surface waters during 7d, under stagnant and isothermal experimental conditions. Natural water samples were collected throughout Flanders (Belgium) and were thoroughly characterized. For the majority of the surface waters, a substantial depletion (>95%) of the initially added CeO2 ENPs was observed just below the liquid surface of the water samples after 7d. In all cases, the reduction was considerably higher for CeO2 ENPs than for Ce(3+) ions (<68%). A first-order kinetics model was able to describe the observed time-dependant removal of both CeO2 ENPs (R(2)≥0.998) and Ce(3+) ions (R(2)≥0.812) from the water column, at least in case notable sedimentation occurred over time. Solution-pH appeared to be a prime parameter governing nanoparticle colloidal stability. Moreover, the suspended solids (TSS) content also seemed to be an important factor affecting the settling rate and residual fraction of CeO2 ENPs as well as Ce(3+) ions in natural surface waters. Correlation results also suggest potential association and co-precipitation of CeO2 ENPs with aluminium- and iron-containing natural colloidal material. The CeO2 ENPs remained stable in dispersion in surface water characterized by a low pH, ionic strength (IS), and TSS content, indicating the eventual stability and settling behaviour of the nanoparticles was likely determined by a combination of physicochemical parameters. Finally, ionic release from the nanoparticle surface was also examined and appeared to be negligible in all of the tested natural waters.

  3. Theoretical Study of Trimethylacetic Acid Adsorption on CeO 2 (111) Surface

    DOE PAGESBeta

    Wang, Weina; Thevuthasan, S.; Wang, Wenliang; Yang, Ping

    2016-01-11

    We investigated trimethylacetic acid (TMAA) adsorption on stoichiometric and oxygen-deficient CeO2(111) surfaces using density functional theory that accounts for the on-site Coulomb interaction via a Hubbard term (DFT+U) and long-range dispersion correction. Both the molecular state and dissociative state (TMAA → TMA– + H+) were identified on stoichiometric and oxygen-deficient CeO2(111) surfaces. For the stoichiometric surface, two thermodynamically favorable configurations with adsorption energies of the order of -30 kcal/mol are identified; one is a molecule adsorption state, and the other one is a dissociative state. For the oxygen-deficient surface, dissociative states are more favorable than molecular states. Moreover, the mostmore » favorable configuration is the dissociative adsorption of TMAA with the adsorption energy of the order of -77 kcal/mol. The dissociated TMA moiety takes the position of oxygen vacancy, forming three Ce–O bonds. The signature vibrational frequencies for these thermodynamically stable structures are reported as well as their electronic structures. The effects of long-range dispersion interactions are found to be negligible for geometries but important for adsorption energies.« less

  4. Portable Enzyme-Paper Biosensors Based on Redox-Active CeO2 Nanoparticles.

    PubMed

    Karimi, A; Othman, A; Andreescu, S

    2016-01-01

    Portable, nanoparticle (NP)-enhanced enzyme sensors have emerged as powerful devices for qualitative and quantitative analysis of a variety of analytes for biomedicine, environmental applications, and pharmaceutical fields. This chapter describes a method for the fabrication of a portable, paper-based, inexpensive, robust enzyme biosensor for the detection of substrates of oxidase enzymes. The method utilizes redox-active NPs of cerium oxide (CeO2) as a sensing platform which produces color in response to H2O2 generated by the action of oxidase enzymes on their corresponding substrates. This avoids the use of peroxidases which are routinely used in conjunction with glucose oxidase. The CeO2 particles serve dual roles, as high surface area supports to anchor high loadings of the enzyme as well as a color generation reagent, and the particles are recycled multiple times for the reuse of the biosensor. These sensors are small, light, disposable, inexpensive, and they can be mass produced by standard, low-cost printing methods. All reagents needed for the analysis are embedded within the paper matrix, and sensors stored over extended periods of time without performance loss. This novel sensor is a general platform for the in-field detection of analytes that are substrates for oxidase enzymes in clinical, food, and environmental samples. PMID:27112400

  5. Dual-functional CeO2:Eu3+ nanocrystals for performance-enhanced dye-sensitized solar cells.

    PubMed

    Roh, Jongmin; Hwang, Sun Hye; Jang, Jyongsik

    2014-11-26

    Single-crystalline, octahedral CeO2:Eu3+ nanocrystals, successfully prepared using a simple hydrothermal method, were investigated to determine their photovoltaic properties in an effort to enhance the light-harvesting efficiency of dye-sensitized solar cells (DSSCs). The size of the CeO2:Eu3+ nanocrystals (300-400 nm), as well as their mirrorlike facets, significantly improved the diffuse reflectance of visible light. Excitation of the CeO2:Eu3+ nanocrystal with 330 nm ultraviolet light was re-emitted via downconversion photoluminescence (PL) from 570 to 672 nm, corresponding to the 5D0→7FJ transition in the Eu3+ ions. Downconversion PL was dominant at 590 nm and had a maximum intensity for 1 mol % Eu3+. The CeO2:Eu3+ nanocrystal-based DSSCs exhibited a power conversion efficiency of 8.36%, an increase of 14%, compared with conventional TiO2 nanoparticle-based DSSCs, because of the strong light-scattering and downconversion PL of the CeO2:Eu3+ nanocrystals.

  6. Infiltration of Metal Substrates with Nanostructured CeO2 by a Room-Temperature Wet Process.

    PubMed

    Presto, Sabrina; Viviani, Massimo

    2015-05-01

    A room-temperature infiltration procedure for the deposition of CeO2 nanopowders on Ni-based foams employing stable CeO2 suspensions in water has been developed. It consists of a two-steps dipping process, the first in nanopowder suspension at pH 6.5 followed by further dipping into a NH3OH solution at pH 12. The pH shift represents a key factor to improve the homogeneity and dispersion of infiltrated powder by avoiding coalescence during the drying step. Water-based suspensions have been prepared starting from a commercial nanostructured CeO2. Powder was characterized by X-ray diffraction, particle size and specific surface area measurements, transmission electron microscopy. Stability of suspensions was studied by zeta potential measurements at low concentration, while sedimentation tests were carried out on highly concentrated suspensions as a function of pH, CeO2 amount and surfactant presence. Effect of CeO2 concentration, surfactant addition, pH value, substrate composition and microstructure were taken in account. Under best conditions, very homogeneous infiltrations could be obtained without any preferential orientation or agglomerates. Thermal stability of the composites infiltrated materials was also tested. The technique seems to be very promising in advanced nanostructured decorations and coating preparation.

  7. Effects of CeO2 Support Facets on VOx/CeO2 Catalysts in Oxidative Dehydrogenation of Methanol

    SciTech Connect

    Li, Yan; Wei, Zhehao; Gao, Feng; Kovarik, Libor; Peden, Charles HF; Wang, Yong

    2014-05-13

    CeO2 supports with dominating facets, i.e., low index (100), (110) and (111) facets, are prepared. The facet effects on the structure and catalytic performance of supported vanadium oxide catalysts are investigated using oxidative dehydrogenation of methanol as a model reaction. In the presence of mixed facets, Infrared and Raman characterizations demonstrate that surface vanadia species preferentially deposit on CeO2 (100) facets, presumably because of its higher surface energy. At the same surface vanadium densities, VOx species on (100) facets show better dispersion, followed by (110) and (111) facets. The VOx species on CeO2 nanorods with (110) and (100) facets display higher activity and lower apparent activation energies compared to that on CeO2 nanopolyhedras with dominating (111) facets and CeO2 nanocubes with dominating (100) facets. The higher activity for VOx/CeO2(110) might be related to the more abundant oxygen vacancies present on the (110) facets, evidenced from Raman spectroscopic measurements.

  8. Influence of two types of organic matter on interaction of CeO2 nanoparticles with plants in hydroponic culture.

    PubMed

    Schwabe, Franziska; Schulin, Rainer; Limbach, Ludwig K; Stark, Wendelin; Bürge, Diane; Nowack, Bernd

    2013-04-01

    An important aspect in risk assessment of nanoparticles (NPs) is to understand their environmental interactions. We used hydroponic plant cultures to study nanoparticle-plant-root interaction and translocation and exposed wheat and pumpkin to suspensions of uncoated CeO2-NP for 8d (primary particle size 17-100 nm, 100 mg L(-1)) in the absence and presence of fulvic acid (FA) and gum arabic (GA) as representatives of different types of natural organic matter. The behavior of CeO2-NPs in the hydroponic solution was monitored regarding agglomeration, sedimentation, particle size distribution, surface charge, amounts of root association, and translocation into shoots. NP-dispersions were stable over 8d in the presence of FA or GA, but with growing plants, changes in pH, particle agglomeration rate, and hydrodynamic diameter were observed. None of the plants exhibited reduced growth or any toxic response during the experiment. We found that CeO2-NPs translocated into pumpkin shoots, whereas this did not occur in wheat plants. The presence of FA and GA affected the amount of CeO2 associated with roots (pure>FA>GA) but did not affect the translocation factor. Additionally, we could confirm via TEM and SEM that CeO2-NPs adhered strongly to root surfaces of both plant species.

  9. Transformation of pristine and citrate-functionalized CeO2 nanoparticles in a laboratory-scale activated sludge reactor.

    PubMed

    Barton, Lauren E; Auffan, Melanie; Bertrand, Marie; Barakat, Mohamed; Santaella, Catherine; Masion, Armand; Borschneck, Daniel; Olivi, Luca; Roche, Nicolas; Wiesner, Mark R; Bottero, Jean-Yves

    2014-07-01

    Engineered nanomaterials (ENMs) are used to enhance the properties of many manufactured products and technologies. Increased use of ENMs will inevitably lead to their release into the environment. An important route of exposure is through the waste stream, where ENMs will enter wastewater treatment plants (WWTPs), undergo transformations, and be discharged with treated effluent or biosolids. To better understand the fate of a common ENM in WWTPs, experiments with laboratory-scale activated sludge reactors and pristine and citrate-functionalized CeO2 nanoparticles (NPs) were conducted. Greater than 90% of the CeO2 introduced was observed to associate with biosolids. This association was accompanied by reduction of the Ce(IV) NPs to Ce(III). After 5 weeks in the reactor, 44 ± 4% reduction was observed for the pristine NPs and 31 ± 3% for the citrate-functionalized NPs, illustrating surface functionality dependence. Thermodynamic arguments suggest that the likely Ce(III) phase generated would be Ce2S3. This study indicates that the majority of CeO2 NPs (>90% by mass) entering WWTPs will be associated with the solid phase, and a significant portion will be present as Ce(III). At maximum, 10% of the CeO2 will remain in the effluent and be discharged as a Ce(IV) phase, governed by cerianite (CeO2).

  10. The Interaction of Carbon Monoxide with Rhodium on Potassium-Modified CeO2(111)

    DOE PAGESBeta

    Mullins, David R.

    2016-02-03

    The adsorption and reactions of CO adsorbed on Rh particles deposited on K-covered CeO2(111) were studied by temperature programmed desorption and photoelectron spectroscopy. K deposited on CeO2(111) forms a KOX over-layer by extracting O from the ceria and partially reducing some of the Ce4+ to Ce3+. CO does not adsorb on the KOX / CeO2-X(111) surface in the absence of Rh particles. CO adsorbed on Rh / K / CeO2(111) adsorbs molecularly on the Rh at 200 K. As the surface is heated the CO spills-over and reacts with the KOX to form carbonate. The carbonate decomposes at elevated temperaturemore » to produce CO and CO2. The carbonate stabilizes the KOX so that K desorbs at a higher temperature than it would in the absence of CO. When the Rh and K deposition are reversed so that K is deposited on both the Rh and the CeO2(111), CO adsorbs as CO2- at 200 K. The CO2- decomposes below 350 K to produce gas phase CO and adsorbed CO32- and CO. The CO is stabilized by the K on the Rh and desorbs above 540 K. The carbonate decomposes into gas phase CO and CO2.« less

  11. An in vivo and in vitro toxicological characterization of realistic nanoscale CeO2 inhalation exposures

    PubMed Central

    Demokritou, Philip; Gass, Samuel; Pyrgiotakis, Georgios; Cohen, Joel M.; Goldsmith, William; McKinney, Walt; Frazer, David; Ma, Jane; Schwegler-Berry, Diane; Brain, Joseph; Castranova, Vincent

    2015-01-01

    Nanoscale CeO2 is increasingly used for industrial and commercial applications, including catalysis, UV-shielding, and as an additive in various nanocomposites. Because of its increasing potential for consumer and occupational exposures, a comprehensive toxicological characterization of this nanomaterial is needed. Preliminary results from intratracheal instillation studies in rats point to cytoxicity and inflammation, though these studies may not accurately use realistic nanoscale exposure profiles. In contrast, published in vitro cellular studies have reported limited toxicological outcomes for the case of nano-ceria. Here, we present an integrative study evaluating the toxicity of nanoscale CeO2 both in vitro, using the A549 lung epithelial cell line, and in vivo using an intact rat model. Realistic nano-ceria exposure atmospheres were generated using the Harvard Versatile Engineered Nanomaterial Generation System (VENGES), and rats were exposed via inhalation. Finally, the use of a nanothin amorphous SiO2 encapsulation coating as a means of mitigating CeO2 toxicity was assessed. Results from the inhalation experiments show lung injury and inflammation with increased PMN and LDH levels in the bronchoalveolar lavage fluid of the CeO2 exposed rats. Moreover, exposure to SiO2-coated CeO2 did not induce any pulmonary toxicity to the animals, representing clear evidence for the safe by design SiO2-encapsualtion concept. PMID:23061914

  12. Different synthesis protocols for Co3O4 -CeO2 catalysts--part 1: influence on the morphology on the nanoscale.

    PubMed

    Yang, Jingxia; Lukashuk, Liliana; Akbarzadeh, Johanna; Stöger-Pollach, Michael; Peterlik, Herwig; Föttinger, Karin; Rupprechter, Günther; Schubert, Ulrich

    2015-01-01

    Co3 O4 -modified CeO2 (Co/Ce 1:4) was prepared by a combination of sol-gel processing and solvothermal treatment. The distribution of Co was controlled by means of the synthesis protocol to yield three different morphologies, namely, Co3 O4 nanoparticles located on the surface of CeO2 particles, coexistent Co3 O4 and CeO2 nanoparticles, or Co oxide structures homogeneously distributed within CeO2 . The effect of the different morphologies on the properties of Co3 O4 -CeO2 was investigated with regard to the crystallite phase(s), particle size, surface area, and catalytic activity for CO oxidation. The material with Co3 O4 nanoparticles finely dispersed on the surface of CeO2 particles had the highest catalytic activity.

  13. A comparative study of CeO2-Al2O3 support prepared with different methods and its application on MoO3/CeO2-Al2O3 catalyst for sulfur-resistant methanation

    NASA Astrophysics Data System (ADS)

    Jiang, Minhong; Wang, Baowei; Yao, Yuqin; Li, Zhenhua; Ma, Xinbin; Qin, Shaodong; Sun, Qi

    2013-11-01

    The CeO2-Al2O3 supports prepared with impregnation (IM), deposition precipitation (DP), and solution combustion (SC) methods for MoO3/CeO2-Al2O3 catalyst were investigated in the sulfur-resistant methanation. The supports and catalysts were characterized by N2-physisorption, transmission electron microscopy (TEM), X-ray diffraction (XRD), Raman spectroscopy (RS), and temperature-programmed reduction (TPR). The N2-physisorption results indicated that the DP method was favorable for obtaining better textural properties. The TEM and RS results suggested that there is a CeO2 layer on the surface of the support prepared with DP method. This CeO2 layer not only prevented the interaction between MoO3 and γ-Al2O3 to form Al2(MoO4)3 species, but also improved the dispersion of MoO3 in the catalyst. Accordingly, the catalysts whose supports were prepared with DP method exhibited the best catalytic activity. The catalysts whose supports were prepared with SC method had the worst catalytic activity. This was caused by the formation of Al2(MoO4)3 and crystalline MoO3. Additionally, the CeO2 layer resulted in the instability of catalysts in reaction process. The increasing of calcination temperature of supports reduced the catalytic activity of all catalysts. The decrease extent of the catalysts whose supports were prepared with DP method was the lowest as the CeO2 layer prevented the interaction between MoO3 and γ-Al2O3.

  14. Facile and Mild Strategy to Construct Mesoporous CeO2-CuO Nanorods with Enhanced Catalytic Activity toward CO Oxidation.

    PubMed

    Chen, Guozhu; Xu, Qihui; Yang, Ying; Li, Cuncheng; Huang, Taizhong; Sun, Guoxin; Zhang, Shuxiang; Ma, Dongling; Li, Xu

    2015-10-28

    CeO2-CuO nanorods with mesoporous structure were synthesized by a facile and mild strategy, which involves an interfacial reaction between Ce2(SO4)3 precursor and NaOH ethanol solution at room temperature to obtain mesoporous CeO2 nanorods, followed by a solvothermal treatment of as-prepared CeO2 and Cu(CH3COO)2. Upon solvothermal treatment, CuO species is highly dispersed onto the CeO2 nanorod surface to form CeO2-CuO composites, which still maintain the mesoporous feature. A preliminary CO catalytic oxidation study demonstrated that the CeO2-CuO samples exhibited strikingly high catalytic activity, and a high CO conversion rate was observed without obvious loss in activity even after thermal treatment at a high temperature of 500 °C. Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and hydrogen temperature-programmed reduction (H2-TPR) analysis revealed that there is a strong interaction between CeO2 and CuO. Moreover, it was found that the introduction of CuO species into CeO2 generates oxygen vacancies, which is highly likely to be responsible for high catalytic activity toward CO oxidation of the mesoporous CeO2-CuO nanorods.

  15. Facile preparation of well-dispersed CeO2-ZnO composite hollow microspheres with enhanced catalytic activity for CO oxidation.

    PubMed

    Xie, Qingshui; Zhao, Yue; Guo, Huizhang; Lu, Aolin; Zhang, Xiangxin; Wang, Laisen; Chen, Ming-Shu; Peng, Dong-Liang

    2014-01-01

    In this article, well-dispersed CeO2-ZnO composite hollow microspheres have been fabricated through a simple chemical reaction followed by annealing treatment. Amorphous zinc-cerium citrate hollow microspheres were first synthesized by dispersing zinc citrate hollow microspheres into cerium nitrate solution and then aging at room temperature for 1 h. By calcining the as-produced zinc-cerium citrate hollow microspheres at 500 °C for 2 h, CeO2-ZnO composite hollow microspheres with homogeneous composition distribution could be harvested for the first time. The resulting CeO2-ZnO composite hollow microspheres exhibit enhanced activity for CO oxidation compared with CeO2 and ZnO, which is due to well-dispersed small CeO2 particles on the surface of ZnO hollow microspheres and strong interaction between CeO2 and ZnO. Moreover, when Au nanoparticles are deposited on the surface of the CeO2-ZnO composite hollow microspheres, the full CO conversion temperature of the as-produced 1.0 wt % Au-CeO2-ZnO composites reduces from 300 to 60 °C in comparison with CeO2-ZnO composites. The significantly improved catalytic activity may be ascribed to the strong synergistic interplay between Au nanoparticles and CeO2-ZnO composites.

  16. ARTICLES: Synthesis of Biomorphic ZrO2-CeO2 Nanostructures by Silkworm Silk Template

    NASA Astrophysics Data System (ADS)

    Zhang, Zong-jian; Li, Jia; Sun, Fu-sheng; Dickon, H. L. Ng; Luen Kwong, Fung

    2010-06-01

    A simple and green technique has been developed to prepare hierarchical biomorphic ZrO2-CeO2, using silkworm silk as the template. Different from traditional immersion technics, the whole synthesis process depends more on the restriction or direction functions of the silkworm silk template. The analytic results showed that ZrO2-CeO2 exhibited a well-crystallized hierarchically interwoven hollow fiber structure with 16-28 μm in diameter. The grain size of the sample calcined at 800 °C was about 14 nm. Consequently, the interwoven meshwork at three dimensions is formed due to the direction of biotemplate. The action mechanism is summarily discussed here. It may bring the biomorphic ZrO2-CeO2 nanomaterials with hierarchical interwoven structures to more applications, such as catalysts.

  17. Stability and migration of charged oxygen interstitials in ThO2 and CeO2

    SciTech Connect

    Xiao, Haiyan; Zhang, Yanwen; Weber, William J

    2013-01-01

    Density functional theory calculations have been carried out to study the stability and migration of charged oxygen interstitial in ThO2 and CeO2. The calculations demonstrate that the oxygen interstitial is likely to lose electrons under p-type conditions and gain electrons under n-type conditions. Neutral (Osplit0) and singly positive (Osplit+) O-O<110> split interstitials, and doubly negative octahedral (Oocta.2-) oxygen interstitial are found to be the lowest-energy configurations within a certain Fermi energy range. In both oxides, the Osplit+ is the most mobile, and the migration energies of the split oxygen interstitials in ThO2 are lower than in CeO2, indicating high oxygen interstitial mobility in ThO2 than in CeO2.

  18. Mild activation of CeO2-supported gold nanoclusters and insight into the catalytic behavior in CO oxidation

    NASA Astrophysics Data System (ADS)

    Li, Weili; Ge, Qingjie; Ma, Xiangang; Chen, Yuxiang; Zhu, Manzhou; Xu, Hengyong; Jin, Rongchao

    2016-01-01

    We report a new activation method and insight into the catalytic behavior of a CeO2-supported, atomically precise Au144(SR)60 nanocluster catalyst (where thiolate -SR = -SCH2CH2Ph) for CO oxidation. An important finding is that the activation of the catalyst is closely related to the production of active oxygen species on CeO2, rather than ligand removal of the Au144(SR)60 clusters. A mild O2 pretreatment (at 80 °C) can activate the catalyst, and the addition of reductive gases (CO or H2) can enhance the activation effects of O2 pretreatment via a redox cycle in which CO could reduce the surface of CeO2 to produce oxygen vacancies--which then adsorb and activate O2 to produce more active oxygen species. The CO/O2 pulse experiments confirm that CO is adsorbed on the cluster catalyst even with ligands on, and active oxygen species present on the surface of the pretreated catalyst reacts with CO pulses to generate CO2. The Au144(SR)60/CeO2 exhibits high CO oxidation activity at 80 °C without the removal of thiolate ligands. The surface lattice-oxygen of the support CeO2 possibly participates in the oxidation of CO over the Au144(SR)60/CeO2 catalyst.We report a new activation method and insight into the catalytic behavior of a CeO2-supported, atomically precise Au144(SR)60 nanocluster catalyst (where thiolate -SR = -SCH2CH2Ph) for CO oxidation. An important finding is that the activation of the catalyst is closely related to the production of active oxygen species on CeO2, rather than ligand removal of the Au144(SR)60 clusters. A mild O2 pretreatment (at 80 °C) can activate the catalyst, and the addition of reductive gases (CO or H2) can enhance the activation effects of O2 pretreatment via a redox cycle in which CO could reduce the surface of CeO2 to produce oxygen vacancies--which then adsorb and activate O2 to produce more active oxygen species. The CO/O2 pulse experiments confirm that CO is adsorbed on the cluster catalyst even with ligands on, and active oxygen species present on the surface of the pretreated catalyst reacts with CO pulses to generate CO2. The Au144(SR)60/CeO2 exhibits high CO oxidation activity at 80 °C without the removal of thiolate ligands. The surface lattice-oxygen of the support CeO2 possibly participates in the oxidation of CO over the Au144(SR)60/CeO2 catalyst. Electronic supplementary information (ESI) available. See DOI: 10.1039/C5NR07498C

  19. Controllable synthesis of CeO2/g-C3N4 composites and their applications in the environment.

    PubMed

    She, Xiaojie; Xu, Hui; Wang, Hefei; Xia, Jiexiang; Song, Yanhua; Yan, Jia; Xu, Yuanguo; Zhang, Qi; Du, Daolin; Li, Huaming

    2015-04-21

    This research has developed a photocatalytic reactor that includes circulating water, light, and a temperature control system. CeO2/g-C3N4 composites with high photocatalytic activity and stability were synthesized by a simple and facile hydrothermal method. The obtained photocatalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). It was found that in the CeO2/g-C3N4 composites, the CeO2 nanoparticles were homogeneously cubic in shape (from 3 to 10 nm) and were evenly dispersed on the surface of the g-C3N4. At constant temperature (30 °C), 5% CeO2/g-C3N4 photocatalyst showed the best photocatalytic activity for degrading organic dye methylene blue (MB) under visible light irradiation. The photocatalytic reaction for degrading MB followed first-order kinetics and 5% CeO2/g-C3N4 exhibited a higher apparent rate of 1.2686 min(-1), 7.8 times higher than that of the pure g-C3N4 (0.1621 min(-1)). In addition, it was found that 5% CeO2/g-C3N4 had a new property that it could be used as a sensor for the determination of trace amounts of Cu(2+). Such unique design and one-step synthesis, with an exposed high-activity surface, are important for both technical applications and theoretical investigations.

  20. Interfacial interactions of semiconductor with graphene and reduced graphene oxide: CeO2 as a case study.

    PubMed

    Xu, Liang; Huang, Wei-Qing; Wang, Ling-Ling; Huang, Gui-Fang

    2014-11-26

    The pursuit of superb building blocks of light harvesting systems has stimulated increasing efforts to develop graphene (GR)-based semiconductor composites for solar cells and photocatalysts. One critical issue for GR-based composites is understanding the interaction between their components, a problem that remains unresolved after intense experimental investigation. Here, we use cerium dioxide (CeO2) as a model semiconductor to systematically explore the interaction of semiconductor with GR and reduced graphene oxide (RGO) with large-scale ab initio calculations. The amount of charge transferred at the interfaces increases with the concentration of O atoms, demonstrating that the interaction between CeO2 and RGO is much stronger than that between CeO2 and GR due to the decrease of the average equilibrium distance between the interfaces. The stronger interaction between semiconductor and RGO is expected to be general, as evidenced by the results of two paradigms of TiO2 and Ag3PO4 coupled with RGO. The interfacial interaction can tune the band structure: the CeO2(111)/GR interface is a type-I heterojunction, while a type-II staggered band alignment exists between the CeO2(111) surface and RGO. The smaller band gap, type-II heterojunction, and negatively charged O atoms on the RGO as active sites are responsible for the enhanced photoactivity of CeO2/RGO composite. These findings can rationalize the available experimental reports and enrich our understanding of the interaction of GR-based composites for developing high-performance photocatalysts and solar cells.

  1. Effect of Dysprosia Additive on the Consolidation of CeO2 by Spark Plasma Sintering

    SciTech Connect

    K. Choi; R. E. Reavis; D. D. Osterberg; B. J. Jacques; D. P. Butt; R. D. Mariani; D. E. Burkes; Z. A. Munir

    2012-05-01

    The influence of dysprosia addition on the sintering and resulting microstructure of nano-grained CeO2 ceramics was investigated as functions of the spark plasma sintering (SPS) parameters. The addition of Dy2O3 (forming a solid solution) resulted in an increase in relative density and a decrease in grain size. The relative density of samples with Dy2O3 content of 6 and 10 mol% was over 95% when sintered at 1050 C under 500 MPa for holding times as short as 5 minutes. The application of high pressure facilitated the consolidation to relatively high densities with minimal grain growth. Heating rate and holding time, however, had insignificant effect on density but a measurable effect on grain size.

  2. Atomic structures and oxygen dynamics of CeO2 grain boundaries

    NASA Astrophysics Data System (ADS)

    Feng, Bin; Sugiyama, Issei; Hojo, Hajime; Ohta, Hiromichi; Shibata, Naoya; Ikuhara, Yuichi

    2016-02-01

    Material performance is significantly governed by grain boundaries (GBs), a typical crystal defects inside, which often exhibit unique properties due to the structural and chemical inhomogeneity. Here, it is reported direct atomic scale evidence that oxygen vacancies formed in the GBs can modify the local surface oxygen dynamics in CeO2, a key material for fuel cells. The atomic structures and oxygen vacancy concentrations in individual GBs are obtained by electron microscopy and theoretical calculations at atomic scale. Meanwhile, local GB oxygen reduction reactivity is measured by electrochemical strain microscopy. By combining these techniques, it is demonstrated that the GB electrochemical activities are affected by the oxygen vacancy concentrations, which is, on the other hand, determined by the local structural distortions at the GB core region. These results provide critical understanding of GB properties down to atomic scale, and new perspectives on the development strategies of high performance electrochemical devices for solid oxide fuel cells.

  3. Enhanced spectral emissivity of CeO2 coating with cauliflower-like microstructure

    NASA Astrophysics Data System (ADS)

    Huang, Jianping; Li, Yibin; He, Xiaodong; Song, Guangping; Fan, Chenglei; Sun, Yue; Fei, Weidong; Du, Shanyi

    2012-10-01

    Cerium dioxide is a transparent oxide with high refractive index (from 1.6 to 2.5 at 633 nm) in the visible and near-IR spectral regions. However, little attention has been paid to its optical property in mid-IR (2.5-25 μm). Here we report that the cauliflower-like microstructured CeO2 coating deposited by electron beam physical vapor deposition technique shows high emissivity up to 0.9 at 873 K in the mid-IR spectral region. The high emissivity is attributed to the coupling between free propagating waves and space-variant polarizations caused by the cauliflower-like microstructure. This high emissivity coating shows a potential application in high temperature components.

  4. Atomic structures and oxygen dynamics of CeO2 grain boundaries

    PubMed Central

    Feng, Bin; Sugiyama, Issei; Hojo, Hajime; Ohta, Hiromichi; Shibata, Naoya; Ikuhara, Yuichi

    2016-01-01

    Material performance is significantly governed by grain boundaries (GBs), a typical crystal defects inside, which often exhibit unique properties due to the structural and chemical inhomogeneity. Here, it is reported direct atomic scale evidence that oxygen vacancies formed in the GBs can modify the local surface oxygen dynamics in CeO2, a key material for fuel cells. The atomic structures and oxygen vacancy concentrations in individual GBs are obtained by electron microscopy and theoretical calculations at atomic scale. Meanwhile, local GB oxygen reduction reactivity is measured by electrochemical strain microscopy. By combining these techniques, it is demonstrated that the GB electrochemical activities are affected by the oxygen vacancy concentrations, which is, on the other hand, determined by the local structural distortions at the GB core region. These results provide critical understanding of GB properties down to atomic scale, and new perspectives on the development strategies of high performance electrochemical devices for solid oxide fuel cells. PMID:26838958

  5. Energetics of mixing in ThO 2-CeO 2 fluorite solid solutions

    NASA Astrophysics Data System (ADS)

    Shvareva, Tatiana Y.; Alexandrov, Vitaly; Asta, Mark; Navrotsky, Alexandra

    2011-12-01

    Mixing enthalpies (Δ Hmix) of ThO 2-CeO 2 solid solutions with respect to cubic fluorite ThO 2 and CeO 2 have been measured by high temperature oxide melt solution calorimetry. The system shows a slightly positive mixing enthalpy, with a maximum value of Δ Hmix = 3.7 ± 2.5 kJ/mol at 50% Ce/(Ce + Th). Based on the regular-solution model, with an interaction parameter of 15.1 ± 2.2 kJ/mol fit to the measured data, the phase diagram is predicted to feature a miscibility gap with a calculated critical temperature of 908 ± 132 K. The results are complemented by density-functional-theory and Monte-Carlo calculations, which provide positive mixing enthalpies and a miscibility-gap phase diagram, in qualitative agreement with calorimetric results. The calculations suggest small effects of short-range order (clustering) on the mixing enthalpy above the miscibility gap. The calculated values of Δ Hmix are within the error bars of the measured values, but consistently smaller in magnitude. An analysis of the calculated results indicates that the dominant contribution to the mixing enthalpy arises from the elastic energy associated with cation size mismatch, allowing predictions of the behavior in ThO 2-UO 2 and ThO 2-PuO 2 systems. The analysis also suggests that the slightly smaller values of the computed Δ Hmix relative to experiment can be attributed to an underestimation of the magnitude of the elastic moduli in the calculations.

  6. NO reduction by CO over CuO supported on CeO2-doped TiO2: the effect of the amount of a few CeO2.

    PubMed

    Deng, Changshun; Li, Bin; Dong, Lihui; Zhang, Feiyue; Fan, Minguang; Jin, Guangzhou; Gao, Junbin; Gao, Liwen; Zhang, Fei; Zhou, Xinpeng

    2015-06-28

    This work is mainly focused on the investigation of the influence of the amount of a few CeO2 on the physicochemical and catalytic properties of CeO2-doped TiO2 catalysts for NO reduction by a CO model reaction. The obtained samples were characterized by means of XRD, N2-physisorption (BET), LRS, UV-vis DRS, XPS, (O2, CO, and NO)-TPD, H2-TPR, in situ FT-IR, and a NO + CO model reaction. These results indicate that a small quantity of CeO2 doping into the TiO2 support will cause an obvious change in the properties of the catalyst and the TC-60 : 1 (the TiO2/CeO2 molar ratio is 60 : 1) support exhibits the most extent of lattice expansion, which indicates that the band lengths of Ce-O-Ti are longer than other TC (the solid solution of TiO2 and CeO2) samples, probably contributing to larger structural distortion and disorder, more defects and oxygen vacancies. Copper oxide species supported on TC supports are much easier to be reduced than those supported on the pure TiO2 and CeO2 surface-modified TiO2 supports. Furthermore, the Cu/TC-60 : 1 catalyst shows the highest activity and selectivity due to more oxygen vacancies, higher mobility of surface and lattice oxygen at lower temperature (which contributes to the regeneration of oxygen vacancies, and the best reducing ability), the most content of Cu(+), and the strongest synergistic effect between Ti(3+), Ce(3+) and Cu(+). On the other hand, the CeO2 doping into TiO2 promotes the formation of a Cu(+)/Cu(0) redox cycle at high temperatures, which has a crucial effect on N2O reduction. Finally, in order to further understand the nature of the catalytic performances of these samples, taking the Cu/TC-60 : 1 catalyst as an example, a possible reaction mechanism is tentatively proposed.

  7. High Thermal Stability of La2O3- and CeO2-Stabilized Tetragonal ZrO2.

    PubMed

    Wang, Shichao; Xie, Hong; Lin, Yuyuan; Poeppelmeier, Kenneth R; Li, Tao; Winans, Randall E; Cui, Yanran; Ribeiro, Fabio H; Canlas, Christian P; Elam, Jeffrey W; Zhang, Hongbo; Marshall, Christopher L

    2016-03-01

    Catalyst support materials of tetragonal ZrO2, stabilized by either La2O3 (La2O3-ZrO2) or CeO2 (CeO2-ZrO2), were synthesized under hydrothermal conditions at 200 °C with NH4OH or tetramethylammonium hydroxide as the mineralizer. From in situ synchrotron powder X-ray diffraction and small-angle X-ray scattering measurements, the calcined La2O3-ZrO2 and CeO2-ZrO2 supports were nonporous nanocrystallites that exhibited rectangular shapes with a thermal stability of up to 1000 °C in air. These supports had an average size of ∼ 10 nm and a surface area of 59-97 m(2)/g. The catalysts Pt/La2O3-ZrO2 and Pt/CeO2-ZrO2 were prepared by using atomic layer deposition with varying Pt loadings from 6.3 to 12.4 wt %. Monodispersed Pt nanoparticles of ∼ 3 nm were obtained for these catalysts. The incorporation of La2O3 and CeO2 into the t-ZrO2 structure did not affect the nature of the active sites for the Pt/ZrO2 catalysts for the water-gas shift reaction.

  8. Facile electrochemical synthesis of CeO2@Ag@CdS nanotube arrays with enhanced photoelectrochemical water splitting performance.

    PubMed

    Zhao, Mi; Li, Haohua; Shen, Xiaoping; Ji, Zhenyuan; Xu, Keqiang

    2015-12-14

    In this work, for the first time, three-component CeO2@Ag@CdS heterostructured nanotube arrays with remarkable photoelectrochemical (PEC) performance have been synthesized by an electrodeposition method. In this configuration, the modification with Ag nanoparticles can significantly strengthen light absorption and provide an interior direct pathway to facilitate the separation and transport of photogenerated carriers. Therefore, the CeO2@Ag@CdS heterostructured nanotubes generate a remarkable photocurrent density of 2.14 mA cm(-2) at a potential of -0.2 V (vs. Ag/AgCl), which is 9.8 and 2.4 times higher than that of the two-component CeO2@Ag system (0.218 mA cm(-2)) and the CeO2@CdS system (0.879 mA cm(-2)), respectively. It also gives efficiency as high as 69% around 360 nm in the incident photon to electron conversion efficiency (IPCE) spectrum. Moreover, the stability of the photoelectrode was tested over 16 min. Furthermore, these results provide a valuable insight for the further development of such materials for PEC water splitting.

  9. Mg Doping Induced Effects on Structural, Optical, and Electrical Properties as Well as Cytotoxicity of CeO2 Nanostructures

    NASA Astrophysics Data System (ADS)

    Iqbal, Javed; Jan, Tariq; Awan, M. S.; Naqvi, Sajjad Haider; Badshah, Noor; ullah, Asmat; Abbas, Fazzal

    2016-04-01

    Here, Mg x Ce1- x O2 (where x = 0, 0.01, 0.02, 0.03, 0.04, and 0.05) nanostructures have been successfully synthesized by using a simple, easy, and cost-effective soft chemical method. X-ray diffraction (XRD) patterns substantiate the single-phase formation of a CeO2 cubic fluorite structure for all samples. Infrared spectroscopy results depict the presence of peaks only related to Ce-O bonding, which confirms the XRD results. It has been observed via ultraviolet (UV)-visible spectroscopy that Mg doping has tuned the optical band gap of CeO2 significantly. The electrical conductivity of CeO2 nanostructures has been found to increase with Mg doping, which is attributed to enhancement in carrier concentration due to the different valance states of dopant and host ions. Selective cytotoxic behavior of Mg x Ce1- x O2 nanostructures has been determined for neuroblastoma (SH-SY5Y) cancerous and HEK-293 healthy cells. Both doped and undoped CeO2 nanostructures have been found to be toxic for cancer cells and safe toward healthy cells. This selective toxic behavior of the synthesized nanostructures has been assigned to the different levels of reactive oxygen species (ROS) generation in different types of cells. This makes the synthesized nanostructures a potential option for cancer therapy in the near future.

  10. The interaction of carbon monoxide with rhodium on potassium-modified CeO2(111)

    NASA Astrophysics Data System (ADS)

    Mullins, David R.

    2016-10-01

    The adsorption and reactions of CO adsorbed on Rh particles deposited on K-covered CeO2(111) were studied by temperature programmed desorption and photoelectron spectroscopy. K deposited on CeO2(111) forms a KOX over-layer by extracting O from the ceria and partially reducing some of the Ce4 + to Ce3 +. CO does not adsorb on the KOX/ CeO2 - X(111) surface in the absence of Rh particles. CO adsorbed on Rh/K/CeO2(111) adsorbs molecularly on the Rh at 200 K. As the surface is heated the CO spills-over and reacts with the KOX to form carbonate. The carbonate decomposes at elevated temperature to produce CO and CO2. The carbonate stabilizes the KOX so that K desorbs at a higher temperature than it would in the absence of CO. When the Rh and K deposition are reversed so that K is deposited on both the Rh and the CeO2(111), CO adsorbs as CO2- at 200 K. The CO2- decomposes below 350 K to produce gas phase CO and adsorbed CO32 - and CO. The CO is stabilized by the K on the Rh and desorbs above 540 K. The carbonate decomposes into gas phase CO and CO2.

  11. High thermal stability of La2O3 and CeO2-stabilized tetragonal ZrO2

    DOE PAGESBeta

    Wang, Shichao; Xie, Hong; Lin, Yuyuan; Poeppelmeier, Kenneth R.; Li, Tao; Winans, Randall E.; Cui, Yanran; Ribeiro, Fabio H.; Canlas, Christian P.; Elam, Jeffrey W.; et al

    2016-02-15

    Catalyst support materials of tetragonal ZrO2, stabilized by either La2O3 (La2O3-ZrO2) or CeO2 (CeO2-ZrO2), were synthesized under hydrothermal conditions at 200 °C with NH4OH or tetramethylammonium hydroxide as the mineralizer. From In Situ synchrotron powder X-ray diffraction and small-angle X-ray scattering measurements, the calcined La2O3-ZrO2 and CeO2-ZrO2 supports were nonporous nanocrystallites that exhibited rectangular shapes with thermal stability up to 1000 °C in air. These supports had an average size of ~10 nm and a surface area of 59-97 m2/g. The catalysts Pt/La2O3-ZrO2 and Pt/CeO2-ZrO2 were prepared by using atomic layer deposition with varying Pt loadings from 6.3-12.4 wt %.more » Mono-dispersed Pt nanoparticles of ~3 nm were obtained for these catalysts. As a result, the incorporation of La2O3 and CeO2 into the t-ZrO2 structure did not affect the nature of the active sites for the Pt/ZrO2 catalysts for the water-gas-shift (WGS) reaction.« less

  12. An electrochemical DNA biosensor for evaluating the effect of mix anion in cellular fluid on the antioxidant activity of CeO2 nanoparticles.

    PubMed

    Zhai, Yanwu; Zhang, Yan; Qin, Fei; Yao, Xin

    2015-08-15

    CeO2 nanoparticles are of particular interest as a novel antioxidant for scavenging free radicals. However, some studies showed that they could cause cell damage or death by generating reactive oxygen species (ROS). Up to now, it is not well understood about these paradoxical phenomena. Therefore, many attentions have been paid to the factors that could affect the antioxidant activity of CeO2 nanoparticles. CeO2 nanoparticles would inevitably encounter body fluid environment for its potential medical application. In this work the antioxidant activity behavior of CeO2 nanoparticles is studied in simulated cellular fluid, which contains main body anions (HPO4(2-), HCO3(-), Cl(-) and SO4(2-)), by a method of electrochemical DNA biosensor. We found that in the solution of Cl(-) and SO4(2-), CeO2 nanoparticles can protect DNA from damage by hydroxyl radicals, while in the presence of HPO4(2-) and HCO3(-), CeO2 nanoparticles lose the antioxidant activity. This can be explained by the cerium phosphate and cerium carbonate formed on the surface of the nanoparticles, which interfere with the redox cycling between Ce(3+) and Ce(4+). These results not only add basic knowledge to the antioxidant activity of CeO2 nanoparticles under different situations, but also pave the way for practical applications of nanoceria. Moreover, it also shows electrochemical DNA biosensor is an effective method to explore the antioxidant activity of CeO2 nanoparticles.

  13. Silver nanoparticles supported on CeO2-SBA-15 by microwave irradiation possess metal-support interactions and enhanced catalytic activity.

    PubMed

    Qian, Xufang; Kuwahara, Yasutaka; Mori, Kohsuke; Yamashita, Hiromi

    2014-11-24

    Metal-support interactions (MSIs) and particle size play important roles in catalytic reactions. For the first time, silver nanoparticles supported on CeO2-SBA-15 supports are reported that possess tunable particle size and MSIs, as prepared by microwave (MW) irradiation, owing to strong charge polarization of CeO2 clusters (i.e., MW absorption). Characterizations, including TEM, X-ray photoelectron spectroscopy, and extended X-ray absorption fine structure, were carried out to disclose the influence of CeO2 contents on the Ag particle size, MSI effect between Ag nanoparticles and CeO2-SBA-15 supports, and the strong MW absorption of CeO2 clusters that contribute to the MSIs during Ag deposition. The Ag particle sizes were controllably tuned from 1.9 to 3.9 nm by changing the loading amounts of CeO2 from 0.5 to 2.0 wt%. The Ag nanoparticle size was predominantly responsible for the high turnover frequency (TOF) of 0.41 min(-1) in ammonia borane dehydrogenation, whereas both particle size and MSIs contributed to the high TOF of 555 min(-1) in 4-nitrophenol reduction for Ag/0.5CeO2-SBA-15, which were twice as large as those of Ag/SBA-15 without CeO2 and Ag/CeO2-SBA-15 prepared by conventional oil-bath heating.

  14. Direct synthesis of dimethyl carbonate from methanol and carbon dioxide over CeO2(X)-ZnO(1-X) nano-catalysts.

    PubMed

    Kang, Ki Hyuk; Joe, Wangrae; Lee, Chang Hoon; Kim, Mieock; Kim, Dong Baek; Jang, Boknam; Song, In Kyu

    2013-12-01

    CeO2(X)-ZnO(1-X) (X = 0, 0.1, 0.3, 0.5, 0.7, 0.9, and 1.0) nano-catalysts were prepared by a co-precipitation method with a variation of CeO2 content (X, mol%), and they were applied to the direct synthesis of dimethyl carbonate from methanol and carbon dioxide. Successful formation of CeO2(X)-ZnO(1-X) nano-catalysts was well confirmed by XRD analysis. The amount of DMC produced over CeO2(X)-ZnO(1-X) catalysts exhibited a volcano-shaped curve with respect to CeO2 content. Acidity and basicity of CeO2(X)-ZnO(1-X) nano-catalysts were measured by NH3-TPD and CO2-TPD experiments, respectively, to elucidate the effect of acidity and basicity on the catalytic performance in the reaction. It was revealed that the catalytic performance of CeO2(X)-ZnO(1-X) nano-catalysts was closely related to the acidity and basicity of the catalysts. Amount of dimethyl carbonate increased with increasing both acidity and basicity of the catalysts. Among the catalysts tested, CeO2(0.7)-ZnO(0.3) with the largest acidity and basicity showed the best catalytic performance in the direct synthesis of dimethyl carbonate from methanol and carbon dioxide. PMID:24266202

  15. Silver nanoparticles supported on CeO2-SBA-15 by microwave irradiation possess metal-support interactions and enhanced catalytic activity.

    PubMed

    Qian, Xufang; Kuwahara, Yasutaka; Mori, Kohsuke; Yamashita, Hiromi

    2014-11-24

    Metal-support interactions (MSIs) and particle size play important roles in catalytic reactions. For the first time, silver nanoparticles supported on CeO2-SBA-15 supports are reported that possess tunable particle size and MSIs, as prepared by microwave (MW) irradiation, owing to strong charge polarization of CeO2 clusters (i.e., MW absorption). Characterizations, including TEM, X-ray photoelectron spectroscopy, and extended X-ray absorption fine structure, were carried out to disclose the influence of CeO2 contents on the Ag particle size, MSI effect between Ag nanoparticles and CeO2-SBA-15 supports, and the strong MW absorption of CeO2 clusters that contribute to the MSIs during Ag deposition. The Ag particle sizes were controllably tuned from 1.9 to 3.9 nm by changing the loading amounts of CeO2 from 0.5 to 2.0 wt%. The Ag nanoparticle size was predominantly responsible for the high turnover frequency (TOF) of 0.41 min(-1) in ammonia borane dehydrogenation, whereas both particle size and MSIs contributed to the high TOF of 555 min(-1) in 4-nitrophenol reduction for Ag/0.5CeO2-SBA-15, which were twice as large as those of Ag/SBA-15 without CeO2 and Ag/CeO2-SBA-15 prepared by conventional oil-bath heating. PMID:25336086

  16. Direct synthesis of dimethyl carbonate from methanol and carbon dioxide over CeO2(X)-ZnO(1-X) nano-catalysts.

    PubMed

    Kang, Ki Hyuk; Joe, Wangrae; Lee, Chang Hoon; Kim, Mieock; Kim, Dong Baek; Jang, Boknam; Song, In Kyu

    2013-12-01

    CeO2(X)-ZnO(1-X) (X = 0, 0.1, 0.3, 0.5, 0.7, 0.9, and 1.0) nano-catalysts were prepared by a co-precipitation method with a variation of CeO2 content (X, mol%), and they were applied to the direct synthesis of dimethyl carbonate from methanol and carbon dioxide. Successful formation of CeO2(X)-ZnO(1-X) nano-catalysts was well confirmed by XRD analysis. The amount of DMC produced over CeO2(X)-ZnO(1-X) catalysts exhibited a volcano-shaped curve with respect to CeO2 content. Acidity and basicity of CeO2(X)-ZnO(1-X) nano-catalysts were measured by NH3-TPD and CO2-TPD experiments, respectively, to elucidate the effect of acidity and basicity on the catalytic performance in the reaction. It was revealed that the catalytic performance of CeO2(X)-ZnO(1-X) nano-catalysts was closely related to the acidity and basicity of the catalysts. Amount of dimethyl carbonate increased with increasing both acidity and basicity of the catalysts. Among the catalysts tested, CeO2(0.7)-ZnO(0.3) with the largest acidity and basicity showed the best catalytic performance in the direct synthesis of dimethyl carbonate from methanol and carbon dioxide.

  17. Biochemical effects of six TiO2 and four CeO2 nanomaterials in HepG2 cells

    EPA Science Inventory

    Biochemical effects of six TiO2 and four CeO2 nanomaterials in HepG2 cellsBecause of their growing number of uses, nanoparticles composed of CeO2 (cosmetics, polishing materials and automotive fuel additives) and TiO2 (pigments, sunscreens and photocatalysts) are of particular to...

  18. 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 corresponding BJH pore-size distribution curves. See DOI: 10.1039/c4nr02485k

  19. The Effect of CeO2 Addition on the Microstructure and Properties of Ni-Based Flame-Spray Coatings

    NASA Astrophysics Data System (ADS)

    Zhang, Zhenyu; Liang, Bunv; Guo, Hongjian

    2014-04-01

    Ni-based alloy with different amount of CeO2 powders were flame sprayed and melted onto 1045 carbon steel substrate. Microstructure and properties of the coatings were studied by XRD, field emission gun scanning electron microscope (FEGSEM) and SEM analyses. The wear behavior of the coatings was investigated under dry sliding wear conditions, and was compared with that of the coatings without CeO2, The results show that the microstructure of the coating with CeO2 differs widely from the coating without CeO2, the novel microstructure is beneficial for wear resistance. Abrasive wear tests without lubricant and analysis of the worn surfaces revealed that the Ni-based alloy coatings with the addition of 0.8% CeO2 exhibit higher wear resistance.

  20. Nanostructured oxide-based powders: investigation of the growth mode of the CeO2 clusters on the YSZ surface.

    PubMed

    Natile, Marta M; Glisenti, Antonella

    2006-02-16

    CeO(2)/YSZ nanocomposite powders, characterized by increasing Ce/Zr atomic ratio, were obtained by depositing, by wet impregnation, different amounts of CeO(2) on the yttria-stabilized zirconia (YSZ) surface. These powders were characterized by means of X-ray photoelectron spectroscopy, transmission electron microscopy, energy dispersive spectroscopy, and X-ray diffraction. Experimental results allow us to obtain interesting information concerning the growth mode, the morphology, and the dimensions of the CeO(2) clusters on the YSZ supporting surface. A 3-D growing mechanism was observed for the CeO(2) nanoparticles. With increasing Ce/Zr atomic ratio the CeO(2) clusters become more and more spherical. Moreover, XPS data also show the presence of Ce(III) and Ce(IV) ions at the interface supported/supporting oxides.

  1. Surface-structure sensitivity of CeO2 nanocrystals in photocatalysis and enhancing the reactivity with nanogold

    DOE PAGESBeta

    Lei, Wanying; Zhang, Tingting; Gu, Lin; Liu, Ping; Rodriguez, José A.; Liu, Gang; Liu, Minghua

    2015-06-19

    Structure–function correlations are a central theme in heterogeneous (photo)catalysis. In this research, using aberration-corrected scanning transmission electron microscopy (STEM), the atomic surface structures of well-defined one-dimensional (1D) CeO2 nanorods (NRs) and 3D nanocubes (NCs) are directly visualized at subangstrom resolution. CeO2 NCs predominantly expose the {100} facet, with {110} and {111} as minor cutoff facets at the respective edges and corners. Notably, the outermost surface layer of the {100} facet is nearly O-terminated. Neither surface relaxations nor reconstructions on {100} are observed, indicating unusual polarity compensation, which is primarily mediated by near-surface oxygen vacancies. The surface of CeO2 NRs ismore » highly stepped, with the enclosed {110} facet exposing Ce cations and O anions on terraces. On the basis of STEM profile-view imaging and electronic structure analysis, the photoreactivity of CeO2 nanocrystals toward aqueous methyl orange degradation under UV is revealed to be surface-structure-sensitive, following the order: {110} >> {100}. The underlying surface-structure sensitivity can be attributed to the variation in low-coordinate surface cerium cations between {110} and {100} facets. To further enhance light absorption, Au nanoparticles (NPs) are deposited on CeO2 NRs to form Au/CeO2 plasmonic nanocomposites, which dramatically promotes the photoreactivity that is Au particle size- and excitation light wavelength-dependent. The mechanisms responsible for the enhancement of photocatalytic activity are discussed, highlighting the crucial role of photoexcited charge carrier transfer.« less

  2. Novel CeO2-CuO-decorated enzymatic lactate biosensors operating in low oxygen environments.

    PubMed

    Uzunoglu, Aytekin; Stanciu, Lia A

    2016-02-25

    The detection of the lactate level in blood plays a key role in diagnosis of some pathological conditions including cardiogenic or endotoxic shocks, respiratory failure, liver disease, systemic disorders, renal failure, and tissue hypoxia. Here, we described for the first time the use of a novel mixed metal oxide solution system to address the oxygen dependence challenge of first generation amperometric lactate biosensors. The biosensors were constructed using ceria-copper oxide (CeO2-CuO) mixed metal oxide nanoparticles for lactate oxidase immobilization and as electrode material. The oxygen storage capacity (OSC, 492 μmol-O2/g) of these metal oxides has the potential to reduce the oxygen dependency, and thus eliminate false results originated from the fluctuations in the oxygen concentration. In an effort to compare the performance of our novel sensor design, ceria nanoparticle decorated lactate sensors were also constructed. The enzymatic activity of the sensors were tested in oxygen-rich and oxygen-lean solutions. Our results showed that the OSC of the electrode material has a big influence on the activity of the biosensors in oxygen-lean environments. While the CeO2 containing biosensor showed an almost 21% decrease in the sensitivity in a O2-depleted solution, the CeO2-CuO containing electrode, with a higher OSC value, experienced no drop in sensitivity when moving from oxygen-rich to oxygen-lean conditions. The CeO2-CuO decorated sensor showed a high sensitivity (89.3 ± 4 μA mM(-1) cm(-2)), a wide linear range up to 0.6 mM, and a low limit of detection of 3.3 μM. The analytical response of the CeO2-CuO decorated sensors was studied by detecting lactate in human serum with good selectivity and reliability. The results revealed that CeO2-CuO containing sensors are promising candidates for continuous lactate detection.

  3. Enhanced transport of CeO2 nanoparticles in porous media by macropores.

    PubMed

    Fang, Jing; Wang, Min-hao; Lin, Dao-hui; Shen, Bing

    2016-02-01

    This is the first study to investigate the effect of macropores on the transport of CeO2 nanoparticles (nCeO2) in quartz sand and soil. The artificial macropore types are the vertical continuous macropore (O-O), and the vertical discontinuous macropore (O-C). The results indicated that the mobility of nCeO2 was significantly enhanced by the macropore in both quartz sand and soil, and the enhancement was greater in the continuous macropore than in the discontinuous macropore. Compared with the homogeneous column, both the O-O and O-C macropores in quartz sand favored an earlier breakthrough and a larger initial effluent recovery rate of nCeO2. However, there was little influence on the plateau concentration and the total effluent recovery rate. In soil, both types of macropores significantly shortened nCeO2 breakthrough time, and favored a higher plateau concentration, and a larger initial and total effluent recovery rate. The O-O macropore which accounted for only 1% of the total pore volume had doubly increased the total mobility of nCeO2 in soil; even the mobility was increased by 30% with the O-C macropore. It was found that the effect of preferential flow on nCeO2 transport was greater in soil than it was in quartz sand. PMID:26584072

  4. High pressure and temperature equation of state and spectroscopic study of CeO2

    NASA Astrophysics Data System (ADS)

    Jacobsen, M. K.; Velisavljevic, N.; Dattelbaum, D. M.; Chellappa, R. S.; Park, C.

    2016-04-01

    One of the most widely used x-ray standards and a highly applied component of catalysis systems, CeO2 has been studied for the purpose of better understanding its equation of state and electronic properties. Diamond anvil cells have been used to extend the equation of state for this material to 130 GPa and explore the electronic behavior with applied load. From the x-ray diffraction studies, it has been determined that the high pressure phase transition extends from approximately 35-75 GPa at ambient temperature. Elevation of temperature is found to decrease the initiation pressure for this transition, with multiple distinct temperature regions which indicate structural related anomalies. In addition, hydrostatic and non-hydrostatic effects are compared and exhibit a drastic difference in bulk moduli. The electronic results indicate a change in the scattering environment of the cerium atom, associated with the high pressure phase transition. Overall, these results present the first megabar pressure study and the first high pressure and temperature study of ceria. Additionally, this shows the first combined study of the K and L III edges of this material to 33 GPa.

  5. 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.

  6. Diffusion Barriers Block Defect Occupation on Reduced CeO2(111 )

    NASA Astrophysics Data System (ADS)

    Lustemberg, P. G.; Pan, Y.; Shaw, B.-J.; Grinter, D.; Pang, Chi; Thornton, G.; Pérez, Rubén; Ganduglia-Pirovano, M. V.; Nilius, N.

    2016-06-01

    Surface defects are believed to govern the adsorption behavior of reducible oxides. We challenge this perception on the basis of a combined scanning-tunneling-microscopy and density-functional-theory study, addressing the Au adsorption on reduced CeO2 -x(111 ) . Despite a clear thermodynamic preference for oxygen vacancies, individual Au atoms were found to bind mostly to regular surface sites. Even at an elevated temperature, aggregation at step edges and not decoration of defects turned out to be the main consequence of adatom diffusion. Our findings are explained with the polaronic nature of the Au-ceria system, which imprints a strong diabatic character onto the diffusive motion of adatoms. Diabatic barriers are generally higher than those in the adiabatic regime, especially if the hopping step couples to an electron transfer into the ad-gold. As the population of O vacancies always requires a charge exchange, defect decoration by Au atoms becomes kinetically hindered. Our study demonstrates that polaronic effects determine not only electron transport in reducible oxides but also the adsorption characteristics and therewith the surface chemistry.

  7. High pressure and temperature equation of state and spectroscopic study of CeO2.

    PubMed

    Jacobsen, M K; Velisavljevic, N; Dattelbaum, D M; Chellappa, R S; Park, C

    2016-04-20

    One of the most widely used x-ray standards and a highly applied component of catalysis systems, CeO2 has been studied for the purpose of better understanding its equation of state and electronic properties. Diamond anvil cells have been used to extend the equation of state for this material to 130 GPa and explore the electronic behavior with applied load. From the x-ray diffraction studies, it has been determined that the high pressure phase transition extends from approximately 35-75 GPa at ambient temperature. Elevation of temperature is found to decrease the initiation pressure for this transition, with multiple distinct temperature regions which indicate structural related anomalies. In addition, hydrostatic and non-hydrostatic effects are compared and exhibit a drastic difference in bulk moduli. The electronic results indicate a change in the scattering environment of the cerium atom, associated with the high pressure phase transition. Overall, these results present the first megabar pressure study and the first high pressure and temperature study of ceria. Additionally, this shows the first combined study of the K and L III edges of this material to 33 GPa. PMID:26987548

  8. Structure and surface chemistry in crystalline mesoporous (CeO(2-δ))-YSZ.

    PubMed

    Somacescu, Simona; Parvulescu, Viorica; Osiceanu, Petre; Calderon-Moreno, Jose Maria; Su, Bao-Lian

    2011-11-01

    Mesoporous metal oxides (CeO(2-δ))-YSZ have been synthesized by a versatile direct synthesis method using ionic cetyltrimethylammonium bromide (CTAB) and different nonionic (block copolymers) as surfactants and urea as hydrolyzing agent. The synthesis was realized at pH=9 using tetraethylammonium hydroxide (TEAOH) as pH mediator. Calcination at 550 °C led to the formation of crystalline metal oxides with uniform mesoporosity. The obtained materials have been characterized by thermogravimetric analysis (TG-DTG), wide and small-angle X-ray diffraction (XRD), Raman spectroscopy, Brunauer, Emmett and Teller (BET) surface area analysis, scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). All the obtained materials exhibits mesoporous structure, crystalline structure indexed in a cubic symmetry, showing a high surface area, a uniform and narrow pore size distribution, spherical morphology typical for the mesoporous materials. The crystalline and mesoporous structures, surface chemistry and stoichiometry for the samples synthesized using ionic and nonionic surfactants have been discussed.

  9. Diffusion Barriers Block Defect Occupation on Reduced CeO_{2}(111).

    PubMed

    Lustemberg, P G; Pan, Y; Shaw, B-J; Grinter, D; Pang, Chi; Thornton, G; Pérez, Rubén; Ganduglia-Pirovano, M V; Nilius, N

    2016-06-10

    Surface defects are believed to govern the adsorption behavior of reducible oxides. We challenge this perception on the basis of a combined scanning-tunneling-microscopy and density-functional-theory study, addressing the Au adsorption on reduced CeO_{2-x}(111). Despite a clear thermodynamic preference for oxygen vacancies, individual Au atoms were found to bind mostly to regular surface sites. Even at an elevated temperature, aggregation at step edges and not decoration of defects turned out to be the main consequence of adatom diffusion. Our findings are explained with the polaronic nature of the Au-ceria system, which imprints a strong diabatic character onto the diffusive motion of adatoms. Diabatic barriers are generally higher than those in the adiabatic regime, especially if the hopping step couples to an electron transfer into the ad-gold. As the population of O vacancies always requires a charge exchange, defect decoration by Au atoms becomes kinetically hindered. Our study demonstrates that polaronic effects determine not only electron transport in reducible oxides but also the adsorption characteristics and therewith the surface chemistry.

  10. Enhancement of room temperature ferromagnetic behavior of rf sputtered Ni-CeO2 thin films

    NASA Astrophysics Data System (ADS)

    Murugan, R.; Vijayaprasath, G.; Mahalingam, T.; Ravi, G.

    2016-12-01

    Ni-doped CeO2 thin films were prepared under Ar+ atmosphere on glass substrates using rf magnetron sputtering. To assess the properties of the prepared thin films, the influence of various amounts of Ni dopant on structural, morphological, optical, vibrational, compositional and magnetic properties of the CeO2 films were studied by using X-Ray diffraction (XRD), atomic force microscope (AFM), photoluminescence (PL), micro-Raman, X-ray photoelectron spectroscopy (XPS) and vibrating sample magnetometer (VSM). XRD patterns for all the samples revealed the expected CeO2 cubic fluorite-type structure and Ni ions were uniformly distributed in the samples. AFM images of the prepared samples indicate high dense, columnar structure with uniform distribution of CeO2. Room-temperature photoluminescence (PL) and micro-Raman spectroscopic studies revealed an increase of oxygen vacancies with higher concentration of Ni in CeO2. XPS results confirm the presence of Ni2p, O1s and Ce and depict that cerium is present as both Ce4+ and Ce3+ oxidation states in Ce1-xNixO2 (x = 15%) thin film. Field dependent magnetization measurements revealed a paramagnetic behavior for pure CeO2, while a ferromagnetic behavior appeared when Ni is doped in CeO2 films. Doping dependent magnetization measurements suggest that the observed ferromagnetism is due to the presence of metallic Ni clusters with nanometric size and broad size distribution.

  11. Thermally Stable Hierarchical Nanostructures of Ultrathin MoS2 Nanosheet-Coated CeO2 Hollow Spheres as Catalyst for Ammonia Decomposition.

    PubMed

    Gong, Xueyun; Gu, Ying-Qiu; Li, Na; Zhao, Hongyang; Jia, Chun-Jiang; Du, Yaping

    2016-04-18

    MoS2 ultrathin nanosheet-coated CeO2 hollow sphere (CeO2@MoS2) hybrid nanostructures with a 3D hierarchical configuration were successfully constructed from a facile two-step wet chemistry strategy: first, CeO2 formed on a silica core which served as a template and was subsequently removed by NaOH solution to attain hollow spheres, and then few-layered ultrathin MoS2 nanosheets were deposited on the CeO2 hollow spheres through a hydrothermal process. As a proof of concept application, the as-prepared CeO2@MoS2 hybrid nanostructures were used as catalytic material, which exhibited enhanced catalytic activity in ammonia decomposition for H2 production at high temperature. It was demonstrated that, even with a structural transformation from MoS2 to MoNx under harsh conditions of ammonia decomposition at high temperature (700 °C), the 3D hierarchical nanostructures of the CeO2@MoNx were well kept, indicating the important role of the CeO2 support.

  12. Effect of surface coating and organic matter on the uptake of CeO2 NPs by corn plants grown in soil: Insight into the uptake mechanism

    PubMed Central

    Zhao, Lijuan; Peralta-Videa, Jose R.; Varela-Ramirez, Armando; Castillo-Michel, Hiram; Li, Chunqiang; Zhang, Jianying; Aguilera, Renato J.; Keller, Arturo A.; Gardea-Torresdey, Jorge L.

    2015-01-01

    Little is known about the fate, transport, and bioavailability of CeO2 nanoparticles (NPs) in soil. Moreover, there are no reports on the effect of surface coating upon NPs uptake by plants. In this study, Zea mays plants were grown for one month in unenriched and organic soils treated with coated and uncoated CeO2 NPs. In addition, plants were exposed to fluorescein isothiocyanate (FITC)-stained CeO2 NPs and analyzed in a confocal microscope. In organic soil, roots from uncoated and coated NPs at 100, 200, 400, and 800 mg kg−1 had 40, 80, 130, and 260% and 10, 70, 90, and 40% more Ce, respectively, compared to roots from unenriched soil. Conversely, shoots of plants from unenriched soil had significantly more Ce compared with shoots from organic soil. Confocal fluorescence images showed FITC-stained CeO2 NP aggregates in cell walls of epidermis and cortex, suggesting apoplastic pathway. The μXRF results revealed the presence of CeO2 NP aggregates within vascular tissues. To the authors knowledge this is the first report on the effects of surface coating and organic matter on Ce uptake from CeO2 NPs and upon the mechanisms of CeO2 NPs uptake by higher plants PMID:22633924

  13. Citric acid modifies surface properties of commercial CeO2 nanoparticles reducing their toxicity and cerium uptake in radish (Raphanus sativus) seedlings.

    PubMed

    Trujillo-Reyes, J; Vilchis-Nestor, A R; Majumdar, S; Peralta-Videa, J R; Gardea-Torresdey, J L

    2013-12-15

    Little is known about the mobility, reactivity, and toxicity to plants of coated engineered nanoparticles (ENPs). Surface modification may change the interaction of ENPs with living organisms. This report describes surface changes in commercial CeO2 NPs coated with citric acid (CA) at molar ratios of 1:2, 1:3, 1:7, and 1:10 CeO2:CA, and their effects on radish (Raphanus sativus) seed germination, cerium and nutrients uptake. All CeO2 NPs and their absorption by radish plants were characterized by TEM, DLS, and ICP-OES. Radish seeds were germinated in pristine and CA coated CeO2 NPs suspensions at 50mg/L, 100mg/L, and 200mg/L. Deionized water and CA at 100mg/L were used as controls. Results showed ζ potential values of 21.6 mV and -56 mV for the pristine and CA coated CeO2 NPs, respectively. TEM images showed denser layers surrounding the CeO2 NPs at higher CA concentrations, as well as better distribution and smaller particle sizes. None of the treatments affected seed germination. However, at 200mg/L the CA coated NPs at 1:7 ratio produced significantly (p ≤ 0.05) more root biomass, increased water content and reduced by 94% the Ce uptake, compared to bare NPs. This suggests that CA coating decrease CeO2 NPs toxicity to plants.

  14. Identification of the arsenic resistance on MoO3 doped CeO2/TiO2 catalyst for selective catalytic reduction of NOx with ammonia.

    PubMed

    Li, Xiang; Li, Xiansheng; Li, Junhua; Hao, Jiming

    2016-11-15

    Arsenic resistance on MoO3 doped CeO2/TiO2 catalysts for selective catalytic reduction of NOx with NH3 (NH3-SCR) is investigated. It is found that the activity loss of CeO2-MoO3/TiO2 caused by As oxide is obvious less than that of CeO2/TiO2 catalysts. The fresh and poisoned catalysts are compared and analyzed using XRD, Raman, XPS, H2-TPR and in situ DRIFTS. The results manifest that the introduction of arsenic oxide to CeO2/TiO2 catalyst not only weakens BET surface area, surface acid sites and adsorbed NOx species, but also destroy the redox circle of Ce(4+) to Ce(3+) because of interaction between Ce and As. When MoO3 is added into CeO2/TiO2 system, the main SCR reaction path are found to be changed from the reaction between coordinated NH3 and ad-NOx species to that between an amide and gaseous NO. Additionally, for CeO2-MoO3/TiO2 catalyst, As toxic effect on active sites CeO2 can be released because of stronger As-Mo interaction. Moreover, not only are the reactable Brønsted and Lewis acid sites partly restored, but the cycle of Ce(4+) to Ce(3+) can also be free to some extent.

  15. CeO2-modified Au@SBA-15 nanocatalysts for liquid-phase selective oxidation of benzyl alcohol

    NASA Astrophysics Data System (ADS)

    Wang, Tuo; Yuan, Xiang; Li, Shuirong; Zeng, Liang; Gong, Jinlong

    2015-04-01

    Tuning the interfacial perimeter and structure is crucial to understanding the origin of catalytic performance. This paper describes the design, characterization, and application of CeO2 modified Au@SBA-15 (Au-CeO2@SBA-15) catalysts in selective oxidation of benzyl alcohol. The reaction results showed that Au-CeO2@SBA-15 catalysts exhibited higher catalytic activity compared with Au@SBA-15 and Au/CeO2 catalysts under identical conditions along with the high selectivity towards benzaldehyde (>99%). The turnover frequency of benzyl alcohol over the Au-100CeO2@SBA-15 catalyst is about nine-fold and four-fold higher than those of Au@SBA-15 and Au/CeO2 catalysts, respectively. The supported catalysts were characterized by N2 adsorption-desorption, inductively coupled plasma optical emission spectroscopy, X-ray diffraction, transmission electron microscopy, high-angle annular dark-field scanning transmission electron microscopy, scanning transmission electron microscopy-energy dispersive spectrometry, and X-ray photoelectron spectroscopy. It was found that the Au and small CeO2 nanoparticles (~5 nm) were homogeneously mixed in the channels of SBA-15, which led to an increase in the interfacial area between Au and CeO2 and consequently a better catalytic performance of Au-CeO2@SBA-15 catalysts for the selective oxidation of benzyl alcohol to benzaldehyde compared with that of Au/CeO2. The prevention of agglomeration and leaching of Au nanoparticles by restricting them inside the mesopores of SBA-15 was conducive to the stable existence of large quantities of Au-CeO2 interface, which leads to high stability of the Au-CeO2@SBA-15 catalyst.Tuning the interfacial perimeter and structure is crucial to understanding the origin of catalytic performance. This paper describes the design, characterization, and application of CeO2 modified Au@SBA-15 (Au-CeO2@SBA-15) catalysts in selective oxidation of benzyl alcohol. The reaction results showed that Au-CeO2@SBA-15 catalysts exhibited higher catalytic activity compared with Au@SBA-15 and Au/CeO2 catalysts under identical conditions along with the high selectivity towards benzaldehyde (>99%). The turnover frequency of benzyl alcohol over the Au-100CeO2@SBA-15 catalyst is about nine-fold and four-fold higher than those of Au@SBA-15 and Au/CeO2 catalysts, respectively. The supported catalysts were characterized by N2 adsorption-desorption, inductively coupled plasma optical emission spectroscopy, X-ray diffraction, transmission electron microscopy, high-angle annular dark-field scanning transmission electron microscopy, scanning transmission electron microscopy-energy dispersive spectrometry, and X-ray photoelectron spectroscopy. It was found that the Au and small CeO2 nanoparticles (~5 nm) were homogeneously mixed in the channels of SBA-15, which led to an increase in the interfacial area between Au and CeO2 and consequently a better catalytic performance of Au-CeO2@SBA-15 catalysts for the selective oxidation of benzyl alcohol to benzaldehyde compared with that of Au/CeO2. The prevention of agglomeration and leaching of Au nanoparticles by restricting them inside the mesopores of SBA-15 was conducive to the stable existence of large quantities of Au-CeO2 interface, which leads to high stability of the Au-CeO2@SBA-15 catalyst. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr00246j

  16. Effect of oxidizer to fuel molar ratio on particle size and DC conductivity of CeO2 nanoparticles

    NASA Astrophysics Data System (ADS)

    Harish, B. M.; Rajeeva, M. P.; Naveen, C. S.; Chaturmukha, V. S.; Avinash, B. S.; Jayanna, H. S.; Lamani, Ashok R.

    2016-05-01

    Cerium oxide nanoparticles were synthesized by solution combustion method with varying the oxidizer (cerium nitrate hexa hydrate) to fuel (Glycine) molar ratio. The prepared samples were characterized by UV-visible spectrometer, X-ray diffractometer (XRD), Scanning electron microscope (SEM) and Energy dispersive X-Ray analysis (EDAX). XRD pattern reveals the formation of cubic fluorite structure of CeO2. It was observed that finest crystallites were found at extreme fuel-deficient condition and it is good enough to produce favorable powder characteristics. The average crystallite size was found to be 14.46 nm to 21.57 nm. The temperature dependent dc conductivity was carried out using Keithley source meter between the temperature range from 300K to 573K. From this study it was found that the conductivity increases with increase of temperature due to semiconducting behavior of CeO2 and it decreases with particle size due to increase in the energy band gap.

  17. CeO2-modified Au@SBA-15 nanocatalysts for liquid-phase selective oxidation of benzyl alcohol.

    PubMed

    Wang, Tuo; Yuan, Xiang; Li, Shuirong; Zeng, Liang; Gong, Jinlong

    2015-05-01

    Tuning the interfacial perimeter and structure is crucial to understanding the origin of catalytic performance. This paper describes the design, characterization, and application of CeO2 modified Au@SBA-15 (Au-CeO2@SBA-15) catalysts in selective oxidation of benzyl alcohol. The reaction results showed that Au-CeO2@SBA-15 catalysts exhibited higher catalytic activity compared with Au@SBA-15 and Au/CeO2 catalysts under identical conditions along with the high selectivity towards benzaldehyde (>99%). The turnover frequency of benzyl alcohol over the Au-100CeO2@SBA-15 catalyst is about nine-fold and four-fold higher than those of Au@SBA-15 and Au/CeO2 catalysts, respectively. The supported catalysts were characterized by N2 adsorption-desorption, inductively coupled plasma optical emission spectroscopy, X-ray diffraction, transmission electron microscopy, high-angle annular dark-field scanning transmission electron microscopy, scanning transmission electron microscopy-energy dispersive spectrometry, and X-ray photoelectron spectroscopy. It was found that the Au and small CeO2 nanoparticles (∼5 nm) were homogeneously mixed in the channels of SBA-15, which led to an increase in the interfacial area between Au and CeO2 and consequently a better catalytic performance of Au-CeO2@SBA-15 catalysts for the selective oxidation of benzyl alcohol to benzaldehyde compared with that of Au/CeO2. The prevention of agglomeration and leaching of Au nanoparticles by restricting them inside the mesopores of SBA-15 was conducive to the stable existence of large quantities of Au-CeO2 interface, which leads to high stability of the Au-CeO2@SBA-15 catalyst.

  18. Designed Synthesis of CeO2 Nanorods and Nanowires for Studying Toxicological Effects of High Aspect Ratio Nanomaterials

    PubMed Central

    Ji, Zhaoxia; Wang, Xiang; Zhang, Haiyuan; Lin, Sijie; Meng, Huan; Sun, Bingbing; George, Saji; Xia, Tian; Nel, André E.; Zink, Jeffrey I.

    2012-01-01

    While it has been shown that high aspect ratio nanomaterials like carbon nanotubes and TiO2 nanowires can induce toxicity by acting as fiber-like substances that damage the lysosome, it is not clear what the critical lengths and aspect ratios are that induce this type of toxicity. To answer this question, we synthesized a series of cerium oxide (CeO2) nanorods and nanowires with precisely controlled lengths and aspect ratios. Both phosphate and chloride ions were shown to play critical roles in obtaining these high aspect ratio nanostructures. High resolution TEM analysis shows that single crystalline CeO2 nanorods/nanowires were formed along the [211] direction by an “oriented attachment” mechanism, followed by Ostwald ripening. The successful creation of a comprehensive CeO2 nanorod/nanowire combinatorial library allows, for the first time, the systematic study of the effect of aspect ratio on lysosomal damage, cytoxicity and IL-1β production by the human myeloid cell line (THP-1). This in vitro toxicity study demonstrated that at lengths ≥200 nm and aspect ratios ≥ 22, CeO2 nanorods induced progressive cytotoxicity and pro-inflammatory effects. The relatively low “critical” length and aspect ratio were associated with small nanorod/nanowire diameters (6–10 nm), which facilitates the formation of stacking bundles due to strong van der Waals and dipole-dipole attractions. Our results suggest that both length and diameter components of aspect ratio should be considered when addressing the cytotoxic effects of long aspect ratio materials. PMID:22564147

  19. CeO2-modified Au@SBA-15 nanocatalysts for liquid-phase selective oxidation of benzyl alcohol.

    PubMed

    Wang, Tuo; Yuan, Xiang; Li, Shuirong; Zeng, Liang; Gong, Jinlong

    2015-05-01

    Tuning the interfacial perimeter and structure is crucial to understanding the origin of catalytic performance. This paper describes the design, characterization, and application of CeO2 modified Au@SBA-15 (Au-CeO2@SBA-15) catalysts in selective oxidation of benzyl alcohol. The reaction results showed that Au-CeO2@SBA-15 catalysts exhibited higher catalytic activity compared with Au@SBA-15 and Au/CeO2 catalysts under identical conditions along with the high selectivity towards benzaldehyde (>99%). The turnover frequency of benzyl alcohol over the Au-100CeO2@SBA-15 catalyst is about nine-fold and four-fold higher than those of Au@SBA-15 and Au/CeO2 catalysts, respectively. The supported catalysts were characterized by N2 adsorption-desorption, inductively coupled plasma optical emission spectroscopy, X-ray diffraction, transmission electron microscopy, high-angle annular dark-field scanning transmission electron microscopy, scanning transmission electron microscopy-energy dispersive spectrometry, and X-ray photoelectron spectroscopy. It was found that the Au and small CeO2 nanoparticles (∼5 nm) were homogeneously mixed in the channels of SBA-15, which led to an increase in the interfacial area between Au and CeO2 and consequently a better catalytic performance of Au-CeO2@SBA-15 catalysts for the selective oxidation of benzyl alcohol to benzaldehyde compared with that of Au/CeO2. The prevention of agglomeration and leaching of Au nanoparticles by restricting them inside the mesopores of SBA-15 was conducive to the stable existence of large quantities of Au-CeO2 interface, which leads to high stability of the Au-CeO2@SBA-15 catalyst. PMID:25670350

  20. Strongly enhanced oxygen ion transport through samarium-doped CeO2 nanopillars in nanocomposite films

    DOE PAGESBeta

    Yang, Sangmo; Lee, Shinbuhm; Jian, Jie; Zhang, Wenrui; Lu, Ping; Jia, Quanxi; Wang, Haiyan; Noh, Tae Won; Kalinin, Sergei V.; MacManus-Driscoll, Judith L.

    2015-10-08

    Enhancement of oxygen ion conductivity in oxides is important for low-temperature (<500 °C) operation of solid oxide fuel cells, sensors and other ionotronic devices. While huge ion conductivity has been demonstrated in planar heterostructure films, there has been considerable debate over the origin of the conductivity enhancement, in part because of the difficulties of probing buried ion transport channels. Here we create a practical geometry for device miniaturization, consisting of highly crystalline micrometre-thick vertical nanocolumns of Sm-doped CeO2 embedded in supporting matrices of SrTiO3. The ionic conductivity is higher by one order of magnitude than plain Sm-doped CeO2 films. Bymore » using scanning probe microscopy, we show that the fast ion-conducting channels are not exclusively restricted to the interface but also are localized at the Sm-doped CeO2 nanopillars. This work offers a pathway to realize spatially localized fast ion transport in oxides of micrometre thickness.« less

  1. Strongly enhanced oxygen ion transport through samarium-doped CeO2 nanopillars in nanocomposite films.

    PubMed

    Yang, Sang Mo; Lee, Shinbuhm; Jian, Jie; Zhang, Wenrui; Lu, Ping; Jia, Quanxi; Wang, Haiyan; Noh, Tae Won; Kalinin, Sergei V; MacManus-Driscoll, Judith L

    2015-10-08

    Enhancement of oxygen ion conductivity in oxides is important for low-temperature (<500 °C) operation of solid oxide fuel cells, sensors and other ionotronic devices. While huge ion conductivity has been demonstrated in planar heterostructure films, there has been considerable debate over the origin of the conductivity enhancement, in part because of the difficulties of probing buried ion transport channels. Here we create a practical geometry for device miniaturization, consisting of highly crystalline micrometre-thick vertical nanocolumns of Sm-doped CeO2 embedded in supporting matrices of SrTiO3. The ionic conductivity is higher by one order of magnitude than plain Sm-doped CeO2 films. By using scanning probe microscopy, we show that the fast ion-conducting channels are not exclusively restricted to the interface but also are localized at the Sm-doped CeO2 nanopillars. This work offers a pathway to realize spatially localized fast ion transport in oxides of micrometre thickness.

  2. Strongly enhanced oxygen ion transport through samarium-doped CeO2 nanopillars in nanocomposite films.

    PubMed

    Yang, Sang Mo; Lee, Shinbuhm; Jian, Jie; Zhang, Wenrui; Lu, Ping; Jia, Quanxi; Wang, Haiyan; Noh, Tae Won; Kalinin, Sergei V; MacManus-Driscoll, Judith L

    2015-01-01

    Enhancement of oxygen ion conductivity in oxides is important for low-temperature (<500 °C) operation of solid oxide fuel cells, sensors and other ionotronic devices. While huge ion conductivity has been demonstrated in planar heterostructure films, there has been considerable debate over the origin of the conductivity enhancement, in part because of the difficulties of probing buried ion transport channels. Here we create a practical geometry for device miniaturization, consisting of highly crystalline micrometre-thick vertical nanocolumns of Sm-doped CeO2 embedded in supporting matrices of SrTiO3. The ionic conductivity is higher by one order of magnitude than plain Sm-doped CeO2 films. By using scanning probe microscopy, we show that the fast ion-conducting channels are not exclusively restricted to the interface but also are localized at the Sm-doped CeO2 nanopillars. This work offers a pathway to realize spatially localized fast ion transport in oxides of micrometre thickness. PMID:26446866

  3. Deactivation analyses of CeO2/CuO catalysts in the preferential oxidation of carbon monoxide

    NASA Astrophysics Data System (ADS)

    Zeng, Shanghong; Liu, Kewei; Zhang, Lu; Qin, Bin; Chen, Tianjia; Yin, Yueling; Su, Haiquan

    2014-09-01

    The hydrothermal in combination with impregnation methods are used to prepare the CeO2/CuO-X catalysts with spherical structure. The catalysts are characterized via SEM, XRD, H2-TPR, HRTEM, XPS and N2 adsorption-desorption techniques. The study shows that the microspheres of CuO consist of the sheet-like CuO and the way of arrangement results in the formation of shell structure. There is a core in the middle of shell structure, which is composed of the nano-sized CuO particles. CeO2 particles are supported on the surface of the CuO microspheres or embedded in the pores of sheet-like CuO. It is found that there is another reason for the decrease of CO conversion above 155 °C except H2 competitive oxidation. It is from the change of the CeO2/CuO catalyst during CO-PROX reaction including the reduction of CuO and the separation of metallic copper from the surface of catalyst.

  4. Synthesis and characterization of molybdenum catalysts supported on γ-Al2O3-CeO2 composite oxides

    NASA Astrophysics Data System (ADS)

    Farooq, Muhammad; Ramli, Anita; Subbarao, Duvvuri

    2012-09-01

    The physical and chemical properties of a catalyst play a vital role in various industrial applications. Molybdenum catalysts supported on γ-Al2O3 and γ-Al2O3-CeO2 mixed oxides with varying loading of CeO2 (5, 10, 15, 20 wt% with respect to γ-Al2O3) were prepared by wet impregnation method. The physiochemical properties of these synthesized Mo catalysts were studied with various characterization techniques such as X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), temperature-programmed reduction (TPR), field emission scanning electron microscopy-energy dispersive analysis (FESEM-EDX) and X-ray fluorescence spectrometer (XRF). The results showed that the addition of CeO2 into the support affected the binding energies of the elements and reducibility of the metal oxides formed after calcination of catalyst samples due to the change in metal-support interaction. Further, the characterization techniques showed that the active metal was well dispersed on the surface of support material.

  5. A Molecular Approach Towards Understanding the Biogenic Formation of CeO2 and its Interactions with Biomolecules

    NASA Astrophysics Data System (ADS)

    Cervini-Silva, J.; Fakra, S.; Gilbert, B.; Banfield, J.

    2005-12-01

    Cerium is the most abundant lanthanide and generally the only one to undergo redox reactions at the Earth's surface. The oxidation state influences the environmental chemistry and toxicology of Ce because it alters the mechanisms of interaction between Ce and biomolecules. For instance, as opposed to Ce(III) or other lanthanide ions, Ce(IV) has shown a remarkable efficiency to hydrolyze DNA. The selectivity of Ce as Ce(IV) relates to the specific coordination of water molecules and their orientation. Ce(IV) may also bind selectivity to biomolecules such as RNA-type substrates, or monocleotides such as AMP, to instigate conformational changes or cleavage of complexes, which affect metabolic pathways pivotal to growth and survival. On the other hand, biogenic ligands can promote the oxidation of Ce(III) to small sized-CeO2 and are subsequently degraded by this product to CO2 and humic material. Here, we study molecular interactions between CeO2 and biomolecules (e.g., catechol) using carbon and cerium, XRD, and IR spectroscopy. Results show a progressive increase in catechol transformation (as % carbon) with decreasing CeO2 particle diameter (13 < d < 84), which substantiates an intimate relation between CeO2 unit cell expansion and reactivity towards organics susceptible to undergo redox transformations. As shown by C and Ce spectroscopy, organic polymers that form because of catechol oxidation are distributed next to the mineral surface and its occurrence is coupled to Ce reduction-oxidation.

  6. Hexahedron Prism-Anchored Octahedronal CeO2: Crystal Facet-Based Homojunction Promoting Efficient Solar Fuel Synthesis.

    PubMed

    Li, Ping; Zhou, Yong; Zhao, Zongyan; Xu, Qinfeng; Wang, Xiaoyong; Xiao, Min; Zou, Zhigang

    2015-08-01

    An unprecedented, crystal facet-based CeO2 homojunction consisting of hexahedron prism-anchored octahedron with exposed prism surface of {100} facets and octahedron surface of {111} facets was fabricated through solution-based crystallographic-oriented epitaxial growth. The photocatalysis experiment reveals that growth of the prism arm on octahedron allows to activate inert CeO2 octahedron for an increase in phototocatalytic reduction of CO2 into methane. The pronounced photocatalytic performance is attributed to a synergistic effect of the following three factors: (1) band alignment of the {100} and {111} drives electrons and holes to octahedron and prism surfaces, respectively, aiming to reach the most stable energy configuration and leading to a spatial charge separation for long duration; (2) crystallographic-oriented epitaxial growth of the CeO2 hexahedron prism arm on the octahedron verified by the interfacial lattice fringe provides convenient and fast channels for the photogenerated carrier transportation between two units of homojuntion; (3) different effective mass of electrons and holes on {100} and {111} faces leads to high charge carrier mobility, more facilitating the charge separation. The proposed facet-based homojunction in this work may provide a new concept for the efficient separation and fast transfer of photoinduced charge carriers and enhancement of the photocatalytic performance.

  7. Strongly enhanced oxygen ion transport through samarium-doped CeO2 nanopillars in nanocomposite films

    PubMed Central

    Yang, Sang Mo; Lee, Shinbuhm; Jian, Jie; Zhang, Wenrui; Lu, Ping; Jia, Quanxi; Wang, Haiyan; Won Noh, Tae; Kalinin, Sergei V.; MacManus-Driscoll, Judith L.

    2015-01-01

    Enhancement of oxygen ion conductivity in oxides is important for low-temperature (<500 °C) operation of solid oxide fuel cells, sensors and other ionotronic devices. While huge ion conductivity has been demonstrated in planar heterostructure films, there has been considerable debate over the origin of the conductivity enhancement, in part because of the difficulties of probing buried ion transport channels. Here we create a practical geometry for device miniaturization, consisting of highly crystalline micrometre-thick vertical nanocolumns of Sm-doped CeO2 embedded in supporting matrices of SrTiO3. The ionic conductivity is higher by one order of magnitude than plain Sm-doped CeO2 films. By using scanning probe microscopy, we show that the fast ion-conducting channels are not exclusively restricted to the interface but also are localized at the Sm-doped CeO2 nanopillars. This work offers a pathway to realize spatially localized fast ion transport in oxides of micrometre thickness. PMID:26446866

  8. Effect of CeO2 coupling on the structural, optical and photocatalytic properties of ZnO nanoparticle

    NASA Astrophysics Data System (ADS)

    Sherly, E. D.; Vijaya, J. Judith; Kennedy, L. John

    2015-11-01

    This research work presents the microwave assisted combustion synthesis, characterization and photocatalytic applications of ZnO-CeO2 coupled nano metal oxide. ZnO, CeO2 and the coupled oxides ZnCe, Zn2Ce and ZnCe2 with ZnO and CeO2 in the molar ratio 1:1, 2:1 and 1:2 respectively were fabricated by microwave assisted metal nitrate-urea solution combustion synthesis, without using any organic solvent or surfactant. As-prepared samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM), energy dispersive X-ray analysis (EDX), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), diffuse reflectance spectroscopy (DRS) and photoluminescence spectroscopy(PL). The experiments of photocatalytic activity indicate that Zn2Ce nanoparticles exhibit excellent photocatalytic performance in the degradation of 2,4-dichlorophenol (2,4-DCP). 95% of 2,4-DCP molecules were decomposed by Zn2Ce in 240 min. The better photocatalytic degradation ability of Zn2Ce compared to ZnCe, ZnCe2 or single component ZnO and CeO2 nanoparticles is attributed to the improved separation of photogenerated electron-hole pairs.

  9. Surface degradation of CeO2 stabilized acrylic polyurethane coated thermally treated jack pine during accelerated weathering

    NASA Astrophysics Data System (ADS)

    Saha, Sudeshna; Kocaefe, Duygu; Boluk, Yaman; Pichette, Andre

    2013-07-01

    The thermally treated wood is a new value-added product and is very important for the diversification of forestry products. It drew the attention of consumers due to its attractive dark brown color. However, it loses its color when exposed to outside environment. Therefore, development of a protective coating for this value added product is necessary. In the present study, the efficiency of CeO2 nano particles alone or in combination with lignin stabilizer and/or bark extracts in acrylic polyurethane polymer was investigated by performing an accelerated weathering test. The color measurement results after accelerated weathering demonstrated that the coating containing CeO2 nano particles was the most effective whereas visual assessment suggested the coating containing CeO2 nano particles and lignin stabilizer as the most effective coating. The surface polarity changed for all the coatings during weathering and increase in contact angle after weathering suggested cross linking and reorientation of the polymer chain during weathering. The surface chemistry altered during weathering was evaluated by ATR-FTIR analysis. It suggested formation of different carbonyl byproducts during weathering. The chain scission reactions of the urethane linkages were not found to be significant during weathering.

  10. Rational design of octahedron and nanowire CeO2@MnO2 core-shell heterostructures with outstanding rate capability for asymmetric supercapacitors.

    PubMed

    Zhu, Shi Jin; Jia, Jia Qi; Wang, Tian; Zhao, Dong; Yang, Jian; Dong, Fan; Shang, Zheng Guo; Zhang, Yu Xin

    2015-10-14

    Two kinds of novel CeO2@MnO2 nanostructures have been synthesized via a self-assembly strategy. The as-prepared CeO2 nanowire@MnO2 nanostructures exhibited unprecedented pseudocapacitance performance (255 F g(-1)) with outstanding rate capability. A new mechanism based on the synergistic effect between CeO2 and MnO2 was proposed to interpret this phenomenon. When assembled as an asymmetric supercapacitor, an energy density of 27.5 W h kg(-1) with a maximum power density of 1.6 kW kg(-1) was achieved for CeO2 nanowire@MnO2 nanostructures.

  11. Utilizing peroxide as precursor for the synthesis of CeO2/ZnO composite oxide with enhanced photocatalytic activity

    NASA Astrophysics Data System (ADS)

    Lv, Zijian; Zhong, Qin; Ou, Man

    2016-07-01

    A facile synthesis method of CeO2/ZnO composite oxides with higher oxygen vacancy concentration was developed by a two-step precipitation method, in which peroxide was used as precursor. The photocatalytic activity of the catalysts under UV irradiation was studied in degradation of methylene blue (MB). All CeO2/ZnO photocatalysts exhibited higher photocatalytic performance than pure ZnO, and 1%CeO2/ZnO showed highest photocatalytic activity among the prepared catalysts. It was confirmed that the synergistic effect of CeO2 and oxygen vacancy caused the improved photocatalytic activity. Furthermore, the mechanism was investigated by introducing different additives, and it was found that the hydroxyl radicals played a crucial role in degradation process.

  12. Stress response and tolerance of Zea mays to CeO2 nanoparticles: cross talk among H2O2, heat shock protein, and lipid peroxidation.

    PubMed

    Zhao, Lijuan; Peng, Bo; Hernandez-Viezcas, Jose A; Rico, Cyren; Sun, Youping; Peralta-Videa, Jose R; Tang, Xiaolei; Niu, Genhua; Jin, Lixin; Varela-Ramirez, Armando; Zhang, Jian-ying; Gardea-Torresdey, Jorge L

    2012-11-27

    The rapid development of nanotechnology will inevitably release nanoparticles (NPs) into the environment with unidentified consequences. In addition, the potential toxicity of CeO(2) NPs to plants and the possible transfer into the food chain are still unknown. Corn plants (Zea mays) were germinated and grown in soil treated with CeO(2) NPs at 400 or 800 mg/kg. Stress-related parameters, such as H(2)O(2), catalase (CAT), and ascorbate peroxidase (APX) activity, heat shock protein 70 (HSP70), lipid peroxidation, cell death, and leaf gas exchange were analyzed at 10, 15, and 20 days post-germination. Confocal laser scanning microscopy was used to image H(2)O(2) distribution in corn leaves. Results showed that the CeO(2) NP treatments increased accumulation of H(2)O(2), up to day 15, in phloem, xylem, bundle sheath cells and epidermal cells of shoots. The CAT and APX activities were also increased in the corn shoot, concomitant with the H(2)O(2) levels. Both 400 and 800 mg/kg CeO(2) NPs triggered the up-regulation of the HSP70 in roots, indicating a systemic stress response. None of the CeO(2) NPs increased the level of thiobarbituric acid reacting substances, indicating that no lipid peroxidation occurred. CeO(2) NPs, at both concentrations, did not induce ion leakage in either roots or shoots, suggesting that membrane integrity was not compromised. Leaf net photosynthetic rate, transpiration, and stomatal conductance were not affected by CeO(2) NPs. Our results suggest that the CAT, APX, and HSP70 might help the plants defend against CeO(2) NP-induced oxidative injury and survive NP exposure. PMID:23050848

  13. MOD approach for the growth of epitaxial CeO2 buffer layers on biaxially textured Ni W substrates for YBCO coated conductors

    NASA Astrophysics Data System (ADS)

    Bhuiyan, M. S.; Paranthaman, M.; Sathyamurthy, S.; Aytug, T.; Kang, S.; Lee, D. F.; Goyal, A.; Payzant, E. A.; Salama, K.

    2003-11-01

    We have grown epitaxial CeO2 buffer layers on biaxially textured Ni-W substrates for YBCO coated conductors using a newly developed metal organic decomposition (MOD) approach. Precursor solution of 0.25 M concentration was spin coated on short samples of Ni-3 at%W (Ni-W) substrates and heat-treated at 1100 °C in a gas mixture of Ar-4%H2 for 15 min. Detailed x-ray studies indicate that CeO2 films have good out-of-plane and in-plane textures with full-width-half-maximum values of 5.8° and 7.5°, respectively. High temperature in situ XRD studies show that the nucleation of CeO2 films starts at 600 °C and the growth completes within 5 min when heated at 1100 °C. SEM and AFM investigations of CeO2 films reveal a fairly dense microstructure without cracks and porosity. Highly textured YSZ barrier layers and CeO2 cap layers were deposited on MOD CeO2-buffered Ni-W substrates using rf-magnetron sputtering. Pulsed laser deposition (PLD) was used to grow YBCO films on these substrates. A critical current, Jc, of about 1.5 MA cm-2 at 77 K and self-field was obtained on YBCO (PLD)/CeO2 (sputtered)/YSZ (sputtered)/CeO2 (spin-coated)/Ni-W.

  14. Electronic storage capacity of ceria: role of peroxide in Aux supported on CeO2(111) facet and CO adsorption.

    PubMed

    Liu, Yinli; Li, Huiying; Yu, Jun; Mao, Dongsen; Lu, Guanzhong

    2015-11-01

    Density functional theory (DFT+U) was used to study the adsorption of Aux (x = 1-4) clusters on the defective CeO2(111) facet and CO adsorption on the corresponding Aux/CeO2-x catalyst, in this work Aux clusters are adsorbed onto the CeO2-x + superoxide/peroxide surface. When Au1 is supported on the CeO2(111) facet with an O vacancy, the strong electronegative Au(δ-) formed is not favorable for CO adsorption. When peroxide is adsorbed on the CeO2(111) facet with the O vacancy, Aux was oxidized, resulting in stable Aux adsorption on the defective ceria surface with peroxide, which promotes CO adsorption on the Aux/CeO2-x catalyst. With more Au atoms in supported Aux clusters, CO adsorption on this surface becomes stronger. During both the Au being supported on CeO2-x and CO being adsorbed on Aux/CeO2-x, CeO2 acts as an electron buffer that can store/release the electrons. These results provide a scientific understanding for the development of high-performance rare earth catalytic materials.

  15. Synthesis of Fe3O4/SiO2/CeO2 core-shell magnetic and their application as photocatalyst.

    PubMed

    Channei, D; Inceesungvorn, B; Wetchakun, N; Phanichphant, S

    2014-10-01

    The Fe3O4/SiO2/CeO2 core-shell magnetic has been successfully synthesized by three steps of hydrothermal, sonochemical and homogeneous precipitation by coating CeO2 nanoparticles onto Fe3O4/SiO2 magnetic core. The prepared samples were characterized by X-ray diffraction (XRD), Field-emission scanning electron microscopy (FESEM) connected with energy dispersive X-ray analysis system (EDS), high resolution transmission electron microscopy (HRTEM), Nitrogen adsorption-desorption analyses (BET), and vibrating sample magnetometer (VSM). The photocatalytic activities for Fe3O4/SiO2/CeO2 core-shell magnetic under UV and visible lights were measured by determining the degradation rate of formic and oxalic acid in spiral reactor for 120 min. The amounts of CO2 generated during the process were compared between the magnetic catalyst and bare CeO2. After the finished photocatalytic degradation, the magnetic catalyst was recovered by external magnetic field at the end of each experiment. The results showed that the photocatalytic activity of Fe3O4/SiO2/CeO2 core-shell magnetic had higher than that of bare CeO2 and was found to be constant for three cycles of the recycled use.

  16. Yb,Er-doped CeO2 nanotubes as an assistant layer for photoconversion-enhanced dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Zhao, Rongfang; Huan, Long; Gu, Peng; Guo, Rong; Chen, Ming; Diao, Guowang

    2016-11-01

    Yb,Er-doped CeO2 nanotubes were successfully synthesized using Ag nanowires as a hard template via a facile hydrothermal reaction and subsequent calcination and leaching processes. Yb,Er-doped CeO2 nanotubes as a promising assistant layer were investigated to determine theirs photovoltaic properties in an effort to enhance the power conversion efficiency of dye-sensitized solar cells (DSSCs). The influence factors of photoelectric properties of CeO2:Yb,Er NTs, including diameter of nanotubes, hydrothermal time, calcination temperature, and elements doping, have been studied. Compared with pristine P25 photoanode, the DSSCs fabricated by CeO2:Yb,Er nanotubes and P25 exhibited a power conversion efficiency (η) of 8.67%, an increase of 34%, and incident photo-to-electric conversion efficiency (IPCE) of 92.96%, an increase of 48.83%, which evidence that CeO2:Yb,Er NTs are a promising assistant photoanode material for DSSCs. The enhance mechanism of CeO2:Yb,Er nanotubes has been further revealed according to experimental results.

  17. Epitaxial growth of ZnO film on Si(1 1 1) with CeO2(1 1 1) as buffer layer

    NASA Astrophysics Data System (ADS)

    Wong, T. I.; Tan, H. R.; Sentosa, D.; Wong, L. M.; Wang, S. J.; Feng, Y. P.

    2012-10-01

    ZnO(0 0 2) epitaxial films have been successfully grown on Si(1 1 1) with CeO2 as a buffer layer by pulsed laser deposition. In spite of large lattice mismatch between ZnO and CeO2, good film quality was achieved, as proven by Fourier filtered high-resolution transmission electron microscopy (HRTEM) image, due to reduction in interface strain by domain matching epitaxy. The epitaxial relationship of ZnO and CeO2 on the Si substrate was determined to be (0 0 2)[2 1 0]ZnO‖(1 1 1)[1 1 2] _CeO_2\\Vert (1 1 1)[1 1 2]Si. The HRTEM images show low defect concentrations in both the deposited ZnO film and CeO2 layer. Ordered crack lines are observed on the surface of the ZnO film which are due to A-type and B-type stackings of CeO2 on Si(1 1 1). Sharp near-band edge emission at 3.253 eV was detected for the ZnO film through photoluminiscence measurement at room temperature.

  18. The effects of physicochemical properties of CeO2 nanoparticles on toxicity to soil denitrification processes

    NASA Astrophysics Data System (ADS)

    Dahle, Jessica Teague

    The studies presented in this thesis identify the impact of NP CeO 2 on soil denitrifying microbial communities and reveal that physical and chemical characteristics including particle size, speciation, concentration, pH, and presence of ligands are key to predicting environmental fate and reactivity of NP CeO2 in the soil. A review of the literature in Chapter 1 revealed a widespread lack of toxicological information for soil exposures to NP CeO2. Soil denitrifying bacteria are a keystone species because they serve an important role in the global nitrogen cycle controlling the atmospheric nitrogen input. Soil denitrifiers are important to this study because the reducing conditions during denitrification could induce phase transformation of Ce(IV) to Ce(III), potentially influencing the toxicity of Ce. Cerium is well known for being the only lanthanide that is thermodynamically stable in both the trivalent and tetravalent state in low temperature geochemical environments. Using well characterized NP Ce(IV)O 2 as well as bulk soluble Ce(III), batch denitrification experiments were conducted to evaluate the toxicity of Ce species to the denitrifying community in a Toccoa sandy loam soil. The statistical analysis on the antimicrobial effect on soil denitrifiers was conducted using both steady-state evaluation and zero-order kinetic models in order to compare the toxicity of the Ce(III) species to the NPs. These studies, presented in Chapter 3, show that soluble Ce(III) is far more toxic than Ce(IV)O2 NPs when an equal total concentration of Ce is used, though both species exhibit toxicity to the denitrifiers via statistically significant inhibition of soil denitrification processes. Particle-size dependent toxicity, species-dependent toxicity, and concentration-dependent toxicity were all observed in this study for both the steady-state and the kinetic evaluations. The possibility of toxicity enhancement and diminishment via dissolution and ligand complexation pathways was investigated thoroughly in Chapter 2. In addition to the equilibrium and kinetic-based toxicological assessments presented in Chapter 1, dissolution and sorption experiments were performed to gain an overall understanding of Ce biogeochemistry in the terrestrial environment post-release and reveal possible geochemical controls on toxicity. It was shown that dissolution of bioavailable Ce is pH-dependent; dissolution is only detectable at acidic pH values (< pH 5) and increases with increasing acidity. Dissolution of Ce from NP CeO2 was identified to be almost 100% Ce(III). It was also demonstrated that this dissolution is suppressed by the addition of phosphate ligand, which is largely bioavailable in soils, especially in agricultural lands. This suppression was explained by the strong sorption of phosphate ligand to NP CeO2. The elimination of bioavailable Ce(III) release from NP CeO2 by phosphate ligand is likely one of the most important controls on toxicity effects and should be a large consideration in determining the fate and transport of NP CeO2 in the aquatic and terrestrial environment. It was also demonstrated that both Ce(III) and NP CeO2 have extremely strong affinity for sorption to soil matter, which could serve as another controlling pathway. Experiments indicated that factors such as reductive transformation of NP CeO2 in soils and exchangeable Ce(III) impurity in the NPs could contribute to controls on toxicity as well. In conclusion, the studies presented in this thesis indicate that the toxicity effects of the studied Ce species to soil denitrifiers are strongly affected by physical and chemical characteristics such as speciation, pH, and bioavailable ligands. As the global market for nanomaterials rapidly expands, so does the need of the scientific community for an understanding of how these influences in environmental fate and reactivity may be key in assessing toxicological risks associated with environmental exposures to NP CeO2 as well as other engineered metal oxide nanoparticles. (Abstract shortened by UMI.)

  19. The Effect of CeO2 Antireflection Layer on the Optical Properties of Thermochromic VO2 Film for Smart Window System

    NASA Astrophysics Data System (ADS)

    Koo, Hyun; Shin, Dongmin; Bae, Sung-Hwan; Ko, Kyeong-Eun; Chang, Se-Hong; Park, Chan

    2013-11-01

    CeO2-VO2 bilayer structure was fabricated to investigate the effect of depositing CeO2 film on the optical properties of VO2 film for smart window application. CeO2 was employed as an antireflection (AR) layer material of VO2 film because of its advantages which include high transparency in the visible-near infrared range and high refractive index. All the films were deposited on soda-lime glass substrate by pulsed laser deposition method. Optical calculations were carried out using transfer-matrix method for the purpose of designing CeO2-VO2 bilayer structure with enhanced integrated luminous transmittance (T lum) and switching efficiency (ΔT sol). The optical constants of VO2 and CeO2 films needed for the optical calculation were measured by spectroscopic ellipsometer. The curve of T lum the shape of which depends on the thickness of CeO2 layer, was calculated in each VO2 sample, which showed two maxima. The samples were divided into two groups; one for the highest enhancement of T lum and the other for balanced enhancement between T lum and ΔT sol. The sample with the structure of ~60 nm CeO2 AR layer on 39-nm thick VO2 film showed large increase of T lum (~27%) with ΔT sol of ~5%, which is the largest increase in T lum reported so far. Two samples in the other group showed the balanced enhancement in T lum (~57, ~50%) and ΔT sol (~9, ~10.5%). The effect of CeO2 AR layer on the optical properties of VO2 film was confirmed with the optical calculation and the experimental results. CeO2-VO2 bilayer structure showed notable improvement of optical properties compared to the single VO2 film, indicating that CeO2 layer can be effectively used as the antireflection layer while working as a protective layer that can prevent the oxidation of VO2 layer as well.

  20. Rose Bengal sensitized bilayered photoanode of nano-crystalline TiO2-CeO2 for dye-sensitized solar cell application

    NASA Astrophysics Data System (ADS)

    Sayyed, Suhail A. A. R.; Beedri, Niyamat I.; Kadam, Vishal S.; Pathan, Habib M.

    2016-08-01

    The present work deals with the study of TiO2-CeO2 bilayered photoanode with low-cost Rose Bengal (RB) dye as sensitizer for dye-sensitized solar cell application. The recombination reactions are reduced in bilayered TiO2-CeO2 photoanode as compared to the single-layered CeO2 photoanode. Once the electrons get transferred from lowest unoccupied molecular orbital level of RB dye to the conduction band (CB) of TiO2, then the possibilities of recombination of electrons with oxidized dye molecules or oxidized redox couple are reduced. This is because the CB position of CeO2 is higher than that of TiO2, which blocks the path of electrons. The electrochemical impedance spectroscopy (EIS) analysis shows negative shift in frequency for bilayered TiO2-CeO2 photoanode as compared to CeO2 photoanode. Hence, in bilayered photoanode lifetime of electrons is more than in single-layered photoanode, confirming reduction in recombination reactions. The X-ray diffraction patterns confirm both anatase TiO2 and CeO2 with crystalline size using Scherrer formula as 24 and 10 nm, respectively. The scanning electron microscopy images of photoanode show the porous structure useful for dye adsorption. The presence of Ti and Ce is confirmed by electron diffraction studies. The band gap values for TiO2 and CeO2 were calculated as 3.20 and 3.11 eV, respectively, using diffused reflectance spectroscopy. The bilayered TiO2-CeO2 photoanode showed open-circuit voltage ( V OC) ~500 mV and short-circuit photocurrent density ( J SC) ~0.29 mA/cm2 with fill factor (FF) ~62.17 %. There is increase in V OC and J SC values by 66.67 and 38.10 %, respectively, compared to RB-sensitized CeO2 photoanode.

  1. Toxicity of CeO2 nanoparticles at different trophic levels--effects on diatoms, chironomids and amphibians.

    PubMed

    Bour, Agathe; Mouchet, Florence; Verneuil, Laurent; Evariste, Lauris; Silvestre, Jérôme; Pinelli, Eric; Gauthier, Laury

    2015-02-01

    The aim of the present work is to provide wider information on the toxicity of cerium dioxide nanoparticles (CeO2 NPs) in aquatic environments, by studying the toxicity of two types of CeO2 NPs for four species (diatoms Nitzschia palea, the sediment-dwelling invertebrate Chironomus riparius, and the amphibian larvae Xenopus laevis and Pleurodeles waltl.). The two types of CeO2 NPs have different intrinsic properties: some of them are small citrate-coated spheres (2-5 nm), and the others are larger uncoated plates (20-60 nm). Acute toxicity (mortality at 48 or 96 h, depending on the test-organism) was assessed for the four species, from 0.1 to 100 mg L(-1) of NPs. Sub-lethal effects were assessed on chironomids exposed between 0.01 and 1 mg L(-1) of NPs. Mortality, growth inhibition and genotoxic effects were evaluated on amphibian larvae from 0.1 to 10 mg L(-1). Results reveal that no acute toxicity occurs on any species after short exposures, even at the highest concentrations. Mortality (35%) is observed on Xenopus larvae after 12d of exposure at the highest concentration of one type of NPs. No significant effects were observed on chironomids during chronic exposure. Xenopus larvae growth was inhibited from 1 mg L(-1) of both NPs while growth inhibition is observed on Pleurodeles only at the highest concentration of one type of NPs. No genotoxicity was observed on Xenopus but Pleurodeles exhibited dose-dependent genotoxic effects when exposed to one type of NPs. Observed differences in toxicity are discussed focusing on the studied compartment, routes of exposure, species and NPs.

  2. CeO2-TiO2 sorbents for the removal of elemental mercury from syngas.

    PubMed

    Zhou, Jinsong; Hou, Wenhui; Qi, Pan; Gao, Xiang; Luo, Zhongyang; Cen, Kefa

    2013-09-01

    A series of CeO2-TiO2 (CeTi) sorbents with different CeO2/TiO2 mass ratios were prepared by an impregnation method and employed to remove elemental mercury (Hg(0)) in simulated syngas. The CeTi sorbents with a CeO2/TiO2 mass ratio of 0.2 exhibited superior Hg(0) removal efficiency from 80 to 150 °C, which could be ascribed to the greater amount of surface chemisorbed oxygen resulted from Ce(3+) on the sample surface. H2S was the most effective syngas component responsible for Hg(0) removal. The use of 400 ppm H2S resulted in 98% Hg(0) removal efficiency under the experimental conditions. H2 and CO had a negligible effect on the efficiency of Hg removal. In the presence of H2S, a prohibitive effect of HCl and NH3 on Hg(0) removal was observed because of the consumption of the surface oxygen. Water vapor also inhibited Hg(0) removal due to competitive adsorption with H2S. Hg(0) removal over CeTi sorbents was proposed to follow the Eley-Rideal mechanism, in which active surface sulfur reacts with gas-phase Hg(0). This large oxygen storage capacity of CeTi sorbents is quite favorable to H2S catalytic oxidation and Hg(0) emission control in an extremely reducing environment, such as when there is a deficiency of O2.

  3. Fabrication and dye removal performance of magnetic CuFe2O4@CeO2 nanofibers

    NASA Astrophysics Data System (ADS)

    Zou, Lianli; Wang, Qiuju; Shen, Xiangqian; Wang, Zhou; Jing, Maoxiang; Luo, Zhou

    2015-03-01

    Novel magnetic adsorbents with CeO2 nanoparticles (about 20 nm) coated on CuFe2O4 nanofibers were fabricated by combining electrospinning technique and chemical precipitation methods. The prepared CuFe2O4@CeO2 composite nanofibers show a diameter of 200 nm with a high specific surface area of 64.12 m2/g. These composite nanofibers exhibit a typical soft-magnetic materials behavior with a specific saturation magnetization (Ms) of 20.51 Am2/kg. The adsorption performances of these composite nanofibers were evaluated by column bed studies for methyl orange (MO) removal from aqueous solution. The effect of pH, flow rate and dye concentration on adsorption performances were investigated. The results show that the adsorption capacity decreases with increase of pH. The largest adsorption capacity of the column beds shows about 100 g/mL under the condition of C0 = 0.05 mg/mL, F = 2.0 mL/min and pH 4.0. The kinetic process is described by Thomas model. The rate constant decreases with the extension of reaction time and decreasing pH. The desorption behaviors are also studied in 0.5 M NaCl solution, ethyl alcohol and deionized water, respectively, which show that the adsorbed MO molecules can be easily desorbed from CuFe2O4@CeO2 composite nanofibers in NaCl solution. The adsorption mechanism of ionic interaction, formation of hydrogen bonds and pore diffusion is rationally proposed.

  4. Extracellular Polymeric Substances (EPS) of Freshwater Biofilms Stabilize and Modify CeO2 and Ag Nanoparticles

    PubMed Central

    Kroll, Alexandra; Behra, Renata; Kaegi, Ralf; Sigg, Laura

    2014-01-01

    Streams are potential receiving compartments for engineered nanoparticles (NP). In streams, NP may remain dispersed or settle to the benthic compartment. Both dispersed and settling NP can accumulate in benthic biofilms called periphyton that are essential to stream ecosystems. Periphytic organisms excrete extracellular polymeric substances (EPS) that interact with any material reaching the biofilms. To understand the interaction of NP with periphyton it is therefore crucial to study the interaction of NP with EPS. We investigated the influence of EPS on the physicochemical properties of selected NP (CeO2, Ag) under controlled conditions at pH 6, 7.6, 8.6 and light or dark exposure. We extracted EPS from five different periphyton communities, characterized the extracts, and exposed CeO2 and carbonate-stabilized Ag NP (0.5 and 5 mg/L, both 25 nm primary particle size) and AgNO3 to EPS (10 mg/L) over two weeks. We measured NP size distribution, shape, primary particle size, surface plasmon resonance, and dissolution. All EPS extracts were composed of biopolymers, building blocks of humic substances, low molecular weight (Mr) acids, and small amphiphilic or neutral compounds in varying concentrations. CeO2 NP were stabilized by EPS independent of pH and light/dark while dissolution increased over time in the dark at pH 6. EPS induced a size increase in Ag NP in the light with decreasing pH and the formation of metallic Ag NP from AgNO3 at the same conditions via EPS-enhanced photoreduction. NP transformation and formation were slower in the extract with the lowest biopolymer and low Mr acid concentrations. Periphytic EPS in combination with naturally varying pH and light/dark conditions influence the properties of the Ag and CeO2 NP tested and thus the exposure conditions within biofilms. Our results indicate that periphytic organisms may be exposed to a constantly changing mixture of engineered and naturally formed Ag NP and Ag+. PMID:25333364

  5. Orange Peel Oxidative Gasification on Ni Catalysts Promoted with CaO, CeO2 or K2O.

    PubMed

    Vargas, G; Zapata, B; Valenzuela, M A; Alfaro, S

    2015-09-01

    Orange peel can be considered as an attractive raw material to be gasified for hydrogen or syngas production. In this work, the catalytic evaluation of several silica-supported nickel catalysts in the oxidative degradation of waste orange peel is reported. It was found that the catalytic gasification with the K2O-Ni/silica catalyst produces more hydrogen than the non-catalytic route at 600 degrees C. Surprisingly, a significant amount of ethene was obtained with the CeO2-Ni/silica catalyst, which was explained in terms of an oxidative dehydrogenation reaction of ethane formed during biomass or tar decomposition. PMID:26716225

  6. Citric acid modifies surface properties of commercial CeO2 nanoparticles reducing their toxicity and cerium uptake in radish (Raphanus sativus) seedlings.

    PubMed

    Trujillo-Reyes, J; Vilchis-Nestor, A R; Majumdar, S; Peralta-Videa, J R; Gardea-Torresdey, J L

    2013-12-15

    Little is known about the mobility, reactivity, and toxicity to plants of coated engineered nanoparticles (ENPs). Surface modification may change the interaction of ENPs with living organisms. This report describes surface changes in commercial CeO2 NPs coated with citric acid (CA) at molar ratios of 1:2, 1:3, 1:7, and 1:10 CeO2:CA, and their effects on radish (Raphanus sativus) seed germination, cerium and nutrients uptake. All CeO2 NPs and their absorption by radish plants were characterized by TEM, DLS, and ICP-OES. Radish seeds were germinated in pristine and CA coated CeO2 NPs suspensions at 50mg/L, 100mg/L, and 200mg/L. Deionized water and CA at 100mg/L were used as controls. Results showed ζ potential values of 21.6 mV and -56 mV for the pristine and CA coated CeO2 NPs, respectively. TEM images showed denser layers surrounding the CeO2 NPs at higher CA concentrations, as well as better distribution and smaller particle sizes. None of the treatments affected seed germination. However, at 200mg/L the CA coated NPs at 1:7 ratio produced significantly (p ≤ 0.05) more root biomass, increased water content and reduced by 94% the Ce uptake, compared to bare NPs. This suggests that CA coating decrease CeO2 NPs toxicity to plants. PMID:24231324

  7. Reel-to-reel continuous simultaneous double-sided deposition of highly textured CeO2 templates for YBa2Cu3O7-δ coated conductors

    NASA Astrophysics Data System (ADS)

    Xiong, J.; Tao, B. W.; Qin, W. F.; Tang, J. L.; Han, X.; Li, Y. R.

    2008-02-01

    A reel-to-reel system which allows simultaneous two-sided deposition of epitaxial CeO2 buffer layers on long length biaxially textured Ni-5 at.%W tape with direct current (dc) reactive magnetron sputtering is described. Deposition is accomplished through two opposite symmetrical sputtering guns with a radiation heater. Meter-long double-sided epitaxial CeO2 buffer layers have been produced for the first time on textured metal substrates in a run using a reel-to-reel process with a speed of about 1.2 m h-1. The CeO2 films were characterized by means of x-ray diffraction (XRD) and atomic force microscopy (AFM). The samples exhibited good epitaxial growth with the c-axis perpendicular to the substrate surface for both sides. Full width at half maximum (FWHM) values of the out-of-plane and in-plane orientation for both sides were 3.2° and 3.1°, 5.3° and 5.1°, respectively. AFM observations revealed a smooth, dense and crack-free surface morphology. In addition, x-ray scans have been performed as a function of length to determine the crystallographic consistency of the epitaxial CeO2 over the length. Subsequently anyttria-stabilized zirconia (YSZ) barrier and CeO2 cap layers were deposited to complete the CeO2/YSZ/CeO2 structure via the same process. Epitaxial YBa2Cu3O7-δ (YBCO) films grown by dc sputtering on the short prototype CeO2/YSZ/CeO2/NiW conductors yielded self-field critical current densities (Jc) as high as 1.3 MA cm-2 at 77 K. An Ic value of 113 A cm-1 was obtained for double-sided YBCO coated conductors.

  8. MnO(x) Nanoparticle-Dispersed CeO2 Nanocubes: A Remarkable Heteronanostructured System with Unusual Structural Characteristics and Superior Catalytic Performance.

    PubMed

    Putla, Sudarsanam; Amin, Mohamad Hassan; Reddy, Benjaram M; Nafady, Ayman; Al Farhan, Khalid A; Bhargava, Suresh K

    2015-08-01

    Understanding the interface-induced effects of heteronanostructured catalysts remains a significant challenge due to their structural complexity, but it is crucial for developing novel applied catalytic materials. This work reports a systematic characterization and catalytic evaluation of MnOx nanoparticle-dispersed CeO2 nanocubes for two important industrial applications, namely, diesel soot oxidation and continuous-flow benzylamine oxidation. The X-ray diffraction and Raman studies reveal an unusual lattice expansion in CeO2 after the addition of MnOx. This interesting observation is due to conversion of smaller sized Ce(4+) (0.097 nm) to larger sized Ce(3+) (0.114 nm) in cerium oxide led by the strong interaction between MnOx and CeO2 at their interface. Another striking observation noticed from transmission electron microscopy, high angle annular dark-field scanning transmission electron microscopy, and electron energy loss spectroscopy studies is that the MnOx species are well-dispersed along the edges of the CeO2 nanocubes. This remarkable decoration leads to an enhanced reducible nature of the cerium oxide at the MnOx/CeO2 interface. It was found that MnOx/CeO2 heteronanostructures efficiently catalyze soot oxidation at lower temperatures (50% soot conversion, T50 ∼660 K) compared with that of bare CeO2 nanocubes (T50 ∼723 K). Importantly, the MnOx/CeO2 heteronanostructures exhibit a noticeable steady performance in the oxidation of benzylamine with a high selectivity of the dibenzylimine product (∼94-98%) compared with that of CeO2 nanocubes (∼69-91%). The existence of a strong synergistic effect at the interface sites between the CeO2 and MnOx components is a key factor for outstanding catalytic efficiency of the MnOx/CeO2 heteronanostructures.

  9. Identification of the arsenic resistance on MoO3 doped CeO2/TiO2 catalyst for selective catalytic reduction of NOx with ammonia.

    PubMed

    Li, Xiang; Li, Xiansheng; Li, Junhua; Hao, Jiming

    2016-11-15

    Arsenic resistance on MoO3 doped CeO2/TiO2 catalysts for selective catalytic reduction of NOx with NH3 (NH3-SCR) is investigated. It is found that the activity loss of CeO2-MoO3/TiO2 caused by As oxide is obvious less than that of CeO2/TiO2 catalysts. The fresh and poisoned catalysts are compared and analyzed using XRD, Raman, XPS, H2-TPR and in situ DRIFTS. The results manifest that the introduction of arsenic oxide to CeO2/TiO2 catalyst not only weakens BET surface area, surface acid sites and adsorbed NOx species, but also destroy the redox circle of Ce(4+) to Ce(3+) because of interaction between Ce and As. When MoO3 is added into CeO2/TiO2 system, the main SCR reaction path are found to be changed from the reaction between coordinated NH3 and ad-NOx species to that between an amide and gaseous NO. Additionally, for CeO2-MoO3/TiO2 catalyst, As toxic effect on active sites CeO2 can be released because of stronger As-Mo interaction. Moreover, not only are the reactable Brønsted and Lewis acid sites partly restored, but the cycle of Ce(4+) to Ce(3+) can also be free to some extent. PMID:27474851

  10. Enhancement of photocatalytic properties of TiO2 nanoparticles doped with CeO2 and supported on SiO2 for phenol degradation

    NASA Astrophysics Data System (ADS)

    Hao, Chunjing; Li, Jing; Zhang, Zailei; Ji, Yongjun; Zhan, Hanhui; Xiao, Fangxing; Wang, Dan; Liu, Bin; Su, Fabing

    2015-03-01

    A series of CeO2-TiO2 and CeO2-TiO2/SiO2 composites were prepared with TiCl4 and Ce (NO3)3·6H2O as precursors via a facile co-precipitation method. The obtained samples were characterized by various techniques such as X-ray diffraction (XRD), nitrogen adsorption (N2-BET), Fourier transformation infrared spectrum (FT-IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and UV-Vis spectroscopy measurements. The results indicated that TiO2 doped with CeO2 and supported on SiO2 could reduce the crystallite size, inhibit the phase transformation, enhance the thermal stability, and effectively extend the spectral response from UV to visible range. When applied to the phenol photodegradation on a homemade batch reactor with an external cooling jacket, the CeO2-TiO2/SiO2 catalysts exhibited significantly enhanced photodegradation efficiency in comparison with commercial Degussa P25 and CeO2-TiO2. The unique catalytic properties of CeO2-TiO2/SiO2 were ascribed to improved electron-hole pairs separation efficiency and formation of more reactive oxygen species owing to the presence of Ce3+/Ce4+, as well as high dispersion of active component of CeO2-TiO2 as a result of the introduction of SiO2 support. Furthermore, the catalysts can be easily recovered from the reaction solution by centrifugation and reused for four cycles without significant loss of activity.

  11. Aspect Ratio Plays a Role in the Hazard Potential of CeO2 Nanoparticles in Mouse Lung and Zebrafish Gastrointestinal Tract

    PubMed Central

    Lin, Sijie; Wang, Xiang; Ji, Zhaoxia; Chang, Chong Hyun; Dong, Yuan; Meng, Huan; Liao, Yu-Pei; Wang, Meiying; Song, Tze-Bin; Kohan, Sirus; Xia, Tian; Zink, Jeffrey I.; Lin, Shuo; Nel, André E.

    2014-01-01

    We have previously demonstrated that there is a relationship between the aspect ratio (AR) of CeO2 nanoparticles and in vitro hazard potential. CeO2 nanorods with AR ≥ 22 induced lysosomal damage and progressive effects on IL-1β production and cytotoxicity in the human myeloid cell line, THP-1. In order to determine whether this toxicological paradigm for long aspect ratio (LAR) CeO2 is also relevant in vivo, we performed comparative studies in the mouse lung and gastrointestinal tract (GIT) of zebrafish larvae. Although oropharyngeal aspiration could induce acute lung inflammation for CeO2 nanospheres and nanorods, only the nanorods with the highest AR (C5) induced significant IL-1β and TGF-β1 production in the bronchoalveolar lavage fluid (BALF) at 21 days but not inducing pulmonary fibrosis. However, after a longer duration (44 days) exposure to 4 mg/kg of the C5 nanorods, more collagen production was seen with CeO2 nanorods vs. nanospheres after correcting for Ce lung burden. Using an oral-exposure model in zebrafish larvae, we demonstrated that C5 nanorods also induced significant growth inhibition, a decrease in body weight, and delayed vertebral calcification. In contrast, CeO2 nanospheres and shorter nanorods had no effect. Histological and transmission electron microscopy (TEM) analyses showed that the key injury mechanism of C5 was in the epithelial lining of the GIT, which demonstrated blunted microvilli and compromised digestive function. All considered, these data demonstrate that, similar to cellular studies, LAR CeO2 nanorods exhibit more toxicity in the lung and GIT, which could be relevant to inhalation and environmental hazard potential. PMID:24720650

  12. Buffer layers for high-Tc thin films on sapphire

    NASA Technical Reports Server (NTRS)

    Wu, X. D.; Foltyn, S. R.; Muenchausen, R. E.; Cooke, D. W.; Pique, A.; Kalokitis, D.; Pendrick, V.; Belohoubek, E.

    1992-01-01

    Buffer layers of various oxides including CeO2 and yttrium-stabilized zirconia (YSZ) have been deposited on R-plane sapphire. The orientation and crystallinity of the layers were optimized to promote epitaxial growth of YBa2Cu3O(7-delta) (YBCO) thin films. An ion beam channeling minimum yield of about 3 percent was obtained in the CeO2 layer on sapphire, indicating excellent crystallinity of the buffer layer. Among the buffer materials used, CeO2 was found to be the best one for YBCO thin films on R-plane sapphire. High Tc and Jc were obtained in YBCO thin films on sapphire with buffer layers. Surface resistances of the YBCO films were about 4 mOmega at 77 K and 25 GHz.

  13. Effects of nanocrystalline CeO2 supports on the properties and performance of Ni–Rh bimetallic catalyst for oxidative steam reforming of ethanol

    SciTech Connect

    Kugai, Junichiro; Subramani, Velu; Song, Chunshan; Engelhard, Mark H.; Chin, Ya-Huei

    2006-03-10

    This study focuses on the effects of the CeO2 support properties on the catalyst properties and performance of bimetallic Ni?Rh/CeO2 catalysts containing 5 wt% Ni and 1 wt% Rh for the oxidative steam reforming (OSR) of ethanol for hydrogen production and fuel cell applications. Three CeO2 supports with different crystal sizes and surface areas were examined. The surface areas of these supports increases in the order of CeO2-I (74 m2/g) < CeO2-II (92 m2/g) < CeO2-III (154 m2/g), but their crystallite sizes were about 10.2, 29.3, and 6.5 nm, respectively. The properties of Ni?Rh/CeO2 catalysts were investigated by XRD, TPR, H2 chemisorption, and in situ XPS techniques. The Rh metal dispersion increased while the Ni metal dispersion decreased with decreasing crystallite sizes of CeO2. TPR studies revealed the existence of a Rh?CeO2 metal?support interaction as well as Ni?Rh interaction in the Ni?Rh bimetallic catalyst supported on CeO2-III with a crystallite size of about 6.5 nm. The in situ XPS studies corroborated the TPR results. The reduced Ni and Rh species were reversibly oxidized, suggesting the existence of Ni?Rh redox species rather than NiRh surface alloy in the present catalyst system. The Rh species became highly dispersed when the crystallite size of CeO2 support was smaller. Comparing the catalytic performance in the OSR of ethanol was compared with the properties of the catalysts demonstrated that both ethanol conversion and H2 selectivity increased and the selectivity for undesirable byproducts decreased with increasing Rh metal dispersion. Best catalytic performance for OSR was achieved by supporting Ni?Rh bimetallic catalysts on the nanocrystalline CeO2-III. The Ni?Rh/CeO2-III catalyst exhibited stable activity and selectivity during on-stream operations at 450 C and as well as at 600 C.

  14. Designing CuOx Nanoparticle-Decorated CeO2 Nanocubes for Catalytic Soot Oxidation: Role of the Nanointerface in the Catalytic Performance of Heterostructured Nanomaterials.

    PubMed

    Sudarsanam, Putla; Hillary, Brendan; Mallesham, Baithy; Rao, Bolla Govinda; Amin, Mohamad Hassan; Nafady, Ayman; Alsalme, Ali M; Reddy, B Mahipal; Bhargava, Suresh K

    2016-03-01

    This work investigates the structure-activity properties of CuOx-decorated CeO2 nanocubes with a meticulous scrutiny on the role of the CuOx/CeO2 nanointerface in the catalytic oxidation of diesel soot, a critical environmental problem all over the world. For this, a systematic characterization of the materials has been undertaken using transmission electron microscopy (TEM), transmission electron microscopy-energy-dispersive X-ray spectroscopy (TEM-EDS), high-angle annular dark-field-scanning transmission electron microscopy (HAADF-STEM), scanning transmission electron microscopy-electron energy loss spectroscopy (STEM-EELS), X-ray diffraction (XRD), Raman, N2 adsorption-desorption, and X-ray photoelectron spectroscopy (XPS) techniques. The TEM images show the formation of nanosized CeO2 cubes (∼25 nm) and CuOx nanoparticles (∼8.5 nm). The TEM-EDS elemental mapping images reveal the uniform decoration of CuOx nanoparticles on CeO2 nanocubes. The XPS and Raman studies show that the decoration of CuOx on CeO2 nanocubes leads to improved structural defects, such as higher concentrations of Ce(3+) ions and abundant oxygen vacancies. It was found that CuOx-decorated CeO2 nanocubes efficiently catalyze soot oxidation at a much lower temperature (T50 = 646 K, temperature at which 50% soot conversion is achieved) compared to that of pristine CeO2 nanocubes (T50 = 725 K) under tight contact conditions. Similarly, a huge 91 K difference in the T50 values of CuOx/CeO2 (T50 = 744 K) and pristine CeO2 (T50 = 835 K) was found in the loose-contact soot oxidation studies. The superior catalytic performance of CuOx-decorated CeO2 nanocubes is mainly attributed to the improved redox efficiency of CeO2 at the nanointerface sites of CuOx-CeO2, as evidenced by Ce M5,4 EELS analysis, supported by XRD, Raman, and XPS studies, a clear proof for the role of nanointerfaces in the performance of heterostructured nanocatalysts. PMID:26886079

  15. Designing CuOx Nanoparticle-Decorated CeO2 Nanocubes for Catalytic Soot Oxidation: Role of the Nanointerface in the Catalytic Performance of Heterostructured Nanomaterials.

    PubMed

    Sudarsanam, Putla; Hillary, Brendan; Mallesham, Baithy; Rao, Bolla Govinda; Amin, Mohamad Hassan; Nafady, Ayman; Alsalme, Ali M; Reddy, B Mahipal; Bhargava, Suresh K

    2016-03-01

    This work investigates the structure-activity properties of CuOx-decorated CeO2 nanocubes with a meticulous scrutiny on the role of the CuOx/CeO2 nanointerface in the catalytic oxidation of diesel soot, a critical environmental problem all over the world. For this, a systematic characterization of the materials has been undertaken using transmission electron microscopy (TEM), transmission electron microscopy-energy-dispersive X-ray spectroscopy (TEM-EDS), high-angle annular dark-field-scanning transmission electron microscopy (HAADF-STEM), scanning transmission electron microscopy-electron energy loss spectroscopy (STEM-EELS), X-ray diffraction (XRD), Raman, N2 adsorption-desorption, and X-ray photoelectron spectroscopy (XPS) techniques. The TEM images show the formation of nanosized CeO2 cubes (∼25 nm) and CuOx nanoparticles (∼8.5 nm). The TEM-EDS elemental mapping images reveal the uniform decoration of CuOx nanoparticles on CeO2 nanocubes. The XPS and Raman studies show that the decoration of CuOx on CeO2 nanocubes leads to improved structural defects, such as higher concentrations of Ce(3+) ions and abundant oxygen vacancies. It was found that CuOx-decorated CeO2 nanocubes efficiently catalyze soot oxidation at a much lower temperature (T50 = 646 K, temperature at which 50% soot conversion is achieved) compared to that of pristine CeO2 nanocubes (T50 = 725 K) under tight contact conditions. Similarly, a huge 91 K difference in the T50 values of CuOx/CeO2 (T50 = 744 K) and pristine CeO2 (T50 = 835 K) was found in the loose-contact soot oxidation studies. The superior catalytic performance of CuOx-decorated CeO2 nanocubes is mainly attributed to the improved redox efficiency of CeO2 at the nanointerface sites of CuOx-CeO2, as evidenced by Ce M5,4 EELS analysis, supported by XRD, Raman, and XPS studies, a clear proof for the role of nanointerfaces in the performance of heterostructured nanocatalysts.

  16. Sm doped mesoporous CeO2 nanocrystals: aqueous solution-based surfactant assisted low temperature synthesis, characterization and their improved autocatalytic activity.

    PubMed

    Mandal, Bappaditya; Mondal, Aparna; Ray, Sirsendu Sekhar; Kundu, Amar

    2016-01-28

    Mesoporous Sm(3+) doped CeO2 (Ce-Sm) with a nanocrystalline framework, a high content of Ce(3+) and surface area (184 m(2) g(-1)), have been synthesized through a facile aqueous solution-based surfactant assisted route by using inorganic precursors and sodium dodecyl sulphate as a template. The XRD results indicate that the calcined Ce-Sm and even the as-prepared material have a cubic fluorite structure of CeO2 with no crystalline impurity phase. XRD studies along with HRTEM results confirmed the formation of mesoporous nanocrystalline CeO2 at a lower temperature as low as 100 °C. A detailed analysis revealed that Sm(3+) doping in CeO2 has increased the lattice volume, surface area, mesopore volume and engineered the surface defects. Higher concentrations of Ce(3+) and oxygen vacancies of Ce-Sm resulted in lowering of the band gap. It is evident from the H2-TPR results that Sm(3+) doping in CeO2 strongly modified the reduction behavior of CeO2 by shifting the bulk reduction at a much lower temperature, indicating increased oxygen mobility in the sample which enables enhanced oxygen diffusion at lower temperatures, thus promoting reducibility, i.e., the process of Ce(4+)→ Ce(3+). UV-visible transmission studies revealed improved autocatalytic performance due to easier Ce(4+)/Ce(3+) recycling in the Sm(3+) doped CeO2 nanoparticles. From the in vitro cytotoxicity of both pure CeO2 and Sm(3+) doped CeO2 calcined at 500 °C in a concentration as high as 100 μg mL(-1) (even after 120 h) on MG-63 cells, no obvious decrease in cell viability is observed, confirming their excellent biocompatibility. The presence of an increased amount of surface hydroxyl groups, mesoporosity, and surface defects have contributed towards an improved autocatalytic activity of mesoporous Ce-Sm, which appear to be a potential candidate for biomedical (antioxidant) applications.

  17. Inclined Substrate Deposited CeO2 Films by Electron Beam Evaporation on Randomly Oriented Metallic Substrate

    NASA Astrophysics Data System (ADS)

    Mancini, A.; Celentano, G.; Fabbri, F.; Galluzzi, V.; Petrisor, T.; Rufoloni, A.; Varesi, E.; Vannozzi, A.; Rogai, R.; Boffa, V.; Gambardella, U.

    A study on CeO2 film growth on randomly oriented metallic substrate using lnclined Substrate Deposition (ISD) technique was performed in order to develop a biaxially aligned buffer layer for YBa2Cu3O7-δ (YBCO) coated conductors. The influence of deposition parameters, as the substrate inclination angle α with respect to the CeO2 vapor direction, deposition temperature and film thickness, on structural and morphological properties of the film was investigated. At substrate temperature between 200°C and 700°C a biaxial texture was observed for α ranging from 150° to 75°. The minimum value of the φ-scan full width at half maximum (FWHM) on (002) poles of about 13.5° was obtained for film 2 μm thick deposited at 200°C and α=55°. Morphological analyses on cross-sectioned samples revealed a columnar structure, typical for this deposition technique, with spaced grains and a tile like surface.

  18. Nonhydrolytic Synthesis and Electronic Structure of Ligand-Capped CeO2-.delta. and CeOCl Nanocrystals

    SciTech Connect

    Depner, S.; Kort, K; Jaye, C; Fischer, D; Banerjee, S

    2009-01-01

    A novel and versatile nonhydrolytic approach is developed for the synthesis of ligand-passivated CeO2-5 and CeOCl nanocrystals soluble in nonpolar organic solvents based on the condensation of cerium alkoxides with cerium halides. The alkyl group on the metal alkoxides and the specific halide used in the synthesis are observed to considerably influence the composition and size of the obtained nanocrystals. The obtained nanocrystals are <3 nm in diameter and, owing to their surface-capping groups, yield homogeneous and clear solutions in nonpolar organic solvents with no evidence of agglomeration. The electronic structure of the obtained CeO2-5 nanocrystals has been studied using optical absorption spectroscopy and near-edge X-ray absorption fine structure spectroscopy at Ce M- and O K-edges. The latter technique provides detailed insight into the metal valence, geometric structure, and atom-projected density of states in these nanocrystals. Finally, this synthesis method has been expanded to explore the doping of La to form solid-solution CexLa1-xO2-5 nanocrystals.

  19. Anchoring noble metal nanoparticles on CeO2 modified reduced graphene oxide nanosheets and their enhanced catalytic properties.

    PubMed

    Ji, Zhenyuan; Shen, Xiaoping; Xu, Yuling; Zhu, Guoxing; Chen, Kangmin

    2014-10-15

    The strategy of structurally integrating noble metal, metal oxide, and graphene is expected to offer prodigious opportunities toward emerging functions of graphene-based nanocomposites. In this study, we develop a facile two-step approach to disperse noble metal (Pt and Au) nanoparticles on the surface of CeO2 functionalized reduced graphene oxide (RGO) nanosheets. It is shown that Pt and Au with particle sizes of about 5 and 2nm are well dispersed on the surface of RGO/CeO2. The reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) by NaBH4 was used as a model reaction to quantitatively evaluate the catalytic properties of the as-synthesized RGO/Pt/CeO2 and RGO/Au/CeO2 ternary nanocomposites. In such triple-component catalysts, CeO2 nanocrystals provide unique and critical roles for optimizing the catalytic performance of noble metallic Pt and Au, allowing them to express enhanced catalytic activities in comparison with RGO/Pt and RGO/Au catalysts. In addition, a possible mechanism for the enhanced catalytic activities of the RGO/Pt/CeO2 and RGO/Au/CeO2 ternary catalysts in the reduction of 4-NP is proposed. It is expected that our prepared graphene-based triple-component composites, which inherit peculiar properties of graphene, metal oxide, and noble metal, are attractive candidates for catalysis and other applications.

  20. Hybrid nanocomposite from aniline and CeO2 nanoparticles: Surface protective performance on mild steel in acidic environment

    NASA Astrophysics Data System (ADS)

    Sasikumar, Y.; Kumar, A. Madhan; Gasem, Zuhair M.; Ebenso, Eno E.

    2015-03-01

    This present work contributes to the development of a new generation of active corrosion inhibitors composed of CeO2 nanoparticles covered with polyaniline that are able to release entrapped nanoparticles in acidic medium. Nanocomposites of aniline and CeO2 nanoparticles have been chemically synthesized by in-situ polymerization. The structural evolutions and morphological characteristics of PANI/CeO2 nanocomposite (PCN) have performed using various techniques such as XRD, IR, XPS, SEM and TEM analysis. It was illustrated from SEM and TEM observation that the PCN has globular particle with core-shell structure. The inhibition properties of synthesized PCN on mild steel (MS) corrosion in 0.5 M HCl were estimated using weight loss and electrochemical techniques. Potentiodynamic polarization results revealed PCN to be a mixed-type inhibitor, while impedance results indicate the adsorption of the PCN film on the MS surface. The inhibition efficiency of PCN was found to increase almost linearly with concentration. Moreover, an increase in the water contact-angle with PCN indicated its adsorption at the MS surface, and ATR-IR, SEM/EDAX and AFM visualization confirmed the formation of a protective film adsorbed on a MS surface. Finally, it was concluded that the PCN is a potential inhibitor for mild steel in HCl medium.

  1. Performance of the nano-structured Cu-Ni (alloy) -CeO2 anode for solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Liu, Minquan; Wang, Shaolan; Chen, Ting; Yuan, Chun; Zhou, Yucun; Wang, Shaorong; Huang, Jun

    2015-01-01

    In this work, copper and nickel oxides (CuO-NiO) powders with various mole ratios were synthesized by the glycine nitrate process (GNP) and the Cu-Ni alloy was obtained by reducing the CuO-NiO powders at 600 °C for 0.75 h. Furthermore, Cu1-xNix (alloy) -CeO2 impregnated YSZ anodes were fabricated by the impregnation method and the optimized anode composition was evaluated. It was found that the optimized mole ratio of Cu:Ni was 5:5, while the weight ratio of Cu-Ni alloy to CeO2 was 3:1. Additionally, impregnated anode with 40 wt % loading of Cu0.5Ni0.5 (alloy)-CeO2 exhibited the best performance and the polarization resistance of such anode was only 0.097, 0.115, 0.145 and 0.212 Ω cm2 at 750, 700, 650 and 600 °C, respectively. Finally, the performance of the optimized anode in methane (CH4) was investigated and the carbon deposition is greatly suppressed compared to the Ni-based anode.

  2. Amorphization of ZrO2 + CeO2 Powders Through Mechanical Milling for the Use of Kinetic Spray

    NASA Astrophysics Data System (ADS)

    Li, Songlin; Wang, Lei; Xiong, Yuming; Bae, Gyuyeol; Lee, Changhee

    2013-12-01

    The coating formation in a kinetic spray process mainly depends on the impact of inflight particles at a high velocity. The plastic deformation at the impact interface would disrupt the native oxide scale on the particle and the substrate to generate the intimate contact of the atomic structures. Accordingly, it poses a challenge in producing ceramic coating during kinetic spray because of the lack of plasticity of ceramic powders at room temperature. In this study, we proposed to prepare ZrO2 ceramic coatings using partially amorphized powder with nanometer size in the kinetic spray process. To prepare the powder for the use of the kinetic spray, the amorphization and grain refinement of ZrO2 powder in mechanical ball milling were studied. The results showed that the amorphization and grain refinement were improved because of the formation of solid solution when the CeO2 agent was added. Subsequently, a nearly spherical powder was achieved via spray drying using the milled powders. The plasticity of the milled powders was tested in the kinetic spray process using Nitrogen as process gas. A dense ZrO2-CeO2 coating with a thickness of 50 μm was formed, whereas spraying milled ZrO2 powder can only lead to an inhomogeneous dispersion of the destructible particles on the surface of the substrate.

  3. Shape tailored green synthesis of CeO2:Ho3+ nanopowders, its structural, photoluminescence and gamma radiation sensing properties

    NASA Astrophysics Data System (ADS)

    Malleshappa, J.; Nagabhushana, H.; Kavyashree, D.; Prashantha, S. C.; Sharma, S. C.; Premkumar, H. B.; Shivakumara, C.

    2015-06-01

    CeO2:Ho3+ (1-9 mol%) nanopowders have been prepared by efficient and environmental friendly green combustion method using Aloe vera gel as fuel for the first time. The final products are well characterized by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), fourier transform infrared (FTIR). Bell, urchin, core shell and flower like morphologies are observed with different concentrations of the A. vera gel. It is apparent that by adjusting the concentration of the gel, considerable changes in the formation of CeO2:Ho3+ nano structures can be achieved. Photoluminescence (PL) studies show green (543, 548 nm) and red (645, 732 nm) emissions upon excited at 400 nm wavelength. The emission peaks at ∼526, 548, 655 and 732 nm are associated with the transitions of 5F3 → 5I8, 5S2 → 5I8, 5F5 → 5I8 and 5S2 → 5I7, respectively. Three TL glow peaks are observed at 118, 267 and 204 °C for all the γ irradiated samples which specify the surface and deeper traps. Linear TL response in the range 0.1-2 kGy shows that phosphor is fairly useful as γ radiation dosimeter. Kinetic parameters associated with the glow peaks are estimated using Chen's half width method. The CIE coordinate values show that phosphor is quite useful for the possible applications in WLEDs as orange red phosphor.

  4. Adsorption and Reaction of Acetaldehyde on Shape-Controlled CeO2 Nanocrystals: Elucidation of Structure-function Relationships

    SciTech Connect

    Mann, Amanda K; Wu, Zili; Calaza, Florencia; Overbury, Steven {Steve} H

    2014-01-01

    CeO2 cubes with {100} facets, octahedra with {111} facets, and wires with highly defective structures were utilized to probe the structure-dependent reactivity of acetaldehyde. Using temperature-programmed desorption (TPD), temperature-programmed surface reactions (TPSR), and in situ infrared spectroscopy it was found that acetaldehyde desorbs unreacted or undergoes reduction, coupling, or C-C bond scission reactions depending on the surface structure of CeO2. Room temperature FTIR indicates that acetaldehyde binds primarily as 1-acetaldehyde on the octahedra, in a variety of conformations on the cubes, including coupling products and acetate and enolate species, and primarily as coupling products on the wires. The percent consumption of acetaldehyde follows the order of wires > cubes > octahedra. All the nanoshapes produce the coupling product crotonaldehyde; however, the selectivity to produce ethanol follows the order wires cubes >> octahedra. The selectivity and other differences can be attributed to the variation in the basicity of the surfaces, defects densities, coordination numbers of surface atoms, and the reducibility of the nanoshapes.

  5. Enhanced Gas Sensing Properties of SnO2 Hollow Spheres Decorated with CeO2 Nanoparticles Heterostructure Composite Materials.

    PubMed

    Liu, Jiangyang; Dai, Mingjun; Wang, Tianshuang; Sun, Peng; Liang, Xishuang; Lu, Geyu; Shimanoe, Kengo; Yamazoe, Noboru

    2016-03-01

    CeO2 decorated SnO2 hollow spheres were successfully synthesized via a two-step hydrothermal strategy. The morphology and structures of as-obtained CeO2/SnO2 composites were analyzed by various kinds of techniques. The SnO2 hollow spheres with uniform size around 300 nm were self-assembled with SnO2 nanoparticles and were hollow with a diameter of about 100 nm. The CeO2 nanoparticles on the surface of SnO2 hollow spheres could be clearly observed. X-ray photoelectron spectroscopy results confirmed the existence of Ce(3+) and the increased amount of both chemisorbed oxygen and oxygen vacancy after the CeO2 decorated. Compared with pure SnO2 hollow spheres, such composites revealed excellent enhanced sensing properties to ethanol. When the ethanol concentration was 100 ppm, the sensitivity of the CeO2/SnO2 composites was 37, which was 2.65-times higher than that of the primary SnO2 hollow spheres. The sensing mechanism of the enhanced gas sensing properties was also discussed.

  6. Distribution of Oxygen Vacancies and Gadolinium Dopants in ZrO2-CeO2 Multi-Layer Films Grown on α-Al2O3

    SciTech Connect

    Wang, Chong M.; Engelhard, Mark H.; Azad, Samina; Saraf, Laxmikant V.; McCready, David E.; Shutthanandan, V.; Yu, Zhongqing; Thevuthasan, Suntharampillai; Watanabe, M.; Williams, D. B.

    2006-06-15

    Gd-doped ZrO2 and CeO2 multi-layer films were deposited on α-Al2O3 (0001) using oxygen plasma assisted molecular beam epitaxy. Oxygen vacancies and Gd dopant distributions were investigated in these multi-layer films using x-ray diffraction (XRD), conventional and high-resolution transmission electron microscopy (HRTEM), annular dark-filed imaging in scanning transmission electron microscopy (STEM), energy dispersive x-ray spectroscopy (EDS) elemental mapping and x-ray photoelectron spectroscopy (XPS) depth profiling. EDS and XPS reveal that Gd concentration in the ZrO2 layer is lower than that in the CeO2 layer. As a result, higher oxygen vacancy concentration exists in CeO2 layers compared to that in ZrO2 layers. In addition, Gd is found to segregate only at the interfaces formed during the deposition of CeO2 layers on ZrO2 layers. On the other hand, the interfaces formed during the deposition of ZrO2 layers on CeO2 layers did not show any Gd segregation. The Gd segregation behavior at the every other interface is believed to be associated with the low solubility of Gd in ZrO2.

  7. Synthesis of Dimethyl Carbonate from Ethylene Carbonate and Methanol Over Nano-Catalysts Supported on CeO2-MgO.

    PubMed

    Jun, Jin Oh; Lee, Joongwon; Kang, Ki Hyuk; Song, In Kyu

    2015-10-01

    A series of CeO2(X)-MgO(1-X) (X = 0, 0.25, 0.5, 0.75, and 1.0) nano-catalysts were prepared by a co-precipitation method for use in the synthesis of dimethyl carbonate from ethylene carbonate and methanol. Among the CeO2(X)-MgO(1-X) catalysts, CeO2(0.25)-MgO(0.75) nano-catalyst showed the best catalytic performance. Alkali and alkaline earth metal oxides (MO = Li2O, K2O, Cs2O, SrO, and BaO) were then supported on CeO2(0.25)-MgO(0.75) by an incipient wetness impregnation method with an aim of improving the catalytic performance of CeO2(0.25)-MgO(0.75). Basicity of the catalysts was determined by CO2-TPD experiments in order to elucidate the effect of basicity on the catalytic performance. The correlation between catalytic performance and basicity showed that basicity played an important role in the reaction. Yield for dimethyl carbonate increased with increasing basicity of the catalysts. Among the catalysts tested, Li2O/CeO2(0.25)-MgO(0.75) nano-catalyst with the largest basicity showed the best catalytic performance in the synthesis of dimethyl carbonate.

  8. CeO2 nanocubes-graphene oxide as durable and highly active catalyst support for proton exchange membrane fuel cell.

    PubMed

    Lei, M; Wang, Z B; Li, J S; Tang, H L; Liu, W J; Wang, Y G

    2014-01-01

    Rapid degradation of cell performance still remains a significant challenge for proton exchange membrane fuel cell (PEMFC). In this work, we develop novel CeO2 nanocubes-graphene oxide nanocomposites as durable and highly active catalyst support for proton exchange membrane fuel cell. We show that the use of CeO2 as the radical scavenger in the catalysts remarkably improves the durability of the catalyst. The catalytic activity retention of Pt-graphene oxide-8 wt.% CeO2 nanocomposites reaches as high as 69% after 5000 CV-cycles at a high voltage range of 0.8-1.23 V, in contrast to 19% for that of the Pt-graphene oxide composites. The excellent durability of the Pt-CeO2 nanocubes-graphene oxide catalyst is attributed to the free radical scavenging activity of CeO2, which significantly slows down the chemical degradation of Nafion binder in catalytic layers, and then alleviates the decay of Pt catalysts, resulting in the excellent cycle life of Pt-CeO2-graphene oxide nanocomposite catalysts. Additionally, the performance of single cell assembled with Nafion 211 membrane and Pt-CeO2-graphene oxide catalysts with different CeO2 contents in the cathode as well as the Pt-C catalysts in the anode are also recorded and discussed in this study.

  9. Effects of CeO2 nanoparticles on biological nitrogen removal in a sequencing batch biofilm reactor and mechanism of toxicity.

    PubMed

    Hou, Jun; You, Guoxiang; Xu, Yi; Wang, Chao; Wang, Peifang; Miao, Lingzhan; Ao, Yanhui; Li, Yi; Lv, Bowen

    2015-09-01

    The effects of CeO2 nanoparticles (CeO2 NPs) exposure on biological nitrogen removal in a sequencing batch biofilm reactor (SBBR) were investigated. At low concentration (1 mg/L), no significant effect was observed on total nitrogen (TN) removal. However, at high concentrations (10 and 50 mg/L), the TN removal efficiency reduced from 74.09% to 64.26% and 55.17%, respectively. Scanning electron microscope imaging showed large amounts of CeO2 NPs adsorbed on the biofilm, which increased the production of reactive oxygen species. The exposure at only 50 mg/L CeO2 NPs measurably affected the lactate dehydrogenase release. Confocal laser scanning microscopy showed that high concentrations of CeO2 NPs reduced bacterial viability. Moreover, after a short-term exposure, extracellular polymeric substances (EPS) were observed to increase, forming a compact matrix to protect the bacteria. The activities of nitrate reductase and ammonia monooxygenase were inhibited, but there was no significant impact on the activity of nitrite oxidoreductase.

  10. CeO2 nanocubes-graphene oxide as durable and highly active catalyst support for proton exchange membrane fuel cell

    PubMed Central

    Lei, M.; Wang, Z. B.; Li, J. S.; Tang, H. L.; Liu, W. J.; Wang, Y. G.

    2014-01-01

    Rapid degradation of cell performance still remains a significant challenge for proton exchange membrane fuel cell (PEMFC). In this work, we develop novel CeO2 nanocubes-graphene oxide nanocomposites as durable and highly active catalyst support for proton exchange membrane fuel cell. We show that the use of CeO2 as the radical scavenger in the catalysts remarkably improves the durability of the catalyst. The catalytic activity retention of Pt-graphene oxide-8 wt.% CeO2 nanocomposites reaches as high as 69% after 5000 CV-cycles at a high voltage range of 0.8–1.23 V, in contrast to 19% for that of the Pt-graphene oxide composites. The excellent durability of the Pt-CeO2 nanocubes-graphene oxide catalyst is attributed to the free radical scavenging activity of CeO2, which significantly slows down the chemical degradation of Nafion binder in catalytic layers, and then alleviates the decay of Pt catalysts, resulting in the excellent cycle life of Pt-CeO2-graphene oxide nanocomposite catalysts. Additionally, the performance of single cell assembled with Nafion 211 membrane and Pt-CeO2-graphene oxide catalysts with different CeO2 contents in the cathode as well as the Pt-C catalysts in the anode are also recorded and discussed in this study. PMID:25491655

  11. Ultrafine Nanocrystalline CeO2@C-Containing NaAlH4 with Fast Kinetics and Good Reversibility for Hydrogen Storage.

    PubMed

    Zhang, Xin; Liu, Yongfeng; Wang, Ke; Li, You; Gao, Mingxia; Pan, Hongge

    2015-12-21

    A nanocrystalline CeO2@C-containing NaAlH4 composite is successfully synthesized in situ by hydrogenating a NaH-Al mixture doped with CeO2@C. Compared with NaAlH4 , the as-prepared CeO2@C-containing NaAlH4 composite, with a minor amount of excess Al, exhibits significantly improved hydrogen storage properties. The dehydrogenation onset temperature of the hydrogenated [NaH-Al-7 wt % CeO2@C]-0.04Al sample is 77 °C lower than that of the pristine sample because of a reduced kinetic barrier. More importantly, the dehydrogenated sample absorbs ∼4.7 wt % hydrogen within 35 min at 100°C and 10 MPa of hydrogen. Compositional and structural analyses reveal that CeO2 is converted to CeH2 during ball milling and that the newly formed CeH2 works with the excess of Al to synergistically improve the hydrogen storage properties of NaAlH4. Our findings will aid in the rational design of novel catalyst-doped complex hydride systems with low operating temperatures, fast kinetics, and long-term cyclability. PMID:26632764

  12. Optimized CeO2 content of the carbon nanofiber support of PtRu catalyst for direct methanol fuel cells

    NASA Astrophysics Data System (ADS)

    Kunitomo, Hikari; Ishitobi, Hirokazu; Nakagawa, Nobuyoshi

    2015-11-01

    A series of CeO2 embedded carbon nanofibers, CECNFs, with different CeO2 contents was prepared by an electrospinning technique. About 15 wt% PtRu nanoparticles were deposited on the fibers, and the effect of the CeO2 content on the methanol oxidation activity of the catalyst, PtRu/CECNF, was investigated. Cyclic voltammetry (CV), chronoamperometry (CA) and CO stripping electrochemical measurements and physical characterization along with X-ray diffraction (XRD) analysis, energy dispersive X-ray (EDX) analysis, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) were carried out on the prepared catalysts. The mass activity of the PtRu was significantly increased by the CeO2 addition up to Ce/C = 0.4, and the maximized activity was 2 times higher than that without CeO2. The increased activity was attributed to the strong interaction between the metal and oxide in the embedded nanofiber structure. A DMFC with the PtRu/CECNF exhibited more than 2.5 times high power density with one half the PtRu loading compared to that of the commercial catalyst, PtRu/Ccom.

  13. Ultrafine Nanocrystalline CeO2@C-Containing NaAlH4 with Fast Kinetics and Good Reversibility for Hydrogen Storage.

    PubMed

    Zhang, Xin; Liu, Yongfeng; Wang, Ke; Li, You; Gao, Mingxia; Pan, Hongge

    2015-12-21

    A nanocrystalline CeO2@C-containing NaAlH4 composite is successfully synthesized in situ by hydrogenating a NaH-Al mixture doped with CeO2@C. Compared with NaAlH4 , the as-prepared CeO2@C-containing NaAlH4 composite, with a minor amount of excess Al, exhibits significantly improved hydrogen storage properties. The dehydrogenation onset temperature of the hydrogenated [NaH-Al-7 wt % CeO2@C]-0.04Al sample is 77 °C lower than that of the pristine sample because of a reduced kinetic barrier. More importantly, the dehydrogenated sample absorbs ∼4.7 wt % hydrogen within 35 min at 100°C and 10 MPa of hydrogen. Compositional and structural analyses reveal that CeO2 is converted to CeH2 during ball milling and that the newly formed CeH2 works with the excess of Al to synergistically improve the hydrogen storage properties of NaAlH4. Our findings will aid in the rational design of novel catalyst-doped complex hydride systems with low operating temperatures, fast kinetics, and long-term cyclability.

  14. Photoluminescence, photocatalytic and antibacterial activities of CeO2·CuO·ZnO nanocomposite fabricated by co-precipitation method.

    PubMed

    Subhan, Md Abdus; Uddin, Nizam; Sarker, Prosenjit; Azad, Abul Kalam; Begum, Kulsuma

    2015-10-01

    A novel tri-metallic oxide nanocomposite CeO2·CuO·ZnO has been synthesized by a simple co-precipitation method. The nanocomposite has been characterized by XRD, SEM, EDS, FTIR and PL spectra. The crystallite size of the CeO2·CuO·ZnO was calculated using XRD data. The crystallite size of the CeO2·CuO·ZnO mixed metal oxide annealed at 600 °C is found to be in range of 15.34-44.81 nm, with an average size of 29.51 nm. Excitation at different wavelengths showed PL in UV and visible regions. It has been found that PL behavior of CeO2·CuO·ZnO is excitation wavelength dependent. This flexible PL property is conflicting to well-known Kasha's rule of excitation wavelength dependence of emission spectrum. The catalyst shows better photo-catalytic dye degradation efficiency in slightly alkaline pH in presence of H2O2. Nanocomposite CeO2·CuO·ZnO was found to be effective against pathogenic bacteria. PMID:26002435

  15. Structure and photoluminescence studies of CeO2·CuAlO2 mixed metal oxide fabricated by co-precipitation method

    NASA Astrophysics Data System (ADS)

    Subhan, Md Abdus; Ahmed, Tanzir; Awal, M. R.; Kim, B. Moon

    2015-01-01

    A novel mixed metal oxide, CeO2·CuAlO2 was fabricated by co-precipitation method in aqueous medium. CeO2·CuAlO2 was characterized by XRD, SEM, EDS, TEM, FTIR and PL spectra. The optical properties of the nanoparticles were studied by photoluminescence (PL) spectra. PL spectra at different excitations were recorded. The composite showed emission in UV, visible and NIR region depending on the excitation wavelength. The special spectral feature observed for this composite is that it showed six emission bands at 364, 409, 434, 448, 465 and 481 nm when excited at 298 nm. The green and red emissions observed at 512 and 669 nm are originated from cubic CeO2 phase when excited at 450 nm. The PL spectra were found to be dependent on excitation wavelength violating Kasha's rule. The X-ray diffraction reveals a cubic CeO2 phase and hexagonal CuAlO2 phase. EDS spectra revealed the presence of cerium (Ce), copper (Cu), aluminum (Al) and oxygen (O) elements. The particle size of the CeO2·CuAlO2 mixed oxide was estimated using Scherrer's formula, which was found to be in the range of 17.2-34.2 nm. The TEM image showed particles are almost uniform size of approximately 15-50 nm with spherical morphology.

  16. Structure and photoluminescence studies of CeO2·CuAlO2 mixed metal oxide fabricated by co-precipitation method.

    PubMed

    Subhan, Md Abdus; Ahmed, Tanzir; Awal, M R; Kim, B Moon

    2015-01-25

    A novel mixed metal oxide, CeO2·CuAlO2 was fabricated by co-precipitation method in aqueous medium. CeO2·CuAlO2 was characterized by XRD, SEM, EDS, TEM, FTIR and PL spectra. The optical properties of the nanoparticles were studied by photoluminescence (PL) spectra. PL spectra at different excitations were recorded. The composite showed emission in UV, visible and NIR region depending on the excitation wavelength. The special spectral feature observed for this composite is that it showed six emission bands at 364, 409, 434, 448, 465 and 481 nm when excited at 298 nm. The green and red emissions observed at 512 and 669 nm are originated from cubic CeO2 phase when excited at 450 nm. The PL spectra were found to be dependent on excitation wavelength violating Kasha's rule. The X-ray diffraction reveals a cubic CeO2 phase and hexagonal CuAlO2 phase. EDS spectra revealed the presence of cerium (Ce), copper (Cu), aluminum (Al) and oxygen (O) elements. The particle size of the CeO2·CuAlO2 mixed oxide was estimated using Scherrer's formula, which was found to be in the range of 17.2-34.2 nm. The TEM image showed particles are almost uniform size of approximately 15-50 nm with spherical morphology. PMID:25113734

  17. Synthesis of Dimethyl Carbonate from Ethylene Carbonate and Methanol Over Nano-Catalysts Supported on CeO2-MgO.

    PubMed

    Jun, Jin Oh; Lee, Joongwon; Kang, Ki Hyuk; Song, In Kyu

    2015-10-01

    A series of CeO2(X)-MgO(1-X) (X = 0, 0.25, 0.5, 0.75, and 1.0) nano-catalysts were prepared by a co-precipitation method for use in the synthesis of dimethyl carbonate from ethylene carbonate and methanol. Among the CeO2(X)-MgO(1-X) catalysts, CeO2(0.25)-MgO(0.75) nano-catalyst showed the best catalytic performance. Alkali and alkaline earth metal oxides (MO = Li2O, K2O, Cs2O, SrO, and BaO) were then supported on CeO2(0.25)-MgO(0.75) by an incipient wetness impregnation method with an aim of improving the catalytic performance of CeO2(0.25)-MgO(0.75). Basicity of the catalysts was determined by CO2-TPD experiments in order to elucidate the effect of basicity on the catalytic performance. The correlation between catalytic performance and basicity showed that basicity played an important role in the reaction. Yield for dimethyl carbonate increased with increasing basicity of the catalysts. Among the catalysts tested, Li2O/CeO2(0.25)-MgO(0.75) nano-catalyst with the largest basicity showed the best catalytic performance in the synthesis of dimethyl carbonate. PMID:26726512

  18. Preparation of bi-axially aligned YBa 2Cu 3O 7- δ film on CeO 2-buffered MgO by chemical solution deposition

    NASA Astrophysics Data System (ADS)

    Yamagiwa, K.; Hiei, H.; Takahashi, Y.; Kim, S. B.; Matsumoto, K.; Ikuta, H.; Mizutani, U.; Hirabayashi, I.

    2000-06-01

    We have succeeded in preparing in-plane aligned YBa 2Cu 3O 7- δ (Y123) film by chemical solution deposition (CSD) processing on CeO 2 (100)-buffered MgO (100) substrates. The CeO 2 buffer film was deposited on MgO (100) single crystalline substrate by pulsed laser deposition (PLD). For CSD coating, a homogeneous coating solution having a molar ratio of Y:Ba:Cu=1:2:3, was prepared by dissolving metal naphthenates in toluene. This solution was spin-coated both on the YSZ (100) and on the CeO 2-buffered MgO (100) single crystalline substrates. The precursor films were calcined at 425°C and fired at various temperatures under low oxygen partial pressure ( pO 2). All Y123 films showed strong (00 n) peaks, which correspond to c-axis orientation perpendicular to the substrates and their a/ b-axes were in-plane aligned. We confirmed that CeO 2 buffer is usable for CSD processing. While the Y123 films on the YSZ reacted with the substrate forming BaZrO 3 phase and did not show sufficient superconducting properties. The Tc,zero value of the Y123 film prepared on CeO 2-buffered MgO substrate was 91.5 K and Jc was 1.2×10 5 A/cm 2 at 77 K, 0 T.

  19. Long and short term impacts of CuO, Ag and CeO2 nanoparticles on anaerobic digestion of municipal waste activated sludge.

    PubMed

    Ünşar, E Kökdemir; Çığgın, A S; Erdem, A; Perendeci, N A

    2016-02-01

    In this study, long and short term inhibition impacts of Ag, CuO and CeO2 nanoparticles (NPs) on anaerobic digestion (AD) of waste activated sludge (WAS) were investigated. CuO NPs were detected as the most toxic NPs on AD. As the CuO NP concentration increased from 5 to 1000 mg per gTS, an increase in the inhibition of AD from 5.8 to 84.0% was observed. EC50 values of short and long term inhibitions were calculated as 224.2 mgCuO per gTS and 215.1 mgCuO per gTS, respectively. Ag and CeO2 NPs did not cause drastic impacts on AD as compared to CuO NPs. In the long term test, Ag NPs created 12.1% decrease and CeO2 NPs caused 9.2% increase in the methane production from WAS at the highest dosage. FISH imaging also revealed that the abundance of Archaea in raw WAS was similar in short and long term tests carried out with WAS containing Ag and CeO2 NPs. On the other hand, CuO NPs caused inhibition of Archaea in the long term test. Digestion kinetics of WAS containing Ag, CeO2, CuO NPs were also evaluated with Gompertz, Logistic, Transference and First Order models. The hydrolysis rate constant (kH) for each concentration of Ag and CeO2 NPs and the raw WAS was 0.027745 d(-1) while the kH of WAS containing high concentrations of CuO NPs was found to be 0.001610 d(-1).

  20. Thiolate ligands as a double-edged sword for CO oxidation on CeO2-supported Au25(SR)18 nanoclusters

    SciTech Connect

    Wu, Zili; Jiang, Deen; Mann, Amanda K; Mullins, David R; Qiao, Zhen-an; Allard Jr, Lawrence Frederick; Zeng, Chenjie; Jin, Rongchao; Overbury, Steven {Steve} H

    2014-01-01

    The effect of thiolate ligands was explored on the catalysis of CeO2-rod supported Au25(SR)18 (SR = -SCH2-CH2-Ph) by using CO oxidation as a probe reaction. Reaction kinetic tests, in situ IR and X-ray absorption spectroscopy, and density functional theory (DFT) were employed to understand how the thiolate ligands affect the nature of active sites, activation of CO and O2, as well as the reaction mechanism and kinetics. The intact Au25(SR)18 on CeO2-rod is found not able to adsorb CO. Only when the thiolate ligands are partially removed, starting from the interface between Au25(SR)18 and CeO2 at temperatures of 423 K and above, can the adsorption of CO be observed by IR. DFT calculations suggest that CO adsorbs favorably on the exposed gold atoms. Accordingly, the CO oxidation light-off temperature shifts to lower temperature. Several types of Au sites are probed by IR of CO adsorption during the ligand removal process. The cationic Au sites (charged between 0 and +1) are found to play the major role for low temperature CO oxidation. Similar activation energy and reaction rate are found for CO oxidation on differently treated Au25(SR)18/CeO2-rod, suggesting a simple site-blocking effect of the thiolate ligands in Au nanoclusters catalysis. Isotopic labelling experiments clearly indicate that CO oxidation on Au25(SR)18/CeO2-rod proceeds predominantly via the redox mechanism where CeO2 activates O2 while CO is activated on the de-thiolated gold sites. These results points to a double-edged sword role played by the thiolate ligands on Au25 nanoclusters for CO oxidation.

  1. Low toxicity of HfO2, SiO2, Al2O3 and CeO2 nanoparticles to the yeast, Saccharomyces cerevisiae.

    PubMed

    García-Saucedo, Citlali; Field, James A; Otero-Gonzalez, Lila; Sierra-Álvarez, Reyes

    2011-09-15

    Increasing use of nanomaterials necessitates an improved understanding of their potential impact on environment health. This study evaluated the cytotoxicity of nanosized HfO(2), SiO(2), Al(2)O(3) and CeO(2) towards the eukaryotic model organism Saccharomyces cerevisiae, and characterized their state of dispersion in bioassay medium. Nanotoxicity was assessed by monitoring oxygen consumption in batch cultures and by analysis of cell membrane integrity. CeO(2), Al(2)O(3), and HfO(2) nanoparticles were highly unstable in yeast medium and formed micron-sized, settleable agglomerates. A non-toxic polyacrylate dispersant (Dispex A40) was used to improve nanoparticle stability and determine the impact of enhanced dispersion on toxicity. None of the NPs tested without dispersant inhibited O(2) uptake by yeast at concentrations as high as 1000 mg/L. Dispersant supplementation only enhanced the toxicity of CeO(2) (47% at 1000 mg/L). Dispersed SiO(2) and Al(2)O(3) (1000 mg/L) caused cell membrane damage, whereas dispersed HfO(2) and CeO(2) did not cause significant disruption of membrane integrity at the same concentration. These results suggest that the O(2) uptake inhibition observed with dispersed CeO(2) NPs was not due to reduced cell viability. This is the first study evaluating toxicity of nanoscale HfO(2), SiO(2), Al(2)O(3) and CeO(2) to S. cerevisiae. Overall the results obtained demonstrate that these nanomaterials display low or no toxicity to yeast.

  2. CO2 reforming of CH4 over CeO2-doped Ni/Al2O3 nanocatalyst treated by non-thermal plasma.

    PubMed

    Rahemi, Nader; Haghighi, Mohammad; Babaluo, Ali Akbar; Jafari, Mahdi Fallah; Estifaee, Pooya

    2013-07-01

    Ni/Al2O3 and Ni/Al2O3-CeO2 nanocatalysts have been prepared with impregnation method, treated with non-thermal plasma, characterized and tested for dry reforming of methane. For catalyst characterization, the following techniques have been used: XRD, FESEM, TEM, EDX dot mapping, BET, FTIR, TG-DTG, and XPS techniques. According to XRD and XPS, Ni in all catalysts exists as NiO and NiAl2O4 that existence of NiAl2O4 reveals strong interaction between active phase and support. Catalyst particles had smaller average particle size in plasma treated Ni/Al2O3-CeO2 nanocatalyst with less agglomeration. Homogenous dispersion of active phase, narrower particle size distribution, and uniform morphology has been observed in ceria containing plasma treated catalyst. The plasma treated Ni/Al2O3-CeO2 nanocatalyst showed bigger NiAl2O4/NiO ratio in XPS analysis that is indicative of stronger interaction between Ni and Al2O3 in the presence of CeO2. The dry reforming of methane was carried out at 550-850 degrees C using a mixture of CH4:CO2 (0.5:2). Improved morphology of the plasma treated Ni/Al2O3-CeO2 nanocatalyst, resulted from both CeO2 and plasma treatment, caused higher ability of catalyst in H2 and CO production. Product yield decreased at higher GHSVs, due to the fact that mass transport limitations will be more severe at low residence time, but this reduction would be less noticeable in the plasma treated Ni/Al2O3-CeO2 nanocatalyst. In addition, the plasma treated Ni/Al2O3-CeO2 nanocatalyst can keep the reactivity without deactivation for either CH4 or CO2 conversion better than other investigated catalysts.

  3. Promoting Effect of CeO2 in the Electrocatalytic Activity of Rhodium for Ethanol Electro-Oxidation

    SciTech Connect

    He, Q.; Mukerjee, S; Shyam, B; Ramaker, D; Parres-Esclapex, D; Illan-Gomez, M; Bueno-Lopez, A

    2009-01-01

    The promoting effect of ceria in the electrocatalytic activity of rhodium for ethanol electro-oxidation in alkali media has been studied. Rh/C, CeO2/C and RhCeO2/C catalysts were synthesized and characterized by TEM, XRD, XPS, TG-MS, H2-TPR and XAS. The electrocatalytic activity was studied by Cyclic Voltammetry (CV) and chronoamperometry. The onset potential of oxidation on RhCeO2/C was shifted negatively as compared to that on Rh/C, despite ceria itself does not show any electrocatalytic activity. The promoting effect of ceria has been attributed to the improved rhodium dispersion, and differences in the oxidation state of rhodium between Rh/C and RhCeO2/C were not found. The carbon support reduces rhodium species to Rh0, and also partially reduces ceria, during the samples preparation, and the surface of the carbon support is oxidised.

  4. Coadsorbed species explain the mechanism of methanol temperature-desorption on CeO2(111)

    DOE PAGESBeta

    Sutton, Jonathan E.; Steven H. Overbury; Beste, Ariana

    2016-03-24

    Here, we have used density functional theory calculations to investigate the temperature-programmed desorption (TPD) of methanol from CeO2(111). For the first time, low-temperature water formation and high-temperature methanol desorption are explained by our calculations. High coverages of methanol, which correspond to experimental conditions, are required to properly describe these features of the TPD spectrum. We identify a mechanism for the low-temperature formation of water involving the dissociation of two methanol molecules on the same surface O atom and filling of the resulting surface vacancy with one of the methoxy products. After water desorption, methoxy groups are stabilized on the surfacemore » and react at higher temperatures to form methanol and formaldehyde by a disproportionation mechanism. Alternatively, the stabilized methoxy groups undergo sequential C–H scission reactions to produce formaldehyde. Calculated energy requirements and methanol/formaldehyde selectivity agree with the experimental data.« less

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

    DOE PAGESBeta

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

    2016-02-09

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

  6. Voltage tunable dielectric properties of oxides at nanoscale: TiO2 and CeO2 as model systems

    NASA Astrophysics Data System (ADS)

    Prakash, T.; Tamil Selvan, A.; Suraiya Begum, S. N.

    2016-03-01

    Carrier transport through electrically active grain boundaries has been studied under biased condition using Solartron 1260 impedance/gain phase analyzer with an applied AC potential of 250 mV in the frequency range 1 Hz-1 MHz for nanocrystalline TiO2 and CeO2 as the model systems. Prior to the measurement both the materials were converted into cylindrical pellets with (8 mm diameter and 1 mm thick) by applying uni-axial pressure of 4 ton using a hydraulic press, then sintered at 300, 450 and 600 °C for 30 min for TiO2 sample and for the case of CeO2 it was done at 300, 600 and 900 °C for 30 min. Further, they were characterized using powder X-ray diffractometer (XRD) and transmission electron microscopy (TEM) to know the crystal structure, average crystallite size and morphology. The impedance measurements were performed at room temperature under applied DC bias voltages from 0 to 3 V in the periodic increment of 0.2 V. The observed applied bias voltage effect on dielectric constant of both the systems was analyzed with 'grain boundary double Schottky potential barrier height model' for different grain sizes. The percentage of voltage tunable dielectric constant (T%) as a function of frequency was estimated for all the grain sizes and it was found to be increase with reduction of grain size. Our experimental findings reveal the possibilities of utilizing these nanocrystals as a potential active material for phased array antenna since both the samples exhibits T% = 85% at 100 Hz frequency.

  7. A DFT+U study on the contribution of 4f electrons to oxygen vacancy formation and migration in Ln-doped CeO2.

    PubMed

    Alaydrus, M; Sakaue, M; Kasai, H

    2016-05-14

    A rare earth doped form of ceria (CeO2) is of interest as a potential candidate for solid oxide fuel cells (SOFCs) because of its relatively high oxygen ion conductivity at temperatures below 600 °C. At the present time, computational chemistry has reached a certain maturity which allows the prediction of materials properties that are difficult to observe experimentally. However, understanding of the roles of dopants in the oxygen ion conduction in CeO2 is still incomplete for quantitatively reliable analysis due to the strong electron correlation of 4f electrons. In this study, density functional theory calculations with Hubbard U corrections are used to discuss ionic/covalent interactions in rare-earth-doped CeO2 and their consequences to oxygen ion conduction. This study suggests that the variable occupancy of empty 4f orbitals is important typically for early Ln elements to produce the covalent interactions that essentially affect the formation and migration of oxygen vacancies. This finding is important in understanding the factors responsible for oxygen ion diffusion in doped CeO2.

  8. Stability of uncoated and fulvic acids coated manufactured CeO2 nanoparticles in various conditions: From ultrapure to natural Lake Geneva waters.

    PubMed

    Oriekhova, Olena; Stoll, Serge

    2016-08-15

    Understanding the behavior of engineered nanoparticles in natural water and impact of water composition in changing conditions is of high importance to predict their fate once released into the environment. In this study we investigated the stability of uncoated and Suwannee River fulvic acids coated CeO2 manufactured nanoparticles in various environmental conditions. The effect of pH changes on the nanoparticle and coating stability was first studied in ultrapure water as well as the variation of zeta potentials and sizes with time in presence of fulvic acids at environmental pH. Then the stability of CeO2 in synthetic and natural Lake Geneva waters was investigated as a function of fulvic acids concentration. Our results indicate that the adsorption of environmentally relevant concentrations of Suwannee River fulvic acids promotes CeO2 stabilization in ultrapure water as well as synthetic water and that the coating stability is high upon pH variations. On the other hand in natural Lake Geneva water CeO2 NPs are found in all cases aggregated due to the effect of heterogeneous organic and inorganic compounds.

  9. Pressure Regulations on the Surface Properties of CeO2 Nanorods and Their Catalytic Activity for CO Oxidation and Nitrile Hydrolysis Reactions.

    PubMed

    Li, Jing; Zhang, Zhiyun; Gao, Wei; Zhang, Sai; Ma, Yuanyuan; Qu, Yongquan

    2016-09-01

    Surface properties of nanoscale CeO2 catalysts in terms of the surface Ce(3+) fraction and concentration of oxygen vacancy can affect their catalytic performance significantly. Continual adjustment on surface properties of CeO2 with the morphological preservation has not been realized by synthetic methods. The revisited studies show that surface properties of CeO2 nanorods can be effectively regulated by synthetic pressures while the rodlike morphology is well-preserved. Such phenomena are ascribed to the contact possibility between Ce(3+) species and dissolved O2, which is balanced by the rapidly increased and gradually saturated dissolution/recrystallization rate of Ce(OH)3 and linearly increased concentration of dissolved O2 with the increase of total air pressure or partial pressure of O2. Surface-property-dependent catalytic activity of CeO2 nanorods synthesized under various pressures was also demonstrated in two benchmark reactions-catalytic oxidation of CO and hydrolysis of nitrile. Such a finding of the pressure regulation on the reducible metal oxides provides an effective approach to rationally design novel catalysts for specific reactions, where ceria are supports, promoters, or actives.

  10. Bioavailability of CeO2 and SnO2 nanoparticles evaluated by dietary uptake in the earthworm Eisenia fetida and sequential extraction of soil and feed.

    PubMed

    Carbone, Serena; Hertel-Aas, Turid; Joner, Erik J; Oughton, Deborah H

    2016-11-01

    The growing number of nanotechnology products on the market will inevitably lead to the release of engineered nanomaterials with potential risk to humans and environment. This study set out to investigate the exposure of soil biota to engineered nanoparticles (NPs). Cerium dioxide (CeO2 NPs) and tin dioxide nanoparticles (SnO2 NPs) were radiolabelled using neutron activation, and employed to assess the uptake and excretion kinetics in the earthworm Eisenia fetida. Through sequential extraction, NPs bioavailability in two contrasting soils and in earthworm feed was also investigated. Neither CeO2 NPs nor SnO2 NPs bioaccumulated in earthworms, and both were rapidly excreted when worms were transferred to clean soil. Low bioavailability was also indicated by low amounts of NPs recovered during extraction with non-stringent extractants. CeO2 NPs showed increasing mobility in organic soil over time (28 days), indicating that organic matter has a strong influence on the fate of CeO2 NPs in soil.

  11. Hydrophilic CeO2 nanocubes protect pancreatic β-cell line INS-1 from H2O2-induced oxidative stress.

    PubMed

    Lyu, Guang-Ming; Wang, Yan-Jie; Huang, Xue; Zhang, Huai-Yuan; Sun, Ling-Dong; Liu, Yan-Jun; Yan, Chun-Hua

    2016-04-21

    Oxidative stress plays a key role in the occurrence and development of diabetes. With their unique redox properties, CeO2 nanoparticles (nanoceria) exhibit promising potential for the treatment of diabetes resulting from oxidative stress. Here, we develop a novel preparation of hydrophilic CeO2 nanocubes (NCs) with two different sizes (5 nm and 25 nm) via an acetate assisted hydrothermal method. Dynamic light scattering, zeta potential measurements and thermogravimetric analyses were utilized to investigate the changes in the physico-chemical characteristics of CeO2 NCs when exposed to in vitro cell culture conditions. CCK-8 assays revealed that the CeO2 NCs did not impair cell proliferation in the pancreatic β-cell line INS-1 at the highest dose of 200 μg mL(-1) over the time scale of 72 h, while being able to protect INS-1 cells from H2O2-induced cytotoxicity even after protein adsorption. It is also noteworthy that nanoceria with a smaller hydrodynamic radius exhibit stronger antioxidant and anti-apoptotic effects, which is consistent with their H2O2 quenching capability in biological systems. These findings suggest that nanoceria can be used as an excellent antioxidant for controlling oxidative stress-induced pancreatic β-cell damage.

  12. Evidence of the differential biotransformation and genotoxicity of ZnO and CeO2 nanoparticles on soybean (Glycine max) plants

    PubMed Central

    López-Moreno, Martha L.; de la Rosa, Guadalupe; Hernández-Viezcas, José Á.; Castillo-Michel, Hiram; Botez, Cristian E.; Peralta-Videa, José R.; Gardea-Torresdey, Jorge L.

    2010-01-01

    Concern and interest related to the effects of nanomaterials on living organisms are growing in both the scientific and public communities. Reports have described the toxicity of nanoparticles (NPs) on micro and macro organisms, including some plant species. Nevertheless, to the authors’ knowledge there are no reports on the biotransformation of NPs by edible terrestrial plants. Here, shown for the first time, is evidence pertaining to the biotransformation of ZnO and CeO2 NPs in plant seedlings. Although the NPs did not affect soybean germination, they produced a differential effect on plant growth and element uptake. By using synchrotron X-ray absorption spectroscopy we obtained clear evidence of the presence of CeO2 NPs in roots, whereas ZnO NPs were not present. Random amplified polymorphic DNA assay was applied to detect DNA damage and mutations caused by NPs. Results obtained from the exposure of soybean plants to CeO2 NPs show the appearance of four new bands at 2000 mg L−1 and three new bands at 4000 mg L−1 treatment. In this study we demonstrated genotoxic effects from the exposure of soybean plants to CeO2 NPs. PMID:20384348

  13. Effect of Nano CeO2 Addition on the Microstructure and Properties of a Cu-Al-Ni Shape Memory Alloy

    NASA Astrophysics Data System (ADS)

    Pandey, Abhishek; Jain, Ashish Kumar; Hussain, Shahadat; Sampath, V.; Dasgupta, Rupa

    2016-08-01

    This article deals with the effect of adding nano CeO2 to act as a grain pinner/refiner to a known Cu-Al-Ni shape memory alloy. Elements were taken in a predefined ratio to prepare 300 g alloy per batch and melted in an induction furnace. Casting was followed by homogenization at 1173 K (900 °C) and rolling to make sheets of 0.5-mm thickness. Further, samples were characterized for microstructure using optical and electron microscope, hardness, and different phase studies by X-ray and transformation temperatures by differential scanning calorimetry. X-ray peak broadenings and changes were investigated to estimate the crystallite size, lattice strain, and phase changes due to different processing steps. A nearly uniform distribution of CeO2 and better martensitic structure were observed with increasing CeO2. The addition of CeO2 also shows a visible effect on the transformation temperature and phase formation.

  14. Dose-Dependent Effects of CeO2 on Microstructure and Antibacterial Property of Plasma-Sprayed TiO2 Coatings for Orthopedic Application

    NASA Astrophysics Data System (ADS)

    Zhao, Xiaobing; Liu, Gaopeng; Zheng, Hai; Cao, Huiliang; Liu, Xuanyong

    2015-02-01

    Titanium and its alloys have been used extensively for orthopedic and dental implants. Although these devices have achieved high rates of success, two major complications may be encountered: the lack of osseointegration and the biomaterial-related infection. Accordingly, cerium oxide (CeO2)-doped titanium oxide (TiO2) materials were coated on titanium by an atmospheric plasma spraying (APS) technique. The phase structures, morphologies, and surface chemical states of the obtained coatings were characterized by x-ray diffraction, scanning electron microscopy, and x-ray photoelectron spectroscopy techniques. The in vitro antibacterial and cytocompatibility of the materials were studied with Staphylococcus aureus ( S. aureus, ATCC25923) and osteoblast precursor cell line MC3T3-E1. The results indicated that the addition of CeO2 shifts slightly the diffraction peaks of TiO2 matrix to low angles but does not change its rutile phase structure. In addition, the CeO2/TiO2 composite coatings possess dose-dependent corrosion resistance and antimicrobial properties. And doping of 10 wt.% CeO2 exhibits the highest activity against S. aureus, improved corrosion resistance, and competitive cytocompatibility, which argues a promising option for balancing the osteogenetic and antibacterial properties of titanium implants.

  15. Germination and early plant development of 10 plant species exposed to Nano TiO2 and CeO2

    EPA Science Inventory

    Ten agronomic plant species were exposed to different concentrations of nano-TiO2 or CeO2 (0, 250, 500 and 1000 ug/l) and followed to examine effects on germination and early seedling development. For TiO2, cabbage showed increased and corn decreased percent germination, while ...

  16. WO3/CeO2/TiO2 Catalysts for Selective Catalytic Reduction of NO(x) by NH3: Effect of the Synthesis Method.

    PubMed

    Michalow-Mauke, Katarzyna A; Lu, Ye; Ferri, Davide; Graule, Thomas; Kowalski, Kazimierz; Elsener, Martin; Kröcher, Oliver

    2015-01-01

    WO3/CeO2/TiO2, CeO2/TiO2 and WO3/TiO2 catalysts were prepared by wet impregnation. CeO2/TiO2 and WO3/TiO2 showed activity towards the selective catalytic reduction (SCR) of NO(x) by NH3, which was significantly improved by subsequent impregnation of CeO/TiO2 with WO3. Catalytic performance, NH3 oxidation and NH3 temperature programmed desorption of wet-impregnated WO3/CeO2/TiO2 were compared to those of a flame-made counterpart. The flame-made catalyst exhibits a peculiar arrangement of W-Ce-Ti-oxides that makes it very active for NH3-SCR. Catalysts prepared by wet impregnation with the aim to mimic the structure of the flame-made catalyst were not able to fully reproduce its activity. The differences in the catalytic performance between the investigated catalysts were related to their structural properties and the different interaction of the catalyst components.

  17. Controlled synthesis of CeO2 microstructures from 1D rod-like to 3D lotus-like and their morphology-dependent properties

    NASA Astrophysics Data System (ADS)

    Gong, Jinfeng; Meng, Fanming; Fan, Zhenghua; Li, Huijie

    2016-10-01

    Monodisperse 3D lotus-like CeO2 microstructures have been successfully synthesized via controlling the morphology of CeCO3OH precursors under hydrothermal condition as well as subsequent calcination. The reaction time was systematically investigated. XRD, FT-IR, SEM, TEM, XPS, Raman scattering and Photoluminescence (PL) spectra were employed to characterize the samples. The lotus-like CeO2 hierarchical structures with an average of 4-6 μm are composed of many nanoplates of 100-200 nm in thickness as the petals stacking together to form open flowers and have a fluorite cubic structure. Based on the time-dependent morphology evolution evidences, a nucleation-dissolution-recrystallization mechanism has been proposed to explain the transformation from rod-like structures to lotus-like CeO2 hierarchical structures with the increase of reaction time. It is found that there are Ce3+ ions and oxygen vacancies in surface of samples. The magnetic and photoluminescence measurements indicated that all CeO2 samples exhibit excellent ferromagnetism and optical properties at room temperature, and while increasing the reaction time, the ferromagnetism and optical properties increase more, which can be reasonably explained for the influences of the different morphology of the particles and the concentration of oxygen vacancies and Ce3+ ions. [Figure not available: see fulltext.

  18. Pressure Regulations on the Surface Properties of CeO2 Nanorods and Their Catalytic Activity for CO Oxidation and Nitrile Hydrolysis Reactions.

    PubMed

    Li, Jing; Zhang, Zhiyun; Gao, Wei; Zhang, Sai; Ma, Yuanyuan; Qu, Yongquan

    2016-09-01

    Surface properties of nanoscale CeO2 catalysts in terms of the surface Ce(3+) fraction and concentration of oxygen vacancy can affect their catalytic performance significantly. Continual adjustment on surface properties of CeO2 with the morphological preservation has not been realized by synthetic methods. The revisited studies show that surface properties of CeO2 nanorods can be effectively regulated by synthetic pressures while the rodlike morphology is well-preserved. Such phenomena are ascribed to the contact possibility between Ce(3+) species and dissolved O2, which is balanced by the rapidly increased and gradually saturated dissolution/recrystallization rate of Ce(OH)3 and linearly increased concentration of dissolved O2 with the increase of total air pressure or partial pressure of O2. Surface-property-dependent catalytic activity of CeO2 nanorods synthesized under various pressures was also demonstrated in two benchmark reactions-catalytic oxidation of CO and hydrolysis of nitrile. Such a finding of the pressure regulation on the reducible metal oxides provides an effective approach to rationally design novel catalysts for specific reactions, where ceria are supports, promoters, or actives. PMID:27534804

  19. Bioavailability of CeO2 and SnO2 nanoparticles evaluated by dietary uptake in the earthworm Eisenia fetida and sequential extraction of soil and feed.

    PubMed

    Carbone, Serena; Hertel-Aas, Turid; Joner, Erik J; Oughton, Deborah H

    2016-11-01

    The growing number of nanotechnology products on the market will inevitably lead to the release of engineered nanomaterials with potential risk to humans and environment. This study set out to investigate the exposure of soil biota to engineered nanoparticles (NPs). Cerium dioxide (CeO2 NPs) and tin dioxide nanoparticles (SnO2 NPs) were radiolabelled using neutron activation, and employed to assess the uptake and excretion kinetics in the earthworm Eisenia fetida. Through sequential extraction, NPs bioavailability in two contrasting soils and in earthworm feed was also investigated. Neither CeO2 NPs nor SnO2 NPs bioaccumulated in earthworms, and both were rapidly excreted when worms were transferred to clean soil. Low bioavailability was also indicated by low amounts of NPs recovered during extraction with non-stringent extractants. CeO2 NPs showed increasing mobility in organic soil over time (28 days), indicating that organic matter has a strong influence on the fate of CeO2 NPs in soil. PMID:27474912

  20. CO, CO2 and H2 adsorption on ZnO, CeO2, and ZnO/CeO2 surfaces: DFT simulations.

    PubMed

    Reimers, Walter G; Baltanás, Miguel A; Branda, María M

    2014-06-01

    The adsorption of the molecules CO, CO2, and H2 on several ceria and zinc oxide surfaces was studied by means of periodical DFT calculations and compared with infrared frequency data. The stable CeO2(111), CeO2(331), and ZnO(0001) perfect faces were the first substrates considered. Afterwards, the same surfaces with oxygen vacancies and a ZnO monolayer grown on Ceria(111) were also studied in order to compare the behaviors and reactivities of the molecules at those surfaces. The ceria surfaces were substantially more reactive than the ZnO surface towards the CO2 molecule. The highest adsorption energy for this molecule was obtained on the CeO2(111) surface with oxygen vacancies. The molecules CO and H2 both presented low or very low reactivities on all of the surfaces studied, although some reactivity was observed for the adsorption of CO onto the surfaces with oxygen vacancies, whereas H2 exhibited reactivity towards the CeO2(111) surface with oxygen vacancies. This work was performed to provide a firm foundation for novel process development in methanol synthesis from carbon oxides, steam reforming of methanol for hydrogen production, and/or the water-gas shift reaction. PMID:24903980

  1. Differential genomic effects on canonical signaling pathways by two different CeO2 nanoparticles in HepG2 cells

    EPA Science Inventory

    Differential genomic effects on signaling pathways by two different CeO2 nanoparticles in HepG2 cells. Sheau-Fung Thai1, Kathleen A. Wallace1, Carlton P. Jones1, Hongzu Ren2, Benjamin T. Castellon1, James Crooks2, Kirk T. Kitchin1. 1Integrated Systems Toxicology Divison, 2Resea...

  2. Mixed-valence metal oxide nanoparticles as electrochemical half-cells: substituting the Ag/AgCl of reference electrodes by CeO(2-x) nanoparticles.

    PubMed

    Nagarale, Rajaram K; Hoss, Udo; Heller, Adam

    2012-12-26

    Cations of mixed valence at surfaces of metal oxide nanoparticles constitute electrochemical half-cells, with potentials intermediate between those of the dissolved cations and those in the solid. When only cations at surfaces of the particles are electrochemically active, the ratio of electrochemically active/all cations is ~0.1 for 15 nm diameter CeO(2-x) particles. CeO(2-x) nanoparticle-loaded hydrogel films on printed carbon and on sputtered gold constitute reference electrodes having a redox potential similar to that of Ag/AgCl in physiological (0.14 M) saline solutions. In vitro the characteristics of potentially subcutaneously implantable glucose monitoring sensors made with CeO(2-x) nanoparticle reference electrodes are undistinguishable from those of sensors made with Ag/AgCl reference electrodes. Cerium is 900 times more abundant than silver, and commercially produced CeO(2-x) nanoparticle solutions are available at prices well below those of the Ag/AgCl pastes used in the annual manufacture of ~10(9) reference electrodes of glucose monitoring strips for diabetes management. PMID:23171288

  3. Dissolved cerium contributes to uptake of Ce in the presence of differently sized CeO2-nanoparticles by three crop plants.

    PubMed

    Schwabe, Franziska; Tanner, Simon; Schulin, Rainer; Rotzetter, Aline; Stark, Wendelin; von Quadt, Albrecht; Nowack, Bernd

    2015-03-01

    We investigated the uptake of cerium (Ce) dioxide nanoparticles (NPs) by hydroponically grown wheat, pumpkin and sunflower plants. The presence of plant roots in nutrient solution led to a substantial increase in the dissolution of CeO2-NP compared to plant-free medium. Experiments with Zr/CeOx-NP revealed that Ce was not only taken up in the form of NPs, but simultaneously to a significant degree also as dissolved Ce(iii) ions, which then re-precipitated in the form of CeO2-NPs inside the leaves. The contribution of dissolved Ce uptake was particularly large for particles smaller than 10 nm due to their higher dissolution rate. Our data also indicate that the translocation of Ce resulting from NP-root-exposure is species dependent. When Ce was supplied as dissolved ions, sunflower had the highest capacity of Ce-ion accumulation inside the leaves, while there was no significant difference between pumpkin and wheat. We found no Ce translocation from roots into shoots when only NPs bigger than 20 nm were applied. This study highlights that plant root activity can have a significant impact on the dissolution of CeO2-NPs in soil solution and that uptake of dissolved Ce(iii) followed by re-precipitation needs to be considered as an important pathway in studies of CeO2-NP uptake by plants. PMID:25634091

  4. Colloidal stability of CeO2 nanoparticles coated with either natural organic matter or organic polymers under various hydrochemical conditions

    NASA Astrophysics Data System (ADS)

    Dippon, Urs; Pabst, Silke; Klitzke, Sondra

    2016-04-01

    The worldwide marked for engineered nanoparticles (ENPs) is growing and concerns on the environmental fate- and toxicity of ENPs are rising. Understanding the transport of ENPs within and between environmental compartments such as surface water and groundwater is crucial for exposition modeling, risk assessment and ultimately the protection of drinking water resources. The transport of ENPs is strongly influenced by the surface properties and aggregation behavior of the particles, which is strongly controlled by synthetic and natural organic coatings. Both, surface properties and aggregation characteristics are also key properties for the industrial application of ENPs, which leads to the development and commercialization of an increasing number of surface-functionalized ENPs. These include metals and oxides such as Cerium dioxide (CeO2) with various organic coatings. Therefore, we investigate CeO2 ENPs with different surface coatings such as weakly anionic polyvinyl alcohol (PVA) or strongly anionic poly acrylic acid (PAA) with respect to their colloidal stability in aqueous matrix under various hydrochemical conditions (pH, ionic strength) and their transport behavior in sand filter columns. Furthermore, we investigate the interaction of naturally occurring organic matter (NOM) with CeO2 ENPs and its effect on surface charge (zeta potential), colloidal stability and transport. While uncoated CeO2 ENPs aggregate at pH > 4 in aqueous matrix, our results show that PAA and PVA surface coatings as well as NOM sorbed to CeO2-NP surfaces can stabilize CeO2 ENPs under neutral and alkaline pH conditions in 1 mM KCl solution. Under slightly acidic conditions, differences between the three particle types were observed. PVA can stabilize particle suspensions in presence of 1 mM KCl at pH > 4.3, PAA at pH >4.0 and NOM at >3.2. While the presence of KCl did not influence particle size of NOM-CeO2 ENPs, CaCl2 at >2 mM lead to aggregation. Further results on the influence of KCl and CaCl2 on aggregation of coated CeO2 ENPs and transport in sand filter columns will be presented.

  5. [Degradation of 3,4- Dichlorobenzotrifluoride by Fe3O4/CeO2-H2O2 Heterogeneous Fenton-Like Systems].

    PubMed

    Sun, Zheng-nan; Yang, Qi; Ji, Dong-li; Zheng, Lin

    2015-06-01

    The 3,4-Dichlorobenzotrifluoride (3,4-DCBTE) was dehalogenated with oxidation treatment by heterogeneous Fenton-like system, using nanoscale Fe304/CeO2 as a catalyst. This nanoscale catalyst was prepared by the impregnated method. As a highly active new heterogeneous Fenton-like catalyst, nanoscale Fe304/CeO2 not only has the characteristics of the traditional Fenton-like catalyst but also can prevent the secondary pollution which caused by Fe2+. To find the optimum catalytic conditions for nanoscale Fe3O4/CeO2, the influence factors were investigated. The results indicated that the degradation ratio of 3,4-DCBTE was significantly improved by adding nanoscale Fe3O4/CeO2, with the removal ratio reaching 97.76% in 120 minutes and 79.85% in 20 minutes. As the temperature increasing, the catalytic effect of nanoscale Fe3O4/CeO2 catalyst had been constantly improved obviously. As the pH decreased, the degradation ratio of 3,4-DCBTE increased. With the increase of dosage of hydrogen peroxide (H2O2), the degradation efficiency of 3,4-DCBTE initially increased and then decreased, because oxygen (O2) was generated in preferential self-reaction when an excess of (H2O2) was added. The optimum removal efficiency was observed with the dosage of 15 mg x L(-1). With the increased amount of catalyst, there was a same trend as dosage of hydrogen peroxide (H2O2). The degradation ratio of 3,4-DCBTE initially increased and then decreased, the optimum amount of catalyst was 0.5 g x L(-1). The results also suggested that the reaction process followed the first-order kinetics and the thermodynamic analysis demonstrated that the reaction was only needed low reaction activation energy.

  6. [Research on SCR denitrification of MnOx/Al2O3 modified by CeO2 and its mechanism at low temperature].

    PubMed

    Guo, Jing; Li, Cai-Ting; Lu, Pei; Cui, Hua-Fei; Peng, Dun-Liang; Wen, Qing-Bo

    2011-08-01

    The Al2O3,which has large specific surface area and is used as carrier,was prepared by sol-gel method in this study. Series catalysts of MnOx, CeO2 plus MnOx supported on Al2O3 by isometric impregnation method. The SCR denitrification experimental conditions were as follows: NH3 as reductive agent, certain gas velocity and suitable ratio of gas mixed was setup. Furthermore, the experiments of BET, XRD and SEM were also carried out respectively in order to obtain physicochemical properties of the prepared catalysts. The experimental results showed that the loading of active component and calcination temperature made a big difference to the catalysts' performance. With appropriate addition of CeO2, MnOx/Al2O3 exhibits better activity and stability. For MnOx/Al2O3, the catalytic activity on NO was greatly influenced by its loaded content, and 7% MnOx/Al2O3 showed superior catalytic activity among the MnOx/Al2O3. The addition of CeO2 could greatly improve the dispersibility of MnOx on the carrier and increase its catalytic activity. The 4% CeO2 addition was the optimum loaded mass precent. Forthermore, 550 degrees C is the best calcination temperature, as MnOx formed different crystalline phases with temperature, at the same time, the addition of CeO2 could affect MnOx crystalline phase. The catalytic mechanism of SCR on NO was also discussed.

  7. Ion-Beam-Induced Chemical Mixing at a Nanocrystalline CeO2 Si Interface

    SciTech Connect

    Edmondson, Dr. Philip; Young, Neil P.; Parish, Chad M; Moll, Sandra; Namavar, Fereydoon; Weber, William J; Zhang, Yanwen

    2013-01-01

    Thin films of nanocrystalline ceria deposited onto a silicon substrate have been irradiated with 3 MeV Au+ ions to a total dose of 34 displacements per atom to examine the film/substrate interfacial response upon displacement damage. Under irradiation, a band of contrast is observed to form that grows under further irradiation. Scanning and high-resolution transmission electron microscopy imaging and analysis suggest that this band of contrast is a cerium silicate phase with an approximate Ce:Si:O composition ratio of 1:1:3 in an amorphous nature. The slightly nonstoichiometric composition arises due to the loss of mobile oxygen within the cerium silicate phase under the current irradiation condition. This nonequilibrium phase is formed as a direct result of ion-beam-induced chemical mixing caused by ballistic collisions between the incoming ion and the lattice atoms. This may hold promise in ion beam engineering of cerium silicates for microelectronic applications e.g., the fabrication of blue LEDs.

  8. Evidence of translocation and physiological impacts of foliar applied CeO2 nanoparticles on cucumber (Cucumis sativus) plants.

    PubMed

    Hong, Jie; Peralta-Videa, Jose R; Rico, Cyren; Sahi, Shivendra; Viveros, Marian N; Bartonjo, Jane; Zhao, Lijuan; Gardea-Torresdey, Jorge L

    2014-04-15

    Currently, most of the nanotoxicity studies in plants involve exposure to the nanoparticles (NPs) through the roots. However, plants interact with atmospheric NPs through the leaves, and our knowledge on their response to this contact is limited. In this study, hydroponically grown cucumber (Cucumis sativus) plants were aerially treated either with nano ceria powder (nCeO2) at 0.98 and 2.94 g/m(3) or suspensions at 20, 40, 80, 160, and 320 mg/L. Fifteen days after treatment, plants were analyzed for Ce uptake by using ICP-OES and TEM. In addition, the activity of three stress enzymes was measured. The ICP-OES results showed Ce in all tissues of the CeO2 NP treated plants, suggesting uptake through the leaves and translocation to the other plant parts. The TEM results showed the presence of Ce in roots, which corroborates the ICP-OES results. The biochemical assays showed that catalase activity increased in roots and ascorbate peroxidase activity decreased in leaves. Our findings show that atmospheric NPs can be taken up and distributed within plant tissues, which could represent a threat for environmental and human health.

  9. L-Arginine-Triggered Self-Assembly of CeO2 Nanosheaths on Palladium Nanoparticles in Water.

    PubMed

    Wang, Xiao; Zhang, Yibo; Song, Shuyan; Yang, Xiangguang; Wang, Zhuo; Jin, Rongchao; Zhang, Hongjie

    2016-03-24

    Pd@CeO2 core-shell nanostructures with a tunable Pd core size, shape, and nanostructure as well as a tunable CeO2 sheath thickness were obtained by a biomolecule-assisted method. The synthetic process is simple and green, as it involves only the heating of a mixture of Ce(NO3 )3 , l-arginine, and preformed Pd seeds in water without additives. Importantly, the synthesis is free of thiol groups and halide ions, thus providing a possible solution to the problem of secondary pollution by Pd nanoparticles in the sheath-coating process. The Pd/CeO2 nanostructures can be composited well with γ-Al2 O3 to create a heterogeneous catalyst. In subsequent tests of catalytic NO reduction by CO, Pd@CeO2 /Al2 O3 samples based on Pd cubes (6, 10, and 18 nm), Pd octahedra (6 nm), and Pd cuboctahedra (9 nm) as well as a simply loaded Pd cube (6 nm)-CeO2 /Al2 O3 sample were used as catalysts to investigate the effects of the Pd core size and shape and the hybrid nanostructure on the catalytic performance.

  10. Catalytic wet air oxidation of phenol using CeO2 as the catalyst. Kinetic study and mechanism development.

    PubMed

    Chang, Dong-Jang; Lin, Shiow-Shyung; Chen, Chun-Liang; Wang, Shu-Pin; Ho, Wei-Lun

    2002-08-01

    Using a CeO2 catalyst prepared from CeCl3.7H2O under high thermal impact, the catalytic wet air oxidation (CWAO) of phenol was effectively implemented. With initial phenol concentrations of between (400 and 2500) mg/L, and at a temperature of 160 degrees C, the rate of phenol conversion increased with increased catalyst loading (0.2g/L-1.0g/L) and oxygen pressure (0.5 MPa-1.5 MPa). Even at an initial concentration of 2500 mg/L, conversion of phenol was as high as 95% after 3 h reaction. The effect of phenol concentration, catalyst loading, and oxygen pressure on the initial rate of phenol conversion was evaluated in a kinetic study. The initial rate equation derived from kinetic study is: Ro=k1 x [Ph]1.3-1.4 x W0.5-0.6 x PO2(0.9-1.1), where k1 is a rate constant, and [Ph], W and PO2 refer to phenol concentration, catalyst loading and oxygen pressure, respectively. A free-radical involved reaction mechanism was proposed and an initial rate expression based on this mechanism was derived: Ro = k2 x [Ph]1.5 x W0.5, where k2 is also a rate constant. Fitting of experimental data with the theoretically derived initial rate equation resulted in good correlation: the coefficient is greater than 0.99.

  11. Effect of poling process on piezoelectric properties of BCZT - 0.08 wt.% CeO2 lead-free ceramics

    NASA Astrophysics Data System (ADS)

    Chandrakala, E.; Praveen, J. Paul; Das, Dibakar

    2016-05-01

    The properties of lead free piezoelectric materials can be tuned by suitable doping in the A and B sites of the perovskite structure. In the present study, cerium has been identified as a dopant to investigate the piezoelectric properties of lead-free BCZT system. BCZT - 0.08 wt.%CeO2 lead-free ceramics have been synthesized using sol-gel technique and the effects of CeO2 dopant on their phase structure and piezoelectric properties were investigated systematically. Poling conditions, such as temperature, electric field, and poling time have been optimized to get enhanced piezoelectric response. The optimized poling conditions (50°C, 3Ec and 30min) resulted in high piezoelectric charge coefficient d33 ~ 670pC/N, high electromechanical coupling coefficient kp ~ 60% and piezoelectric voltage coefficient g33 ~ 14 mV.m/N for BCZT - 0.08wt.% CeO2 ceramics.

  12. Near-infrared emissions from Yb3+-doped CeO2 and Ce2Si2O7 films based on silicon substrates subjected to thermal treatment

    NASA Astrophysics Data System (ADS)

    Mu, Guangyao; Wang, Shenwei; Li, Ling; Yin, Xue; Huang, Miaoling; Yi, Lixin

    2016-05-01

    Photoluminescence properties of Yb3+-doped CeO2 films annealed in different atmospheres were investigated. CeO2:Yb3+ films were deposited by electron-beam evaporation technique. Near-infrared emission around 970 nm was observed after annealing the films both in air and in Ar-H2 atmosphere, which is attributed to the Yb3+:2F5/2 → 2F7/2 transition. Optimization of the Yb3+ concentration for the 970 nm luminescence yield was also investigated. Characterized by different methods, Ce2Si2O7 was formed in the films annealed in reducing atmosphere, which was expected to be more applicable for the silicon-based optoelectronic applications.

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

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

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

  14. Flowerlike CeO2 microspheres coated with Sr2Fe1.5Mo0.5Ox nanoparticles for an advanced fuel cell

    PubMed Central

    Liu, Yanyan; Tang, Yongfu; Ma, Zhaohui; Singh, Manish; He, Yunjuan; Dong, Wenjing; Sun, Chunwen; Zhu, Bin

    2015-01-01

    Flowerlike CeO2 coated with Sr2Fe1.5Mo0.5Ox (Sr-Fe-Mo-oxide) nanoparticles exhibits enhanced conductivity at low temperatures (300–600 oC), e.g. 0.12 S cm−1 at 600 oC, this is comparable to pure ceria (0.1 S cm−1 at 800 oC). Advanced single layer fuel cell was constructed using the flowerlike CeO2/Sr-Fe-Mo-oxide layer attached to a Ni-foam layer coated with the conducting transition metal oxide. Such fuel cell has yielded a peak power density of 802 mWcm−2 at 550 oC. The mechanism of enhanced conductivity and cell performance were analyzed. These results provide a promising strategy for developing advanced low-temperature SOFCs. PMID:26154917

  15. Hydrophilic CeO2 nanocubes protect pancreatic β-cell line INS-1 from H2O2-induced oxidative stress

    NASA Astrophysics Data System (ADS)

    Lyu, Guang-Ming; Wang, Yan-Jie; Huang, Xue; Zhang, Huai-Yuan; Sun, Ling-Dong; Liu, Yan-Jun; Yan, Chun-Hua

    2016-04-01

    Oxidative stress plays a key role in the occurrence and development of diabetes. With their unique redox properties, CeO2 nanoparticles (nanoceria) exhibit promising potential for the treatment of diabetes resulting from oxidative stress. Here, we develop a novel preparation of hydrophilic CeO2 nanocubes (NCs) with two different sizes (5 nm and 25 nm) via an acetate assisted hydrothermal method. Dynamic light scattering, zeta potential measurements and thermogravimetric analyses were utilized to investigate the changes in the physico-chemical characteristics of CeO2 NCs when exposed to in vitro cell culture conditions. CCK-8 assays revealed that the CeO2 NCs did not impair cell proliferation in the pancreatic β-cell line INS-1 at the highest dose of 200 μg mL-1 over the time scale of 72 h, while being able to protect INS-1 cells from H2O2-induced cytotoxicity even after protein adsorption. It is also noteworthy that nanoceria with a smaller hydrodynamic radius exhibit stronger antioxidant and anti-apoptotic effects, which is consistent with their H2O2 quenching capability in biological systems. These findings suggest that nanoceria can be used as an excellent antioxidant for controlling oxidative stress-induced pancreatic β-cell damage.Oxidative stress plays a key role in the occurrence and development of diabetes. With their unique redox properties, CeO2 nanoparticles (nanoceria) exhibit promising potential for the treatment of diabetes resulting from oxidative stress. Here, we develop a novel preparation of hydrophilic CeO2 nanocubes (NCs) with two different sizes (5 nm and 25 nm) via an acetate assisted hydrothermal method. Dynamic light scattering, zeta potential measurements and thermogravimetric analyses were utilized to investigate the changes in the physico-chemical characteristics of CeO2 NCs when exposed to in vitro cell culture conditions. CCK-8 assays revealed that the CeO2 NCs did not impair cell proliferation in the pancreatic β-cell line INS-1 at the highest dose of 200 μg mL-1 over the time scale of 72 h, while being able to protect INS-1 cells from H2O2-induced cytotoxicity even after protein adsorption. It is also noteworthy that nanoceria with a smaller hydrodynamic radius exhibit stronger antioxidant and anti-apoptotic effects, which is consistent with their H2O2 quenching capability in biological systems. These findings suggest that nanoceria can be used as an excellent antioxidant for controlling oxidative stress-induced pancreatic β-cell damage. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr00826g

  16. Photocatalytic activity of binary metal oxide nanocomposites of CeO2/CdO nanospheres: Investigation of optical and antimicrobial activity.

    PubMed

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

    2016-10-01

    We report the synthesis of high quality CeO2-CdO binary metal oxide nanocomposites were synthesized by a simple chemical precipitation and hydrothermal method. Cerium nitrate and cadmium nitrate were used as precursors. Composition, structure and morphology of the nanocomposites were analyzed by X-ray diffraction (XRD) and high resolution transmission electron microscopy (HRTEM). XRD pattern proves that the final product has cubic phase and the particle size diameter of the nanocomposites are 27nm, XRD results also indicated that the crystalline properties of the nanocomposite were improved without affecting the parent lattice, FESEM analysis indicates that the product is composed of spherical particles in clusters. The morphological and optical properties of CeO2-CdO nanosamples were characterized by HRTEM and DRS spectroscopy. The IR results showed high purity of products and indicated that the nanocomposites are made up of CeO2 and CdO bonds. Absorption spectra exhibited an upward shift in characteristic peaks caused by the addition of transition metal oxide, suggesting that crystallinity of both the metal oxide is improved due to specific doping level. TGA plots further confirmed the purity and stability of nanomaterials prepared. Hence the nanocomposite has cubic crystal lattice and form a homogeneous solid structure. From the result, Cd(2+) ions are embedded in the cubic crystal lattice of ceria. The growth rate increases which are ascribed to the cationic doping with a lower valence cation. Ce-Cd binary metal oxide nanocomposites showed antibacterial activity, it showed the better growth inhibition towards p.aeruginosa. Exploit of photodegradation and photocatalytic activity of large scale synthesis of CeO2-CdO binary metal oxide nanocomposites was reported.

  17. Anchoring High-Concentration Oxygen Vacancies at Interfaces of CeO(2-x)/Cu toward Enhanced Activity for Preferential CO Oxidation.

    PubMed

    Chen, Shaoqing; Li, Liping; Hu, Wanbiao; Huang, Xinsong; Li, Qi; Xu, Yangsen; Zuo, Ying; Li, Guangshe

    2015-10-21

    Catalysts are urgently needed to remove the residual CO in hydrogen feeds through selective oxidation for large-scale applications of hydrogen proton exchange membrane fuel cells. We herein propose a new methodology that anchors high concentration oxygen vacancies at interface by designing a CeO2-x/Cu hybrid catalyst with enhanced preferential CO oxidation activity. This hybrid catalyst, with more than 6.1% oxygen vacancies fixed at the favorable interfacial sites, displays nearly 100% CO conversion efficiency in H2-rich streams over a broad temperature window from 120 to 210 °C, strikingly 5-fold wider than that of conventional CeO2/Cu (i.e., CeO2 supported on Cu) catalyst. Moreover, the catalyst exhibits a highest cycling stability ever reported, showing no deterioration after five cycling tests, and a super long-time stability beyond 100 h in the simulated operation environment that involves CO2 and H2O. On the basis of an arsenal of characterization techniques, we clearly show that the anchored oxygen vacancies are generated as a consequence of electron donation from metal copper atoms to CeO2 acceptor and the subsequent reverse spillover of oxygen induced by electron transfer in well controlled nanoheterojunction. The anchored oxygen vacancies play a bridging role in electron capture or transfer and drive molecule oxygen into active oxygen species to interact with the CO molecules adsorbed at interfaces, thus leading to an excellent preferential CO oxidation performance. This study opens a window to design a vast number of high-performance metal-oxide hybrid catalysts via the concept of anchoring oxygen vacancies at interfaces. PMID:26444246

  18. Oxygen diffusion in ThO2-CeO2 and ThO2-UO2 solid solutions from atomistic calculations.

    PubMed

    Aidhy, Dilpuneet S

    2016-06-01

    We elucidate oxygen diffusivity in ThO2-CeO2 and ThO2-UO2 solid solutions across their whole concentration ranges in the phase diagram using static pair-potential calculations and molecular dynamics simulations. Between pure CeO2 (and UO2) and pure ThO2, oxygen diffusivity is higher in CeO2 (and UO2) due to lower oxygen migration barriers. With the addition of Th to CeO2 (and UO2) in the phase diagram, the diffusivity decreases due to the increase in the migration barriers introduced by a larger ionic radius of Th. On the other side of the phase diagram, with the addition of Ce to ThO2 oxygen diffusion decreases due to oxygen vacancy binding with Ce, even though the migration barriers decrease due to the smaller size of Ce than the host Th. Using these calculations, we provide a schematic of high oxygen diffusivity regions in the phase diagram. We also compare the impact of tetravalent dopants (e.g. actinides) on oxygen vacancy energetics to that of trivalent dopants (e.g. lanthanides). We find that trivalent dopants bind much more strongly with oxygen vacancy than the tetravalent dopants. We also find that the tetravalent dopants that have larger radii than the host cation have negative oxygen vacancy binding energy, whereas all trivalent dopants have positive binding energy irrespective of their ionic radii. This work thus highlights key differences in the oxygen vacancy energetics between the trivalent and tetravalent cations.

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

    PubMed

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

    2016-07-28

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

  20. Towards the standardization of nanoecotoxicity testing: Natural organic matter 'camouflages' the adverse effects of TiO2 and CeO2 nanoparticles on green microalgae.

    PubMed

    Cerrillo, Cristina; Barandika, Gotzone; Igartua, Amaya; Areitioaurtena, Olatz; Mendoza, Gemma

    2016-02-01

    In the last few years, the emission of CeO2 and TiO2 nanoparticles (NPs) into the environment has been raising concerns about their potential adverse effects on wildlife and human health. Aquatic organisms constitute one of the most important pathways for the entrance of these NPs and transfer throughout the food web, but divergences exist in the experimental data published on their aquatic toxicity. The pressing need for standardization of methods to analyze their ecotoxicity requires aquatic media representing realistic environmental conditions. The present study aimed to determine the usefulness of Suwannee River natural organic matter (SR-NOM) in the assessment of the agglomeration kinetics and ecotoxicity of CeO2 and TiO2 NPs towards green microalgae Pseudokirchneriella subcapitata. SR-NOM alleviated the adverse effects of NPs on algal growth, completely in the case of TiO2 NPs and partially in the case of CeO2 NPs, suggesting a 'camouflage' of toxicity. This behavior has been observed also for other algal species and types of natural organic matter in the literature. Furthermore, SR-NOM markedly increased the stability of the NPs in algal medium, which led to a better reproducibility of the toxicity test results, and provided an electrophoretic mobility similar to that previously reported in various river and groundwaters. Thus, SR-NOM can be a representative sample of what is found in many different ecosystems, and the observed 'camouflage' of the effects of CeO2 and TiO2 NPs on algal cells might be considered as a natural interaction occurring in their standardized ecotoxicological assessment. PMID:26580731

  1. Low temperature destruction of PCDD/Fs over V2O5-CeO2/TiO2 catalyst with ozone.

    PubMed

    Yu, Ming-Feng; Lin, Xiao-Qing; Yan, Mi; Li, Xiao-Dong; Chen, Tong; Yan, Jian-Hua

    2016-09-01

    Catalytic destruction of PCDD/Fs (polychlorinated dibenzo-p-dioxins and furans) over V2O5-CeO2/TiO2 catalyst was investigated at a low temperature range of 140-180 °C, in the absence and presence of ozone (200 ppm). Nano-TiO2 support was used to prepare the catalyst by step impregnation method. A stable PCDD/Fs-generating system was established to support the catalytic destruction tests. In the presence of ozone alone, destruction efficiencies of PCDD/Fs are between 32.2 and 43.1 % with temperature increasing from 140 to 180 °C. The activity of V2O5-CeO2/TiO2 catalyst alone on PCDD/Fs destruction is also studied. The increase of temperature from 140 to 180 °C enhances the activity of catalyst with destruction efficiencies increasing from 54.7 to 73.4 %. However, ozone addition greatly enhances the catalytic activity of V2O5-CeO2/TiO2 catalyst on PCDD/Fs decomposition. At 180 °C, the destruction efficiency of PCDD/Fs achieved with V2O5-CeO2/TiO2 catalyst and ozone is above 86.0 %. It indicates that the combined use of ozone and catalyst reduces the reaction temperature of PCDD/Fs oxidation and offers a new method to destroy PCDD/Fs with high destruction efficiency at a low temperature. Furthermore, the destruction efficiencies of 17 toxic PCDD/F congeners, achieved with ozone alone, catalyst alone, and catalyst/ozone are analyzed. PMID:27234830

  2. Photocatalytic activity of binary metal oxide nanocomposites of CeO2/CdO nanospheres: Investigation of optical and antimicrobial activity.

    PubMed

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

    2016-10-01

    We report the synthesis of high quality CeO2-CdO binary metal oxide nanocomposites were synthesized by a simple chemical precipitation and hydrothermal method. Cerium nitrate and cadmium nitrate were used as precursors. Composition, structure and morphology of the nanocomposites were analyzed by X-ray diffraction (XRD) and high resolution transmission electron microscopy (HRTEM). XRD pattern proves that the final product has cubic phase and the particle size diameter of the nanocomposites are 27nm, XRD results also indicated that the crystalline properties of the nanocomposite were improved without affecting the parent lattice, FESEM analysis indicates that the product is composed of spherical particles in clusters. The morphological and optical properties of CeO2-CdO nanosamples were characterized by HRTEM and DRS spectroscopy. The IR results showed high purity of products and indicated that the nanocomposites are made up of CeO2 and CdO bonds. Absorption spectra exhibited an upward shift in characteristic peaks caused by the addition of transition metal oxide, suggesting that crystallinity of both the metal oxide is improved due to specific doping level. TGA plots further confirmed the purity and stability of nanomaterials prepared. Hence the nanocomposite has cubic crystal lattice and form a homogeneous solid structure. From the result, Cd(2+) ions are embedded in the cubic crystal lattice of ceria. The growth rate increases which are ascribed to the cationic doping with a lower valence cation. Ce-Cd binary metal oxide nanocomposites showed antibacterial activity, it showed the better growth inhibition towards p.aeruginosa. Exploit of photodegradation and photocatalytic activity of large scale synthesis of CeO2-CdO binary metal oxide nanocomposites was reported. PMID:27541568

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

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

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

  4. Towards the standardization of nanoecotoxicity testing: Natural organic matter 'camouflages' the adverse effects of TiO2 and CeO2 nanoparticles on green microalgae.

    PubMed

    Cerrillo, Cristina; Barandika, Gotzone; Igartua, Amaya; Areitioaurtena, Olatz; Mendoza, Gemma

    2016-02-01

    In the last few years, the emission of CeO2 and TiO2 nanoparticles (NPs) into the environment has been raising concerns about their potential adverse effects on wildlife and human health. Aquatic organisms constitute one of the most important pathways for the entrance of these NPs and transfer throughout the food web, but divergences exist in the experimental data published on their aquatic toxicity. The pressing need for standardization of methods to analyze their ecotoxicity requires aquatic media representing realistic environmental conditions. The present study aimed to determine the usefulness of Suwannee River natural organic matter (SR-NOM) in the assessment of the agglomeration kinetics and ecotoxicity of CeO2 and TiO2 NPs towards green microalgae Pseudokirchneriella subcapitata. SR-NOM alleviated the adverse effects of NPs on algal growth, completely in the case of TiO2 NPs and partially in the case of CeO2 NPs, suggesting a 'camouflage' of toxicity. This behavior has been observed also for other algal species and types of natural organic matter in the literature. Furthermore, SR-NOM markedly increased the stability of the NPs in algal medium, which led to a better reproducibility of the toxicity test results, and provided an electrophoretic mobility similar to that previously reported in various river and groundwaters. Thus, SR-NOM can be a representative sample of what is found in many different ecosystems, and the observed 'camouflage' of the effects of CeO2 and TiO2 NPs on algal cells might be considered as a natural interaction occurring in their standardized ecotoxicological assessment.

  5. Metabolomic effects in HepG2 cells exposed to CeO2, SiO2 and CuO nanomaterials.

    EPA Science Inventory

    To better assess potential hepatotoxicity of nanomaterials, human liver HepG2 cells were exposed for three days to 5 different CeO2 (either 30 or 100 ug/ml), 3 SiO2 based (30 ug/ml) or 1 CuO (3 ug/ml) nanomaterials with dry primary particle sizes ranging from 15 to 213 nm. Metab...

  6. A competitive coordination-based CeO2 nanowire-DNA nanosensor: fast and selective detection of hydrogen peroxide in living cells and in vivo.

    PubMed

    Gao, Wen; Wei, Xueping; Wang, Xuejun; Cui, Guanwei; Liu, Zhenhua; Tang, Bo

    2016-03-01

    A competitive coordination-based hydrogen peroxide (H2O2) nanosensor is constructed by the assembly of FAM-tagged single-strand (ss) DNA on cerium oxide nanowires (CeO2 NWs). This fluorescent nanosensor is capable of rapidly and selectively tracking H2O2 within living cells, as well as directly visualizing H2O2 generated by wound-induced oxidative damage in zebrafish larvae. PMID:26848646

  7. Low temperature destruction of PCDD/Fs over V2O5-CeO2/TiO2 catalyst with ozone.

    PubMed

    Yu, Ming-Feng; Lin, Xiao-Qing; Yan, Mi; Li, Xiao-Dong; Chen, Tong; Yan, Jian-Hua

    2016-09-01

    Catalytic destruction of PCDD/Fs (polychlorinated dibenzo-p-dioxins and furans) over V2O5-CeO2/TiO2 catalyst was investigated at a low temperature range of 140-180 °C, in the absence and presence of ozone (200 ppm). Nano-TiO2 support was used to prepare the catalyst by step impregnation method. A stable PCDD/Fs-generating system was established to support the catalytic destruction tests. In the presence of ozone alone, destruction efficiencies of PCDD/Fs are between 32.2 and 43.1 % with temperature increasing from 140 to 180 °C. The activity of V2O5-CeO2/TiO2 catalyst alone on PCDD/Fs destruction is also studied. The increase of temperature from 140 to 180 °C enhances the activity of catalyst with destruction efficiencies increasing from 54.7 to 73.4 %. However, ozone addition greatly enhances the catalytic activity of V2O5-CeO2/TiO2 catalyst on PCDD/Fs decomposition. At 180 °C, the destruction efficiency of PCDD/Fs achieved with V2O5-CeO2/TiO2 catalyst and ozone is above 86.0 %. It indicates that the combined use of ozone and catalyst reduces the reaction temperature of PCDD/Fs oxidation and offers a new method to destroy PCDD/Fs with high destruction efficiency at a low temperature. Furthermore, the destruction efficiencies of 17 toxic PCDD/F congeners, achieved with ozone alone, catalyst alone, and catalyst/ozone are analyzed.

  8. Rapid deposition of biaxially-textured CeO 2 buffer layers on polycrystalline nickel alloy for superconducting tapes by ion assisted pulsed laser deposition

    NASA Astrophysics Data System (ADS)

    Xiong, Xuming; Winkler, Dag

    2000-07-01

    The long deposition time of sharply textured buffer layer was the main obstacle for the ion beam assisted deposition (IBAD) process to go to large scale fabrication of superconducting tapes. This paper shows that this obstacle can be overcome. (002)-oriented, sharply-textured CeO 2 buffer layers with (111) phi-scan full width of half maximum (FWHM) of 10° were deposited by ion beam assisted pulsed laser deposition (PLD) on polycrystalline Hastelloy C in 10 min. The deposition rate was about 3 nm/s. CeO 2 film surface was smooth and free of cracks compared with film by inclined substrate deposition (ISD). The IBAD was carried out at small ion-to-atom ratio values, which resulted in CeO 2 (200) plane aligned along the incident plane of the ion beam. The Jc of Y 1Ba 2Cu 3O 7- δ (YBCO) film deposited on the buffer layer was 7.3×10 5 A/cm 2.

  9. Catalytic Activity and Thermal Stability of Arc Plasma Deposited Pt Nano-Particles on CeO2-Al2O3.

    PubMed

    Jeong, Young Eun; Kumar, Pullur Anil; Choi, Hee Lack; Lee, Kwan-Young; Ha, Heon Phil

    2015-11-01

    In this study, catalytic activity and thermal stability of the arc plasma deposited (APD) Pt nano-particles on A12O3 and CeO2-Al2O3 were compared with that of the conventionally prepared Pt/Al2O3. All the catalysts were characterized by BET-surface area, transmission electron microscopy, X-ray photoelectron spectroscopy, CO-pulse chemisorption, H2-temperarture programmed reduction and X-ray absorption near edge spectroscopy. Through the quantum chemical calculations of different metal oxide support, CeO2 was identified as a suitable anchoring material with high energy level between the Pt species (Pt(0) and PtO(x)) on ceria. Subsequently, the results of XPS and XANES revealed the presence of abundant Pt(0) metal species in APD catalysts. The addition of ceria to Al2O3 support enhanced the dispersion of Pt nano-particles. The H2-TPR of Pt/CeO2-Al2O3 (APD) catalyst showed high-temperature reduction peaks corresponding to the interaction of Pt with ceria on alumina by Pt-O-Ce. Consequently, the Pt nano-particles deposited on CeO2-Al2O3 by APD attained strong thermal resistance at high temperatures. In addition, superior catalytic activities for CO and C3H6 oxidation and NO(x) reduction were obtained for the Pt/CeO2- Al2O3 (APD) catalyst.

  10. Acetic Acid Reforming over Rh Supported on La2O3/CeO2-ZrO2: Catalytic Performance and Reaction Pathway Analysis

    SciTech Connect

    Lemonidou, Angeliki A.; Vagia, Ekaterini C.; Lercher, Johannes A.

    2013-07-11

    Reforming of acetic acid was investigated on Rh supported on CeO2-ZrO2 modified with 3 wt % La. The active catalyst converted acetic acid to H-2-rich gas and hardly formed coke. The low rate of coke formation is concluded to be related to the presence of redox-active oxygen limiting the concentration of coke precursors. Temperature-programmed O-18(2)) isotope exchange measurements showed that the La2O3 and Rh enhanced the mobility of lattice oxygen compared with that of the parent CeO2-ZrO2. Ketonization and decarboxylation of acetic acid are the dominating reactions over the latter up to 600 degrees C, whereas above 600 degrees C, steam reforming and water gas shift also contribute. Over 0.5 wt % Rh on La2O3/CeO2-ZrO2, reforming and water gas shift reactions dominate, even below 300 degrees C, producing mostly H-2 and CO2. Using isotope labeling, it is shown that acetic acid adsorbs dissociatively on Rh, forming acetates, which sequentially decarboxylate and form surface methyl groups. The latter are in turn converted to CO, CO2, and H-2.

  11. Reverse micelles directed synthesis of TiO2-CeO2 mixed oxides and investigation of their crystal structure and morphology

    NASA Astrophysics Data System (ADS)

    Matějová, Lenka; Valeš, Václav; Fajgar, Radek; Matěj, Zdeněk; Holý, Václav; Šolcová, Olga

    2013-02-01

    The synthesis of TiO2-CeO2 mixed oxides based on the sol-gel process controlled within reverse micelles of non-ionic surfactant Triton X-114 in cyclohexane is reported. The crystallization, phase composition, trends in nanoparticles growth and porous structure properties are studied as a function of Ti:Ce molar composition and annealing temperature by in-situ X-ray diffraction, Raman spectroscopy and physisorption. The brannerite-type CeTi2O6 crystallizes as a single crystalline phase at Ti:Ce molar composition of 70:30 and in the mixture with cubic CeO2 and anatase TiO2 for composition 50:50. At Ti:Ce molar ratios 90:10 and 30:70 the mixtures of TiO2 anatase, rutile and cubic CeO2 appear. In these mixtures TiO2 rutile is formed at higher temperatures than conventionally. Additionally, the amount of a present amorphous phase in individual mixtures was estimated from diffraction data. The porous structure morphology depends both on molar composition and annealing temperature. This is correlated with the presence of carbon impurities of different character.

  12. Assessing the axonal translocation of CeO2 and SiO2 nanoparticles in the sciatic nerve fibers of the frog: an ex vivo electrophysiological study

    PubMed Central

    Kastrinaki, Georgia; Samsouris, Christos; Kosmidis, Efstratios K; Papaioannou, Eleni; Konstandopoulos, Athanasios G; Theophilidis, George

    2015-01-01

    The axonal translocation of two commonly used nanoparticles in medicine, namely CeO2 and SiO2, is investigated. The study was conducted on frog sciatic nerve fibers in an ex vivo preparation. Nanoparticles were applied at the proximal end of the excised nerve. A nerve stimulation protocol was followed for over 35 hours. Nerve vitality curve comparison between control and exposed nerves showed that CeO2 has no neurotoxic effect at the concentrations tested. After exposure, specimens were fixed and then screen scanned every 1 mm along their length for nanoparticle presence by means of Fourier transform infrared microscopy. We demonstrated that both nanoparticles translocate within the nerve by formation of narrow bands in the Fourier transform infrared spectrum. For the CeO2, we also demonstrated that the translocation depends on both axonal integrity and electrical activity. The speed of translocation for the two species was estimated in the range of 0.45–0.58 mm/h, close to slow axonal transportation rate. Transmission electron microscopy provided direct evidence for the presence of SiO2 in the treated nerves. PMID:26648718

  13. One-pot hydrothermal growth of raspberry-like CeO2 on CuO microsphere as copper-based catalyst for Rochow reaction

    NASA Astrophysics Data System (ADS)

    Jin, Zheying; Li, Jing; Shi, Laishun; Ji, Yongjun; Zhong, Ziyi; Su, Fabing

    2015-12-01

    In this work, we prepared a novel structure comprising of raspberry-like CeO2 deposited on CuO microspheres (Ce-CuO) for Rochow reaction. The synthesis was carried out via a facile one-pot hydrothermal reaction without using any template, in which, the basic copper carbonate microspheres were first formed via self-assembly of basic copper carbonate nanorods, followed with deposition of cerium hydroxide. After calcination, they were transformed into Ce-CuO but still maintained the hierarchical structure, and meanwhile, mesoporous structure was formed (for simplicity, we will only state them as metal oxide in the following context). The samples were characterized by X-ray diffraction (XRD), temperature-programmed reduction (TPR), X-ray photoelectron spectroscopy (XPS), high-resolution transmission electron microscopy (HRTEM), and scanning electron microscopy (SEM) techniques. When used as a Cu-based catalyst, Ce-CuO exhibited superior catalytic property to the single CuO, CeO2 and their physically mixture in the Rochow reaction with dimethyldichlorosilane (M2) selectivity increased from ca. 65 to 83.7%. The higher M2 selectivity of Ce-CuO is mainly due to its larger surface area and the synergistic effect between CuO and CeO2. This work demonstrates that catalytic performance of the Cu-based can be improved by adding Ce rare-earth element and by carefully controlling their structures.

  14. Single particle ICP-MS method development for the determination of plant uptake and accumulation of CeO2 nanoparticles.

    PubMed

    Dan, Yongbo; Ma, Xingmao; Zhang, Weilan; Liu, Kun; Stephan, Chady; Shi, Honglan

    2016-07-01

    Cerium dioxide nanoparticles (CeO2NPs) are among the most broadly used engineered nanoparticles that will be increasingly released into the environment. Thus, understanding their uptake, transportation, and transformation in plants, especially food crops, is critical because it represents a potential pathway for human consumption. One of the primary challenges for the endeavor is the inadequacy of current analytical methodologies to characterize and quantify the nanomaterial in complex biological samples at environmentally relevant concentrations. Herein, a method was developed using single particle-inductively coupled plasma-mass spectrometry (SP-ICP-MS) technology to simultaneously detect the size and size distribution of particulate Ce, particle concentration, and dissolved cerium in the shoots of four plant species including cucumber, tomato, soybean, and pumpkin. An enzymatic digestion method with Macerozyme R-10 enzyme previously used for gold nanoparticle extraction from the tomato plant was adapted successfully for CeO2NP extraction from all four plant species. This study is the first to report and demonstrate the presence of dissolved cerium in plant seedling shoots exposed to CeO2NPs hydroponically. The extent of plant uptake and accumulation appears to be dependent on the plant species, requiring further systematic investigation of the mechanisms. PMID:27129977

  15. Epitaxial growth of CeO2(111) film on Ru(0001): Scanning tunneling microscopy (STM) and x-ray photoemission spectroscopy (XPS) study

    NASA Astrophysics Data System (ADS)

    Hasegawa, Tomo; Shahed, Syed Mohammad Fakruddin; Sainoo, Yasuyuki; Beniya, Atsushi; Isomura, Noritake; Watanabe, Yoshihide; Komeda, Tadahiro

    2014-01-01

    We formed an epitaxial film of CeO2(111) by sublimating Ce atoms on Ru(0001) surface kept at elevated temperature in an oxygen ambient. X-ray photoemission spectroscopy measurement revealed a decrease of Ce4+/Ce3+ ratio in a small temperature window of the growth temperature between 1070 and 1096 K, which corresponds to the reduction of the CeO2(111). Scanning tunneling microscope image showed that a film with a wide terrace and a sharp step edge was obtained when the film was grown at the temperatures close to the reduction temperature, and the terrace width observed on the sample grown at 1060 K was more than twice of that grown at 1040 K. On the surface grown above the reduction temperature, the surface with a wide terrace and a sharp step was confirmed, but small dots were also seen in the terrace part, which are considerably Ce atoms adsorbed at the oxygen vacancies on the reduced surface. This experiment demonstrated that it is required to use the substrate temperature close to the reduction temperature to obtain CeO2(111) with wide terrace width and sharp step edges.

  16. Immunomodulation and T Helper TH1/TH2 Response Polarization by CeO2 and TiO2 Nanoparticles

    PubMed Central

    Schanen, Brian C.; Das, Soumen; Reilly, Christopher M.; Warren, William L.; Self, William T.; Seal, Sudipta; Drake, Donald R.

    2013-01-01

    Immunomodulation by nanoparticles, especially as related to the biochemical properties of these unique materials, has scarcely been explored. In an in vitro model of human immunity, we demonstrate two catalytic nanoparticles, TiO2 (oxidant) and CeO2 (antioxidant), have nearly opposite effects on human dendritic cells and T helper (TH) cells. For example, whereas TiO2 nanoparticles potentiated DC maturation that led towards TH1-biased responses, treatment with antioxidant CeO2 nanoparticles induced APCs to secrete the anti-inflammatory cytokine, IL-10, and induce a TH2-dominated T cell profile. In subsequent studies, we demonstrate these results are likely explained by the disparate capacities of the nanoparticles to modulate ROS, since TiO2, but not CeO2 NPs, induced inflammatory responses through an ROS/inflammasome/IL-1β pathway. This novel capacity of metallic NPs to regulate innate and adaptive immunity in profoundly different directions via their ability to modulate dendritic cell function has strong implications for human health since unintentional exposure to these materials is common in modern societies. PMID:23667525

  17. Methanol conversion over a Pd 5Cu/Al 2O 3-CeO 2 catalyst: An FT-IR study and reaction mechanism

    NASA Astrophysics Data System (ADS)

    Sánchez Escribano, V.; del Hoyo Martínez, C.; Castro Baz, A.; Gallardo Amores, J. M.; Fernández López, E.

    2011-12-01

    A catalyst composed of a Pd 5Cu mixed oxide supported over Al 2O 3-CeO 2 with general formula Pd 5CuO x/Al 2O 3-CeO 2 (Al/Ce atomic ratio = 1/1) has been prepared by a wet impregnation method and tested in the methanol conversion. The structural and morphological characterization of the catalyst evidences that it is a mesoporous material thermally stable up to 873 K. At that temperature the specific surface area value is 170 m 2/g, and a CeO 2 cubic phase is identified together with ill-defined diffraction peaks tentatively assigned to Cu-Pd clusters, suggesting that the active phase is well dispersed over the support. Infrared studies prove that methanol conversion takes place over the catalyst to a high extent yielding syngas as main product in the range 473-723 K and methane at higher temperatures. Oxygenated intermediates containing methoxy, carbonile or formiate species are not detected, which evidences that methanol conversion to methane very probably takes place according to a via-carbide mechanism.

  18. Methanol conversion over a Pd5Cu/Al2O3-CeO2 catalyst: an FT-IR study and reaction mechanism.

    PubMed

    Sánchez Escribano, V; del Hoyo Martínez, C; Castro Baz, A; Gallardo Amores, J M; Fernández López, E

    2011-12-01

    A catalyst composed of a Pd(5)Cu mixed oxide supported over Al(2)O(3)-CeO(2) with general formula Pd(5)CuO(x)/Al(2)O(3)-CeO(2) (Al/Ce atomic ratio=1/1) has been prepared by a wet impregnation method and tested in the methanol conversion. The structural and morphological characterization of the catalyst evidences that it is a mesoporous material thermally stable up to 873 K. At that temperature the specific surface area value is 170 m(2)/g, and a CeO(2) cubic phase is identified together with ill-defined diffraction peaks tentatively assigned to Cu-Pd clusters, suggesting that the active phase is well dispersed over the support. Infrared studies prove that methanol conversion takes place over the catalyst to a high extent yielding syngas as main product in the range 473-723 K and methane at higher temperatures. Oxygenated intermediates containing methoxy, carbonile or formiate species are not detected, which evidences that methanol conversion to methane very probably takes place according to a via-carbide mechanism. PMID:21930417

  19. Experimental study on a room temperature urea-SCR of NO over activated carbon fibre-supported CeO2-CuO.

    PubMed

    Jiang, Xiao; Lu, Pei; Li, Caiting; Zeng, Zheng; Zeng, Guangming; Hu, Luping; Mai, Lei; Li, Zhi

    2013-01-01

    In order to establish a desirable method for NO reduction, selective catalytic reduction (SCR) of NO by urea-CeO2/ACF and urea-CeO2-CuO/ACF was carried out at room temperature. The experimental results showed that 10% urea-9% CeO2/ACF could yield the highest NO conversion of 85% among the series of urea-CeO2/ACF prepared. When urea-CeO2-CuO/ACF was compared with urea-CeO2/ACF, it achieved higher NO conversion to a certain degree with the addition of CuO, which was attributed to the synergistic effect between cerium and copper. The effect of the mass ratio of CeO2 and CuO was also observed. The desirable mass ratio of CeO2 and CuO was 1:1, which yielded about 90% NO conversion when ACF was loaded with 10% urea. Furthermore, the influence of O2 concentration and NO concentration was also observed. In this study, NO conversion increased with increasing O2 concentration. In addition, some samples were further characterized by BET, X-ray diffraction, X-ray photoelectron spectroscopy and Fourier transform infrared methods.

  20. Selective catalytic reduction (SCR) of NO by urea loaded on activated carbon fibre (ACF) and CeO2/ACF at 30 degrees C: the SCR mechanism.

    PubMed

    Zeng, Zheng; Lu, Pei; Li, Caiting; Zeng, Guangming; Jiang, Xiao; Zhai, Yunbo; Fan, Xiaopeng

    2012-06-01

    Selective catalytic reduction (SCR) of NO by urea loaded on rayon-based activated carbon fibre (ACF) and CeO2/ACF (CA) was studied at ambient temperature (30 degrees C) to establish a basic scheme for its reduction. Nitric oxide was found to be reduced to N2 with urea deposited on the ACF and CA. When oxygen was present, the greater the amount of loaded urea (20-60%), the greater the NO(x) conversions, which were between 72.03% and 77.30%, whereas the NO(x) conversions were about 50% when oxygen was absent. Moreover, when the urea was loaded on CA, a catalyst containing 40% urea/ACF loaded with 10% CeO2 (UCA4) could yield a NO(x) conversion of about 80% for 24.5 h. Based on the experimental results, the catalytic mechanisms of SCR with and without oxygen are discussed. The enhancing effect of oxygen resulted from the oxidation of NO to NO2, and urea was the main reducing agent in the SCR of loaded catalysts. ACF-C was the catalytic centre in the SCR of NO of ACF, while CeO2 of urea-loaded CA was the catalytic centre.

  1. Hot Corrosion Studies of Detonation-Gun-Sprayed NiCrAlY + 0.4 wt.% CeO2 Coated Superalloys in Molten Salt Environment

    NASA Astrophysics Data System (ADS)

    Kamal, Subhash; Jayaganthan, R.; Prakash, Satya

    2011-08-01

    Rare earth oxide (CeO2) has been incorporated in NiCrAlY alloy and hot corrosion resistance of detonation-gun-sprayed NiCrAlY + 0.4 wt.% CeO2 coatings on superalloys, namely, superni 75, superni 718, and superfer 800H in molten 40% Na2SO4-60% V2O5 salt environment were investigated at 900 °C for 100 cycles. The coatings exhibited characteristic splat globular dendritic structure with diameter similar to the original powder particles. The weight change technique was used to establish corrosion kinetics. X-ray diffraction (XRD), field emission scanning electron microscopy/energy-dispersive analysis (FE-SEM/EDAX), and x-ray mapping techniques were used to analyze the corrosion products. Coated superfer 800H alloy showed the highest corrosion resistance among the examined superalloys. CeO2 was found to be distributed in the coating along the splat boundaries, whereas Al streaks distributed non-uniformly. The main phases observed for the coated superalloys are oxides of Ni, Cr, Al, and spinels, which are suggested to be responsible for developing corrosion resistance.

  2. Microstructure and wear properties of Al2O3-CeO2/Ni-base alloy composite coatings on aluminum alloys by plasma spray

    NASA Astrophysics Data System (ADS)

    He, Long; Tan, Yefa; Wang, Xiaolong; Xu, Ting; Hong, Xiang

    2014-09-01

    Al2O3 and CeO2 particles reinforced Ni-base alloy composite coatings were prepared on aluminum alloy 7005 by plasma spray. The microstructure, microhardness, fracture toughness, critical bonding force and the wear behavior and mechanisms of the composite coatings were investigated. It is found that CeO2 particles can refine crystal grains, reduce porosity and unmelted Al2O3 particles in the composite coatings. The microhardness, fracture toughness, critical bonding force and wear resistance of the composite coatings are enhanced due to synergistic strengthening effects of Al2O3 and CeO2 particles. The friction coefficients and wear losses increase as loads increase. At the loads of 3-6 N, the composite coatings experience local plastic deformation and micro-cutting wear. At the loads in the range of 9-12 N, the calculated maximum contact stress and maximum tensile stress on friction surfaces increase leading to plastic deformation induced working hardening. The wear mechanisms change into micro-brittle fracture wear and slight oxidative wear.

  3. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  5. Hydrogen activation, diffusion, and clustering on CeO2(111): A DFT+U study

    NASA Astrophysics Data System (ADS)

    Fernández-Torre, Delia; Carrasco, Javier; Ganduglia-Pirovano, M. Verónica; Pérez, Rubén

    2014-07-01

    We present a comprehensive density functional theory+U study of the mechanisms underlying the dissociation of molecular hydrogen, and diffusion and clustering of the resulting atomic species on the CeO2(111) surface. Contrary to a widely held view based solely on a previous theoretical prediction, our results show conclusively that H2 dissociation is an activated process with a large energy barrier ˜1.0 eV that is not significantly affected by coverage or the presence of surface oxygen vacancies. The reaction proceeds through a local energy minimum - where the molecule is located close to one of the surface oxygen atoms and the H-H bond has been substantially weaken by the interaction with the substrate -, and a transition state where one H atom is attached to a surface O atom and the other H atom sits on-top of a Ce4+ ion. In addition, we have explored how several factors, including H coverage, the location of Ce3+ ions as well as the U value, may affect the chemisorption energy and the relative stability of isolated OH groups versus pair and trimer structures. The trimer stability at low H coverages and the larger upward relaxation of the surface O atoms within the OH groups are consistent with the assignment of the frequent experimental observation by non-contact atomic force and scanning tunneling microscopies of bright protrusions on three neighboring surface O atoms to a triple OH group. The diffusion path of isolated H atoms on the surface goes through the adsorption on-top of an oxygen in the third atomic layer with a large energy barrier of ˜1.8 eV. Overall, the large energy barriers for both, molecular dissociation and atomic diffusion, are consistent with the high activity and selectivity found recently in the partial hydrogenation of acetylene catalyzed by ceria at high H2/C2H2 ratios.

  6. Temperature evolution of structure and bonding of formic acid and formate on fully oxidized and highly reduced CeO2(111)

    SciTech Connect

    Gordon, Wesley O; Xu, Ye; Mullins, David R; Overbury, Steven {Steve} H

    2009-01-01

    Adsorption of formate on oxide surfaces plays a role in water-gas shift (WGS) and other reactions related to H2 production and CO2 utilization. CeO2 is of particular interest because its reducibility affects the redox of organic molecules. In this work, the adsorption and thermal evolution of formic acid and formate on highly ordered films of fully oxidized CeO2(111) and highly reduced CeOx(111) surfaces have been studied using reflection absorption infrared spectroscopy (RAIRS) under ultra-high vacuum conditions, and the experimental results are combined with density functional theory (DFT) calculations to probe the identity, symmetry, and bonding of the surface intermediates. Disordered ice, ordered a-polymorph and molecular formic acid bonded through the carbonyl are observed at low temperatures. By 250 K, desorption and deprotonation lead to formate coexisting with hydroxyl on CeO2(111), identified to be a bridging bidentate formate species that is coordinated to Ce cations in nearly C2v symmetry and interacting strongly with neighboring H. Changes in the spectra at higher temperatures are consistent with additional tilting of the formate, resulting in Cs(2) or lower symmetry. This change in bonding is caused primarily by interaction with oxygen vacancies introduced by water desorption at 300 K. On reduced CeOx, multiple low-symmetry formate states exist likewise due to interactions with oxygen vacancies. Isotopic studies demonstrate that the formyl hydrogen does not contribute to H incorporated in hydroxyl on the surface, and that both formate oxygen atoms may exchange with lattice oxygen at 400 K. The combined experimental and theoretical results thus provide important insights on the surface reaction pathways of formic acid on ceria.

  7. Simultaneous removal of elemental mercury and NO from flue gas by V2O5-CeO2/TiO2 catalysts

    NASA Astrophysics Data System (ADS)

    Zhang, Xunan; Li, Caiting; Zhao, Lingkui; Zhang, Jie; Zeng, Guangming; Xie, Yin'e.; Yu, Ming'e.

    2015-08-01

    A series of Ce-doped V2O5/TiO2 catalysts synthesized by an ultrasound assisted impregnation method were employed to investigate simultaneous removal of elemental mercury (Hg0) and NO in lab-scale experiments. Scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET), X-ray diffractogram (XRD), and X-ray photoelectron spectroscopy (XPS) analyses were used to characterize the samples. Compared to TiO2 support, the catalytic performance of CeO2 doped on both TiO2 and V2O5/TiO2 catalysts have been improved. Remarkably, 1%V2O5-10% CeO2/TiO2 (V1Ce10Ti) exhibited the highest Hg0 oxidation efficiency of 81.55% at 250 °C with a desired NO removal efficiency under the same condition. Both the NO conversion and Hg0 oxidation efficiency were enhanced in the presence of O2. The activity was inhibited by the injection of NH3 with the increase of NH3/NO. When in the presence of 400 ppm SO2, Hg0 oxidation was slightly affected. Furthermore, Hg0 removal behavior under both oxidation and selective catalytic reduction (SCR) condition over V1Ce10Ti were well investigated to further probe into the feasibility of one single unit for multi-pollutants control in industry application. The existence of the redox cycle of V4+ + Ce4+ ↔ V5+ + Ce3+ in V2O5-CeO2/TiO2 catalyst could not only greatly improve the NO conversion, but also promote the oxidation of Hg0.

  8. WO3/CeO2-ZrO2, a promising catalyst for selective catalytic reduction (SCR) of NOx with NH3 in diesel exhaust.

    PubMed

    Li, Ye; Cheng, Hao; Li, Deyi; Qin, Yongsheng; Xie, Yuming; Wang, Shudong

    2008-03-28

    A WO3/CeO2-ZrO2 catalyst system was discovered for selective catalytic reduction of NOx with NH3; the catalyst (10 wt% WO3 loading) showed nearly 100% NOx conversion in a temperature range of 200-500 degrees C, at a space velocity of 90 000 h(-1) in a simulated diesel exhaust containing 550 ppm NOx (NO : NO2 feed ratio at 1.0), 10 vol% H2O and 10 vol% CO2; the catalyst also exhibited high temperature stability.

  9. Enhancement of solar light photocatalytic activity of TiO2-CeO2 composite by Er3+:Y3Al5O12 in organic dye degradation

    NASA Astrophysics Data System (ADS)

    Li, Y.; Li, S. G.; Zhang, L.; Wang, J.; Li, Y.; Ma, C. H.

    2014-12-01

    The Er3+:Y3Al5O12, as an upconversion luminescence agent which is able to transform the visible part of the solar light to ultraviolet light, was prepared by nitrate-citrate sol-gel method. A novel solar light photocatalyst, Er3+:Y3Al5O12/TiO2-CeO2 composite was synthesized using ultrasonic treatment. The X-ray diffraction (XRD) and scanning election microscopy (SEM) were used to characterize the structural morphology of the Er3+:Y3Al5O12/TiO2-CeO2 composite. In order to evaluate the solar light photocatalytic activity of Er3+:Y3Al5O12/TiO2-CeO2 composite, the Azo Fuchsine dye was used as a model organic pollutant. The progress of the degradation reaction was monitored by UV-Vis spectroscopy and ion chromatography. The key influences on the solar light photocatalytic activity of Er3+:Y3Al5O12/TiO2-CeO2 were studied, such as Ti/Ce molar ratio, heat-treatment temperature and heat-treatment time. Otherwise, the effects of initial dye concentration, Er3+:Y3Al5O12/TiO2-CeO2 amount, solar light irradiation time and the nature of the dye on the solar light photocatalytic degradation process were investigated. It was found that the solar light photocatalytic activity of Er3+:Y3Al5O12/TiO2-CeO2 composite was superior to Er3+:Y3Al5O12/TiO2 and Er3+:Y3Al5O12/CeO2 powder in the similar conditions.

  10. The role of the cationic Pt sites in the adsorption properties of water and ethanol on the Pt4/Pt(111) and Pt4/CeO2(111) substrates: A density functional theory investigation

    NASA Astrophysics Data System (ADS)

    Seminovski, Yohanna; Tereshchuk, Polina; Kiejna, Adam; Da Silva, Juarez L. F.

    2016-09-01

    Finite site platinum particles, Ptn, supported on reduced or unreduced cerium oxide surfaces, i.e., CeO2-x(111) ( 0 < x < /1 2 ), have been employed and studied as catalysts for a wide range of applications, which includes hydrogen production using the ethanol steam reforming processes. Our atomic-level understanding of the interaction of Pt with CeO2-x has been improved in the last years; however, the identification of the active sites on the Ptn/CeO2-x(111) substrates is still far from complete. In this work, we applied density functional theory based calculations with the addition of the on-site Coulomb interactions (DFT+U) for the investigation of the active sites and the role of the Pt oxidation state on the adsorption properties of water and ethanol (probe molecules) on four selected substrates, namely, Pt(111), Pt4/Pt(111), CeO2(111), and Pt4/CeO2(111). Our results show that water and ethanol preferentially bind in the cationic sites of the base of the tetrahedron Pt4 cluster instead of the anionic lower-coordinated Pt atoms located on the cluster-top or in the surface Ce (cationic) and O (anionic) sites. The presence of the Pt4 cluster contributes to increase the adsorption energy of both molecules on Pt(111) and CeO2(111) surfaces; however, its magnitude increases less for the case of Pt4/CeO2(111). Thus, the cationic Pt sites play a crucial role in the adsorption properties of water and ethanol. Both water and ethanol bind to on-top sites via the O atom and adopt parallel and perpendicular configurations on the Pt(111) and CeO2(111) substrates, respectively, while their orientation is changed once the Pt4 cluster is involved, favoring H binding with the surface sites.

  11. Acetaldehyde Adsorption and Reaction onCeO2(100) Thin Films

    SciTech Connect

    Mullins, David R; Albrecht, Peter M

    2013-01-01

    This study reports and compares the adsorption and dissociation of acetaldehyde on oxidized and reduced CeOX(100) thin films. Acetaldehyde reacts and decomposes on fully oxidized CeO2(100) whereas it desorbs molecularly at low temperature on CeO2(111). The primary products are CO, CO2 and water along with trace amounts of crotonaldehyde and acetylene. The acetaldehyde adsorbs as the 2-acetaldehyde species, dioxyethylene. Decomposition proceeds by dehydrogenation through acetate and enolate intermediates. The reaction pathway is similar on the reduced CeO2-X(100) surface however the inability to react with surface O on the reduced surface results in H2 rather than H2O desorption and C is left on the surface rather than producing CO and CO2. C-O bond cleavage in the enolate intermediate followed by reaction with surface H results in ethylene desorption.

  12. CeO2-TiO2 catalysts for catalytic oxidation of elemental mercury in low-rank coal combustion flue gas.

    PubMed

    Li, Hailong; Wu, Chang-Yu; Li, Ying; Zhang, Junying

    2011-09-01

    CeO(2)-TiO(2) (CeTi) catalysts synthesized by an ultrasound-assisted impregnation method were employed to oxidize elemental mercury (Hg(0)) in simulated low-rank (sub-bituminous and lignite) coal combustion flue gas. The CeTi catalysts with a CeO(2)/TiO(2) weight ratio of 1-2 exhibited high Hg(0) oxidation activity from 150 to 250 °C. The high concentrations of surface cerium and oxygen were responsible for their superior performance. Hg(0) oxidation over CeTi catalysts was proposed to follow the Langmuir-Hinshelwood mechanism whereby reactive species from adsorbed flue gas components react with adjacently adsorbed Hg(0). In the presence of O(2), a promotional effect of HCl, NO, and SO(2) on Hg(0) oxidation was observed. Without O(2), HCl and NO still promoted Hg(0) oxidation due to the surface oxygen, while SO(2) inhibited Hg(0) adsorption and subsequent oxidation. Water vapor also inhibited Hg(0) oxidation. HCl was the most effective flue gas component responsible for Hg(0) oxidation. However, the combination of SO(2) and NO without HCl also resulted in high Hg(0) oxidation efficiency. This superior oxidation capability is advantageous to Hg(0) oxidation in low-rank coal combustion flue gas with low HCl concentration.

  13. Probing the interaction of Rh, Co and bimetallic Rh-Co nanoparticles with the CeO2 support: catalytic materials for alternative energy generation.

    PubMed

    Varga, E; Pusztai, P; Óvári, L; Oszkó, A; Erdőhelyi, A; Papp, C; Steinrück, H-P; Kónya, Z; Kiss, J

    2015-10-28

    The interaction of CeO2-supported Rh, Co and bimetallic Rh-Co nanoparticles, which are active catalysts in hydrogen production via steam reforming of ethanol, a process related to renewable energy generation, was studied by X-ray diffraction (XRD), high resolution electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS) and low energy ion scattering (LEIS). Furthermore, diffuse reflectance infrared spectroscopy (DRIFTS) of adsorbed CO as a probe molecule was used to characterize the morphology of metal particles. At small loadings (0.1%), Rh is in a much dispersed state on ceria, while at higher contents (1-5%), Rh forms 2-8 nm particles. Between 473-673 K pronounced oxygen transfer from ceria to Rh is observed and at 773 K significant agglomeration of Rh occurs. On reduced ceria, XPS indicates a possible electron transfer from Rh to ceria. The formation of smaller ceria crystallites upon loading with Co was concluded from XRD and HRTEM; for 10% Co, the CeO2 particle size decreased from 27.6 to 10.7 nm. A strong dissolution of Co into ceria and a certain extent of encapsulation by ceria were deduced by XRD, XPS and LEIS. In the bimetallic system, the presence of Rh enhances the reduction of cobalt and ceria. During thermal treatments, reoxidation of Co occurs, and Rh agglomeration as well as oxygen migration from ceria to Rh are hindered in the presence of cobalt.

  14. Hydrocracking of cumene over Ni/Al 2O 3 as influenced by CeO 2 doping and γ-irradiation

    NASA Astrophysics Data System (ADS)

    El-Shobaky, G. A.; Doheim, M. M.; Ghozza, A. M.

    2004-01-01

    Cumene hydrocracking was carried out over pure and doped Ni/Al 2O 3 solids and also, on these solids after exposure to different doses of γ-rays between 0.4 and 1.6 MGy. The dopant concentration was varied between 1 and 4 mol% CeO 2. Pure and doped samples were subjected to heat treatment at 400°C and cumene hydrocracking reaction was carried out using various solids at temperatures between 250°C and 400°C by means of micropulse technique. The results showed that both CeO 2 doping and γ-irradiation of the investigated system brought about an increase in its specific surface area. γ-irradiation of pure samples increased their catalytic activities effectively. However, the doping caused a decrease in the catalytic activity. γ-irradiation of the doped samples brought about a net decrease in the catalytic activity. The catalytic reaction products over different investigated solids were ethylbenzene as a major product together with different amounts of toluene, benzene and C 1-C 3 gaseous hydrocarbons. The selectivity towards the formation of various reaction products varies with the reaction temperature, doping and γ-irradiation.

  15. Active sites over CuO/CeO2 and inverse CeO2/CuO catalysts for preferential CO oxidation

    NASA Astrophysics Data System (ADS)

    Zeng, Shanghong; Wang, Yan; Ding, Suping; Sattler, Jesper J. H. B.; Borodina, Elena; Zhang, Lu; Weckhuysen, Bert M.; Su, Haiquan

    2014-06-01

    A series of CuO/CeO2 and inverse CeO2/CuO catalysts are prepared by the surfactant-templated method and characterized via XRD, HRTEM, H2-TPR, SEM, XPS, in situ XRD, in situ UV-Vis and N2 adsorption-desorption techniques. It is found that there are two kinds of surface sites in the CuO-CeO2 system, including CuO surface sites for CO chemisorption and CeO2 surface sites with oxygen vacancies for oxygen sorption. The active sites for CO oxidation are located on the contact interface of two-kind surface sites and the lattice oxygen can make a significant contribution to the CO-PROX reaction. The resistance to H2O and CO2 is related to BET surface area, the crystallite sizes of CuO and the reduction behavior of catalysts. The Ce4Cu4 and Ce4Cu1 catalysts exhibit the best resistance against H2O and CO2.

  16. Thermal Treatment of Al2O3, MgO, and CeO2 Granulated Powders by Induction Thermal Plasma: A Numerical Approach

    NASA Astrophysics Data System (ADS)

    Hossain, M. Mofazzal; Alam, M. Rafiqul; Watanabe, Takayuki

    2013-01-01

    A plasma--particle interactive flow model has been developed for the investigation of plasma temperature, velocity, particle temperature, diameter, and flight path during in-fight thermal treatment of granulated powders --- Al2O3, MgO, and CeO2 in induction thermal plasma, taking into account of plasma particle interaction and particle loading effects. In this model, the conservative equations are solved to investigate the influence of feed-rate and particle diameter on the melting behavior of granulated powders and to predict particle trajectories, temperature histories etc. In this paper attention is given to the effects of carrier gas flow-rate, powder feed-rate and secondary gas (oxygen) flow-rate on the particles' final diameter and trajectory for Al2O3, MgO, and CeO2 powders. Results show that the particles diameter after thermal treatment is strongly dependent on the powder feed-rate, oxygen gas flow-rate and carrier gas flow-rate. Among the three types of powders, particle diameter decrement is significant in case of MgO and less significant in case of Al2O3; and the effect of oxygen flow-rate on the particle diameter decrement is significant in case of MgO. Particles trajectories are wider for smaller particles than that of larger particles. Particle temperature is lowest for MgO and highest for Al2O3 particles.

  17. Thermal Treatment of Al2O3, MgO, and CeO2 Granulated Powders by Induction Thermal Plasma: A Numerical Approach

    NASA Astrophysics Data System (ADS)

    Mofazzal Hossain, M.; Rafiqul Alam, M.; Watanabe, Takayuki

    2013-01-01

    A plasma-particle interactive flow model has been developed for the investigation of plasma temperature, velocity, particle temperature, diameter, and flight path during in-fight thermal treatment of granulated powders - Al2O3, MgO, and CeO2 in induction thermal plasma, taking into account of plasma particle interaction and particle loading effects. In this model, the conservative equations are solved to investigate the influence of feed-rate and particle diameter on the melting behavior of granulated powders and to predict particle trajectories, temperature histories etc. In this paper attention is given to the effects of carrier gas flow-rate, powder feed-rate and secondary gas (oxygen) flow-rate on the particles' final diameter and trajectory for Al2O3, MgO, and CeO2 powders. Results show that the particles diameter after thermal treatment is strongly dependent on the powder feed-rate, oxygen gas flow-rate and carrier gas flow-rate. Among the three types of powders, particle diameter decrement is significant in case of MgO and less significant in case of Al2O3; and the effect of oxygen flow-rate on the particle diameter decrement is significant in case of MgO. Particles trajectories are wider for smaller particles than that of larger particles. Particle temperature is lowest for MgO and highest for Al2O3 particles.

  18. Visible light-sensitive MnO 2- and CeO 2-loaded ZrO 2/carbon cluster/Pt nanocomposite materials

    NASA Astrophysics Data System (ADS)

    Matsui, H.; Ikegami, M.; Karuppuchamy, S.; Hassan, M. A.; Yoshihara, M.

    2012-02-01

    Nano-sized ZrO 2/carbon cluster composite materials (I c's) were successfully prepared by the calcination of ZrOCl 2/starch complex I. I c's were found to reduce methylene blue under the irradiation of visible light ( λ > 460 nm). The materials obtained by calcining at 400 and 500 °C were selectively loaded with Pt particles to obtain Pt-loaded ZrO 2/carbon cluster composite materials denoted as I c400Pt and I c500Pt, respectively. In addition, the resultant materials were modified with MnO 2 and CeO 2 particles to achieve MnO 2- and CeO 2-loaded ZrO 2/carbon cluster/Pt composite materials denoted as I c400PtMn, I c500PtMn, I c400PtCe and I c500PtCe, respectively. The metal oxides-loaded ZrO 2/carbon cluster/Pt composite materials thus synthesized could decompose an aqueous silver nitrate solution by visible light irradiation to give Ag and O 2 with the [Ag]/[O 2] ratios of ca. 4. Visible light-irradiated water splitting examinations with I c400PtMn and I c400PtCe were also investigated and found to yield H 2 and O 2 with the [H 2]/[O 2] ratios of ca. 2.

  19. Designed synthesis of multi-functional PEGylated Yb2O3:Gd@SiO2@CeO2 islands core@shell nanostructure.

    PubMed

    Li, Junqi; Yao, Shuang; Song, Shuyan; Wang, Xiao; Wang, Yinghui; Ding, Xing; Wang, Fan; Zhang, Hongjie

    2016-07-28

    Nanomaterials that can restrain or reduce the production of excessive reactive oxygen species such as H2O2 to defend and treat against Alzheimer's disease (AD) have attracted much attention. In this paper, we adopt the strategy of layer-by-layer deposition; namely, first synthesizing available gadolinium-doped ytterbia nanoparticles (Yb2O3:Gd NPs) as cores, and then coating them with silica via the classical Stöber method to prevent leakage and act as a carrier for subsequent ceria deposition and PEGylation, and finally obtain the expected core@shell-structured nanocomposite of PEGylated Yb2O3:Gd@SiO2@CeO2 islands. The nanomaterial has proved not only to be a high-performance dual-modal contrast agent for use in MRI and CT, but also to exhibit excellent catalase mimetic activity, which may help the prognosis, diagnosis and treatment of AD in the future. In addition, scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared (FTIR) spectroscopy characterization have revealed the successful design and synthesis of the cores with remarkable size uniformity, with well-distributed CeO2 islands decorated on the surface of SiO2 shells, and tightly immobilized PEG. PMID:27351951

  20. Low-temperature selective catalytic reduction of NO on CeO2-CuO/Al2O3 catalysts prepared by different methods.

    PubMed

    Guo, Rui-Tang; Zhen, Wen-Long; Pan, Wei-Guo; Hong, Jie-Nan; Jin, Qiang; Ding, Cheng-Gang; Guo, Shi-Yi

    2014-08-01

    CeO2-CuO/Al2O3 catalysts were prepared by three different methods and their activities for selective catalytic reduction (SCR) of NO with NH3 were investigated. As can be seen from the experimental results, the catalyst prepared by the single-step sol-gel (SG) method showed the best SCR activity and resistance to SO2 and H2O. In order to investigate the relationship between the preparation method and the performance of SCR catalysts, the catalysts were characterized by using Brunauer-Emmett-Teller, X-ray diffraction, temperature programmed reduction with hydrogen, temperature programmed desorption with ammonia, X-ray photoelectron spectroscopy, Fourier transform infrared and thermo-gravimetric analysis techniques. It was found that the excellent performance of CeO2-CuO/Al2O3 catalyst prepared by the single-step SG method should be resulted from its large surface area, low crystallinity, high oxygen storage capacity, high NH3 adsorption capacity, high concentration of surface chemisorbed oxygen, weak sulphation process and weak water absorption.

  1. CeO2-TiO2 catalysts for catalytic oxidation of elemental mercury in low-rank coal combustion flue gas.

    PubMed

    Li, Hailong; Wu, Chang-Yu; Li, Ying; Zhang, Junying

    2011-09-01

    CeO(2)-TiO(2) (CeTi) catalysts synthesized by an ultrasound-assisted impregnation method were employed to oxidize elemental mercury (Hg(0)) in simulated low-rank (sub-bituminous and lignite) coal combustion flue gas. The CeTi catalysts with a CeO(2)/TiO(2) weight ratio of 1-2 exhibited high Hg(0) oxidation activity from 150 to 250 °C. The high concentrations of surface cerium and oxygen were responsible for their superior performance. Hg(0) oxidation over CeTi catalysts was proposed to follow the Langmuir-Hinshelwood mechanism whereby reactive species from adsorbed flue gas components react with adjacently adsorbed Hg(0). In the presence of O(2), a promotional effect of HCl, NO, and SO(2) on Hg(0) oxidation was observed. Without O(2), HCl and NO still promoted Hg(0) oxidation due to the surface oxygen, while SO(2) inhibited Hg(0) adsorption and subsequent oxidation. Water vapor also inhibited Hg(0) oxidation. HCl was the most effective flue gas component responsible for Hg(0) oxidation. However, the combination of SO(2) and NO without HCl also resulted in high Hg(0) oxidation efficiency. This superior oxidation capability is advantageous to Hg(0) oxidation in low-rank coal combustion flue gas with low HCl concentration. PMID:21770402

  2. Probing the interaction of Rh, Co and bimetallic Rh-Co nanoparticles with the CeO2 support: catalytic materials for alternative energy generation.

    PubMed

    Varga, E; Pusztai, P; Óvári, L; Oszkó, A; Erdőhelyi, A; Papp, C; Steinrück, H-P; Kónya, Z; Kiss, J

    2015-10-28

    The interaction of CeO2-supported Rh, Co and bimetallic Rh-Co nanoparticles, which are active catalysts in hydrogen production via steam reforming of ethanol, a process related to renewable energy generation, was studied by X-ray diffraction (XRD), high resolution electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS) and low energy ion scattering (LEIS). Furthermore, diffuse reflectance infrared spectroscopy (DRIFTS) of adsorbed CO as a probe molecule was used to characterize the morphology of metal particles. At small loadings (0.1%), Rh is in a much dispersed state on ceria, while at higher contents (1-5%), Rh forms 2-8 nm particles. Between 473-673 K pronounced oxygen transfer from ceria to Rh is observed and at 773 K significant agglomeration of Rh occurs. On reduced ceria, XPS indicates a possible electron transfer from Rh to ceria. The formation of smaller ceria crystallites upon loading with Co was concluded from XRD and HRTEM; for 10% Co, the CeO2 particle size decreased from 27.6 to 10.7 nm. A strong dissolution of Co into ceria and a certain extent of encapsulation by ceria were deduced by XRD, XPS and LEIS. In the bimetallic system, the presence of Rh enhances the reduction of cobalt and ceria. During thermal treatments, reoxidation of Co occurs, and Rh agglomeration as well as oxygen migration from ceria to Rh are hindered in the presence of cobalt. PMID:26415514

  3. Design and Preparation of MnO2/CeO2-MnO2 Double-Shelled Binary Oxide Hollow Spheres and Their Application in CO Oxidation.

    PubMed

    Zhang, Jian; Cao, Yidan; Wang, Chang-An; Ran, Rui

    2016-04-01

    Herein, we designed an extremely facile method to prepare well-defined MnO2@CeO2-MnO2 ball-in-ball binary oxide hollow spheres by employing carbon spheres (CSs) as sacrificial templates. The synthesis process involves a novel self-assembled approach to prepare core-shell CSs@CeO2 precursor, which would directly react with KMnO4 aqueous solution to form yolk-shell CSs@MnO2/CeO2-MnO2 precursor in the following step. Well-dispersed Ce-Mn binary oxide with double-shelled hollow sphere structure could be achieved after annealing the precursor in air. The evolution process and formation mechanism of this novel structure were thoroughly studied in this paper. Especially the as-prepared double-shell MnO2/CeO2-MnO2 hollow spheres exhibited enhanced catalytic activity for CO oxidation compared with the pure MnO2 hollow spheres and pure CeO2 hollow spheres. We believe the high surface area, hierarchical porous structures, and strong synergistic interaction between CeO2 and MnO2 contribute to the excellent catalytic activity. Most importantly, this method could be extended to prepare other transition metal oxides. As an example, triple-shelled Co-Mn composite hollow spheres assembled by ultrathin nanoplates were successfully prepared.

  4. 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).

  5. Grain-boundary phases in hot-pressed silicon nitride containing Y2O3 and CeO2 additives

    NASA Technical Reports Server (NTRS)

    Guha, J. P.; Hench, L. L.

    1983-01-01

    Auger electron spectroscopy in conjunction with X-ray powder diffraction and scanning electron microscopy is used to analyze the grain-boundary phases of Y2O3- and CeO2-doped Si3N4 hot-pressed materials in order to demonstrate that the additives concentrate predominantly in the grain boundaries of Si3N4 in the form of various oxynitride phases. A high oxygen content observed in sample fracture surfaces was found to be consistent with the existence of an oxygen-enriched phase in the grain boundaries. The presence of yttrium and cerium in the fracture surfaces and an overall increase in the O/N ratio imply that the additive oxides are predominantly concentrated in the intergranular phases.

  6. Ab Initio Molecular Dynamics Simulations of Low-Energy Recoil Events in ThO2, CeO2, and ZrO2

    SciTech Connect

    Xiao, Haiyan Y.; Zhang, Yanwen; Weber, William J.

    2012-08-13

    Ab initio molecular dynamics simulations of low-energy recoil events in ThO2, CeO2, and ZrO2 have been carried out to determine the threshold displacement energies, resulting defect configurations, dynamics of defect generation, and role of charge transfer during the process. The results reveal that, in most cases, these fluorite structure oxides exhibit a similar response to low-energy recoils. A variety of different defect configurations are created, consisting mainly of vacancies and interstitials. Charge transfer occurs during the dynamic displacement process. Local charge redistribution leads to cation and O vacancies being negatively and positively charged, respectively. Likewise, due to charge redistribution, the cation and O interstitials are less positively and negatively charged, respectively, than the ions on lattice sites in perfect MO2.

  7. Ab initio molecular dynamics simulations of low energy recoil events in ThO2, CeO2 and ZrO2

    SciTech Connect

    Xiao, Haiyan; Zhang, Yanwen; Weber, William J

    2012-01-01

    Ab initio molecular dynamics simulations of low energy recoil events in ThO2, CeO2 and ZrO2 have been carried out to determine the threshold displacement energies, resulting defect configurations, dynamics of defect generation, and role of charge transfer during the process. The results reveal that, in most cases, these fluorite structure oxides exhibit a similar response to low-energy recoils. A variety of different defect configurations are created, consisting mainly of vacancies and interstitials. Charge transfer occurs during the dynamic displacement process. Local charge redistribution leads to cation and O vacancies being negatively and positively charged, respectively. Likewise, due to charge redistribution, the cation and O interstitials are less positively and negatively charged, respectively, than the ions on lattice sites in perfect MO2.

  8. Influence of the Electronic Structure and Optical Properties of CeO2 and UO2 for Characterization with UV-Laser Assisted Atom Probe Tomography

    SciTech Connect

    Billy Valderrama; H.B. Henderson; C. Yablinsky; J. Gan; T.R. Allen; M.V. Manuel

    2015-09-01

    Oxide materials are used in numerous applications such as thermal barrier coatings, nuclear fuels, and electrical conductors and sensors, all applications where nanometer-scale stoichiometric changes can affect functional properties. Atom probe tomography can be used to characterize the precise chemical distribution of individual species and spatially quantify the oxygen to metal ratio at the nanometer scale. However, atom probe analysis of oxides can be accompanied by measurement artifacts caused by laser-material interactions. In this investigation, two technologically relevant oxide materials with the same crystal structure and an anion to cation ratio of 2.00, pure cerium oxide (CeO2) and uranium oxide (UO2) are studied. It was determined that electronic structure, optical properties, heat transfer properties, and oxide stability strongly affect their evaporation behavior, thus altering their measured stoichiometry, with thermal conductance and thermodynamic stability being strong factors.

  9. CeO2 doped anatase TiO2 with exposed (001) high energy facets and its performance in selective catalytic reduction of NO by NH3

    NASA Astrophysics Data System (ADS)

    Wang, Haiqiang; Cao, Shuang; Fang, Zheng; Yu, Feixiang; Liu, Yue; Weng, Xiaole; Wu, Zhongbiao

    2015-03-01

    Ceria doped on anatase TiO2 with high energy (001) facets was synthesized in this paper, which was subsequently utilized for selective catalytic reduction (SCR) of NO by NH3. After subjected to a range of analytical techniques, such as XRD, BET, TEM, XPS ESR, H2-TPR and NH3-TPD, it was found that compared with Ce/P25 catalyst, the presence of (001) facets over the TiO2 support had yielded a remarkably high activity at 390-490 °C for NO removal. The unique feature of active-energy (001) facets had enhanced the thermal stability of CeO2 whilst the presence of Ti3+ over the TiO2 surface had effectively facilitated the SCR process, both of which resulted in the remarkable catalytic performance for the catalyst.

  10. A New Strategy for Humidity Independent Oxide Chemiresistors: Dynamic Self-Refreshing of In2 O3 Sensing Surface Assisted by Layer-by-Layer Coated CeO2 Nanoclusters.

    PubMed

    Yoon, Ji-Wook; Kim, Jun-Sik; Kim, Tae-Hyung; Hong, Young Jun; Kang, Yun Chan; Lee, Jong-Heun

    2016-08-01

    The humidity dependence of the gas sensing characteristics of metal oxide semiconductors has been one of the greatest obstacles for gas sensor applications during the last five decades because ambient humidity dynamically changes with the environmental conditions. Herein, a new and novel strategy is reported to eliminate the humidity dependence of the gas sensing characteristics of oxide chemiresistors via dynamic self-refreshing of the sensing surface affected by water vapor chemisorption. The sensor resistance and gas response of pure In2 O3 hollow spheres significantly change and deteriorate in humid atmospheres. In contrast, the humidity dependence becomes negligible when an optimal concentration of CeO2 nanoclusters is uniformly loaded onto In2 O3 hollow spheres via layer-by-layer (LBL) assembly. Moreover, In2 O3 sensors LBL-coated with CeO2 nanoclusters show fast response/recovery, low detection limit (500 ppb), and high selectivity to acetone even in highly humid conditions (relative humidity 80%). The mechanism underlying the dynamic refreshing of the In2 O3 sensing surfaces regardless of humidity variation is investigated in relation to the role of CeO2 and the chemical interaction among CeO2 , In2 O3 , and water vapor. This strategy can be widely used to design high performance gas sensors including disease diagnosis via breath analysis and pollutant monitoring.

  11. CeO2/rGO/Pt sandwich nanostructure: rGO-enhanced electron transmission between metal oxide and metal nanoparticles for anodic methanol oxidation of direct methanol fuel cells.

    PubMed

    Yu, Xue; Kuai, Long; Geng, Baoyou

    2012-09-21

    Pt-based nanocomposites have been of great research interest. In this paper, we design an efficient MO/rGO/Pt sandwich nanostructure as an anodic electrocatalyst for DMFCs with combination of the merits of rigid structure of metallic oxides (MOs) and excellent electronic conductivity of reduced oxidized graphene (rGO) as well as overcoming their shortcomings. In this case, the CeO(2)/rGO/Pt sandwich nanostructure is successfully fabricated through a facile hydrothermal approach in the presence of graphene oxide and CeO(2) nanoparticles. This structure has a unique building architecture where rGO wraps up the CeO(2) nanoparticles and Pt nanoparticles are homogeneously dispersed on the surface of rGO. This novel structure endows this material with great electrocatalytic performance in methanol oxidation: it reduces the overpotential of methanol oxidation significantly and its electrocatalytic activity and stability are much enhanced compared with Pt/rGO, CeO(2)/Pt and Pt/C catalysts. This work supplies a unique MO/rGO/Pt sandwich nanostructure as an efficient way to improve the electrocatalytic performance, which will surely shed some light on the exploration of some novel structures of electrocatalyst for DMFCs.

  12. Investigation of the Poisoning Mechanism of Lead on the CeO2-WO3 Catalyst for the NH3-SCR Reaction via in Situ IR and Raman Spectroscopy Measurement.

    PubMed

    Peng, Yue; Si, Wenzhe; Li, Xiang; Chen, Jianjun; Li, Junhua; Crittenden, John; Hao, Jiming

    2016-09-01

    The in situ IR and Raman spectroscopy measurements were conducted to investigate lead poisoning on the CeO2-WO3 catalysts. The deactivation mechanisms were studied with respect to the changes of surface acidity, redox property, nitrate/nitrite adsorption behaviors, and key active sites (note that the results of structure-activity relationship of CeO2-WO3 were based on our previous research). (1) Lewis acid sites originated from CeO2 and crystalline WO3, whereas Brønsted acid sites originated from Ce2(WO4)3. The poisoned catalysts exhibited a lower surface acidity than the fresh catalysts: the number of acid sites decreased, and their thermal stability weakened. (2) The reducibility of catalysts and the amount of active oxygen exhibited a smaller influence after poisoning because lead preferred to bond with surface WOx species rather than CeO2. (3) The quantity of active nitrate species decreased due to the lead coverage on the catalyst and the partial bridged-nitrate species induced by lead exhibited a low degree of activity at 200 °C. (4) Crystalline WO3 and Ce2(WO4)3 originated from the transformation of polytungstate sites. These sites were the key active sites during the SCR process. The formation temperatures of polytungstate on the poisoned catalysts were higher than those on the fresh catalysts. PMID:27480109

  13. Effect of CeO2 and Y2O3 on microstructure, bioactivity and degradability of laser cladding CaO-SiO2 coating on titanium alloy.

    PubMed

    Li, H C; Wang, D G; Chen, C Z; Weng, F

    2015-03-01

    To solve the lack of strength of bulk biomaterials for load-bearing applications and improve the bioactivity of titanium alloy (Ti-6Al-4V), CaO-SiO2 coatings on titanium alloy were fabricated by laser cladding technique. The effect of CeO2 and Y2O3 on microstructure and properties of laser cladding coating was analyzed. The cross-section microstructure of ceramic layer from top to bottom gradually changes from cellular-dendrite structure to compact cellular crystal. The addition of CeO2 or Y2O3 refines the microstructure of the ceramic layer in the upper and middle regions. The refining effect on the grain is related to the kinds of additives and their content. The coating is mainly composed of CaTiO3, CaO, α-Ca2(SiO4), SiO2 and TiO2. Y2O3 inhibits the formation of CaO. After soaking in simulated body fluid (SBF), the calcium phosphate layer is formed on the coating surface, indicating the coating has bioactivity. After soaking in Tris-HCl solution, the samples doped with CeO2 or Y2O3 present a lower weight loss, indicating the addition of CeO2 or Y2O3 improves the degradability of laser cladding sample.

  14. The effects of H2O and SO2 on the behaviour of CuSO4-CeO2/TS for low temperature catalytic reduction of NO with NH3.

    PubMed

    Tong, Hua; Dai, Junhong; He, Yong; Tong, Zhiquan

    2011-01-01

    The catalyst CuSO4-CeO2/TiO2-SiO2 (CuSO4-CeO2/TS), for low temperature catalytic reduction (LT-SCR) of NO with NH was prepared by the impregnation method. The impacts of H2O and SO2 on the catalyst were investigated. Experiments showed that H2O brought down the catalyst's activity at low reaction temperature. However, this negative effect of H2O could be mostly eliminated with a raised temperature of above 220 degrees C. In a 10-hour experiment on the catalyst's resistibility to SO2 poisoning, NO conversion increased slightly by the promoting effect of SO2. The same catalyst underwent continuous examination with both SO2 and H2O in the feed gas; NO conversion of around 90.2% was maintained for 37 hours, showing better performance than CuSO4-CeO2/TiO2. This suggested that SiO2 in the TiO2-SiO2 catalyst supported the supression of the oxidization of SO2 to SO3. Therefore, the formation of ammonium sulphate over the catalyst and the sulphation of CeO2 in the catalyst were greatly alleviated, leading to a better resistibility of the catalyst to SO2 poisioning. After the 37 hours, the catalyst activity began to fall, and an irrecoverable deactivation of the catalyst was observed. PMID:21879564

  15. Investigation of the Poisoning Mechanism of Lead on the CeO2-WO3 Catalyst for the NH3-SCR Reaction via in Situ IR and Raman Spectroscopy Measurement.

    PubMed

    Peng, Yue; Si, Wenzhe; Li, Xiang; Chen, Jianjun; Li, Junhua; Crittenden, John; Hao, Jiming

    2016-09-01

    The in situ IR and Raman spectroscopy measurements were conducted to investigate lead poisoning on the CeO2-WO3 catalysts. The deactivation mechanisms were studied with respect to the changes of surface acidity, redox property, nitrate/nitrite adsorption behaviors, and key active sites (note that the results of structure-activity relationship of CeO2-WO3 were based on our previous research). (1) Lewis acid sites originated from CeO2 and crystalline WO3, whereas Brønsted acid sites originated from Ce2(WO4)3. The poisoned catalysts exhibited a lower surface acidity than the fresh catalysts: the number of acid sites decreased, and their thermal stability weakened. (2) The reducibility of catalysts and the amount of active oxygen exhibited a smaller influence after poisoning because lead preferred to bond with surface WOx species rather than CeO2. (3) The quantity of active nitrate species decreased due to the lead coverage on the catalyst and the partial bridged-nitrate species induced by lead exhibited a low degree of activity at 200 °C. (4) Crystalline WO3 and Ce2(WO4)3 originated from the transformation of polytungstate sites. These sites were the key active sites during the SCR process. The formation temperatures of polytungstate on the poisoned catalysts were higher than those on the fresh catalysts.

  16. Effect of CeO2 and Y2O3 on microstructure, bioactivity and degradability of laser cladding CaO-SiO2 coating on titanium alloy.

    PubMed

    Li, H C; Wang, D G; Chen, C Z; Weng, F

    2015-03-01

    To solve the lack of strength of bulk biomaterials for load-bearing applications and improve the bioactivity of titanium alloy (Ti-6Al-4V), CaO-SiO2 coatings on titanium alloy were fabricated by laser cladding technique. The effect of CeO2 and Y2O3 on microstructure and properties of laser cladding coating was analyzed. The cross-section microstructure of ceramic layer from top to bottom gradually changes from cellular-dendrite structure to compact cellular crystal. The addition of CeO2 or Y2O3 refines the microstructure of the ceramic layer in the upper and middle regions. The refining effect on the grain is related to the kinds of additives and their content. The coating is mainly composed of CaTiO3, CaO, α-Ca2(SiO4), SiO2 and TiO2. Y2O3 inhibits the formation of CaO. After soaking in simulated body fluid (SBF), the calcium phosphate layer is formed on the coating surface, indicating the coating has bioactivity. After soaking in Tris-HCl solution, the samples doped with CeO2 or Y2O3 present a lower weight loss, indicating the addition of CeO2 or Y2O3 improves the degradability of laser cladding sample. PMID:25637793

  17. Temperature-dependent void formation and growth at ion-irradiated nanocrystalline CeO2 Si interfaces

    SciTech Connect

    Perez-Bergquist, Alex G; Zhang, Yanwen; Varga, Tamas; Moll, Sandra; Weber, William J

    2014-01-01

    Ceria is a thermally stable ceramic that has numerous applications in the nuclear industry, including use in nuclear fuels and waste forms. Recently, interest has surged in nanostructured ceria due to its increased mechanical properties and electronic conductivity in comparison with bulk ceria and its ability to self-heal in response to energetic ion bombardment. Here, nanocrystalline ceria thin films grown over a silicon substrate are irradiated to fluences of up to 4 1016 ions/cm2 under different irradiation conditions: with differing ion species (Si+ and Ni+), different ion energies (1.0 1.5 MeV), and at varying temperatures (160 600 K). While the nanocrystalline ceria is found to exhibit exceptional radiation resistance under all tested conditions, severe ion irradiation-induced mixing, void formation, and void growth are observed at the ceria/silicon interface, with the degree of damage proving to be temperature dependent.

  18. Physico-Chemical Property and Catalytic Activity of a CeO2-Doped MnO(x)-TiO2 Catalyst with SO2 Resistance for Low-Temperature NH3-SCR of NO(x).

    PubMed

    Shin, Byeongkil; Chun, Ho Hwan; Cha, Jin-Sun; Shin, Min-Chul; Lee, Heesoo

    2016-05-01

    The effects of CeO2 addition on the catalytic activity and the SO2 resistance of CeO2-doped MnO(x)-TiO2 catalysts were investigated for the low-temperature selective catalytic reduction (SCR) with NH3 of NO(x) emissions in marine applications. The most active catalyst was obtained from 30 wt% CeO2-MnO(x)-TiO2 catalyst in the whole temperature range of 100-300 degrees C at a low gas hourly space velocity (GHSV) of 10,000 h(-)1, and its de-NO(x) efficiency was higher than 90% over 250 degrees C. The enhanced catalytic activity may contribute to the dispersion state and catalytic acidity on the catalyst surface, and the highly dispersed Mn and Ce on the nano-scaled TiO2 catalyst affects the increase of Lewis and Brønsted acid sites. A CeO2-rich additive on MnO(x)-TiO2 could provide stronger catalytic acid sites, associated with NH3 adsorption and the SCR performance. As the results of sulfur resistance in flue gas that contains SO2, the de-NO(x) efficiency of MnO(x)-TiO2 decreased by 15% over 200 degrees C, whereas that of 30 wt% ceria-doped catalyst increased by 14-21% over 150 degrees C. The high SO2 resistance of CeO2-MnO(x)-TiO2 catalysts that resulted from the addition of ceria suppressed the formation of Mn sulfate species, which led to deactivation on the surface of nano-catalyst. PMID:27483759

  19. Physico-Chemical Property and Catalytic Activity of a CeO2-Doped MnO(x)-TiO2 Catalyst with SO2 Resistance for Low-Temperature NH3-SCR of NO(x).

    PubMed

    Shin, Byeongkil; Chun, Ho Hwan; Cha, Jin-Sun; Shin, Min-Chul; Lee, Heesoo

    2016-05-01

    The effects of CeO2 addition on the catalytic activity and the SO2 resistance of CeO2-doped MnO(x)-TiO2 catalysts were investigated for the low-temperature selective catalytic reduction (SCR) with NH3 of NO(x) emissions in marine applications. The most active catalyst was obtained from 30 wt% CeO2-MnO(x)-TiO2 catalyst in the whole temperature range of 100-300 degrees C at a low gas hourly space velocity (GHSV) of 10,000 h(-)1, and its de-NO(x) efficiency was higher than 90% over 250 degrees C. The enhanced catalytic activity may contribute to the dispersion state and catalytic acidity on the catalyst surface, and the highly dispersed Mn and Ce on the nano-scaled TiO2 catalyst affects the increase of Lewis and Brønsted acid sites. A CeO2-rich additive on MnO(x)-TiO2 could provide stronger catalytic acid sites, associated with NH3 adsorption and the SCR performance. As the results of sulfur resistance in flue gas that contains SO2, the de-NO(x) efficiency of MnO(x)-TiO2 decreased by 15% over 200 degrees C, whereas that of 30 wt% ceria-doped catalyst increased by 14-21% over 150 degrees C. The high SO2 resistance of CeO2-MnO(x)-TiO2 catalysts that resulted from the addition of ceria suppressed the formation of Mn sulfate species, which led to deactivation on the surface of nano-catalyst.

  20. Ion-Beam-Induced Chemical Mixing at a Nanocrystalline CeO2–Si Interface

    SciTech Connect

    Edmondson, P. D.; Young, Niel P.; Parish, Chad M.; Moll, Sandra J.; Namavar, Fereydoon; Weber, William J.; Zhang, Yanwen

    2013-02-28

    Thin films of nanocrystalline ceria deposited onto a silicon substrate have been irradiated with 3 MeV Au+ ions to a total dose of 34 displacements per atom to examine the film/substrate interfacial response upon displacement damage. Under irradiation, a band of contrast is observed to form that grows under further irradiation. Scanning and high-resolution transmission electron microscopy imaging and analysis suggest that this band of contrast is a cerium silicate phase with an approximate Ce:Si:O composition ratio of 1:1:3 in an amorphous nature. The slightly nonstoichiometric composition arises due to the loss of mobile oxygen within the cerium silicate phase under the current irradiation condition. This nonequilibrium phase is formed as a direct result of ion-beam-induced chemical mixing caused by ballistic collisions between the incoming ion and the lattice atoms. This may hold promise in ion beam engineering of cerium silicates for microelectronic applications e.g., the fabrication of blue LEDs.

  1. Characteristics of Desulfation Behavior for Pre-Sulfated Pt-BaO/CeO2 Lean NOx Trap Catalysts: The Role of the CeO2 Support

    SciTech Connect

    Kim, Do Heui; Kwak, Ja Hun; Szanyi, Janos; Wang, Xianqin; Li, Guosheng; Hanson, Jonathan C.; Peden, Charles HF

    2009-12-17

    The desulfation of pre-sulfated Pt-BaO/CeO2 lean NOx trap catalysts was investigated by H2 TPRX (temperature programmed reaction), in-situ TR-XRD (time-resolved X-ray diffraction) and in-situ S K-edge XANES (X-ray absorption near edge spectroscopy) techniques. Compared with Pt-BaO/Al2O3 materials, the reductive treatment in H2 for a CeO2 supported sample up to 1073 K hardly removes any sulfur species. However, the results of in-situ TR-XRD measurements demonstrate that the quantity of a BaS phase formed on Pt-BaO/CeO2 is much smaller than that on Pt-BaO/Al2O3, implying that the formation of BaS crystallites, which occurs during the reduction from sulfate (SO42-) to sulfide (S2-), is significantly suppressed in the CeO2-supported catalyst. As the desulfation temperature increases under reducing conditions (in H2), the in-situ S XANES spectra show that, compared with alumina-supported samples, the reduction temperature for sulfates (S6+) decreases by about 150 K. Concomitantly, the formation of sulfur species with lower oxidation states (S2- - S4+) is enhanced. The step jump of S XANES spectra before and after desulfation are very similar, implying that the amount of sulfur-containing species removed during the reductive treatment is negligible, in agreement with the results of H2 TPRX. These results suggest that H2S produced by the reduction of BaSO4 is readily re-adsorbed on the ceria support to form ceria-sulfur complexes (e.g. CeS2). The high affinity of ceria for H2S, combined with the ease of reducibility of the ceria support gives rise to various oxidation states of sulfur after high temperature H2 treatments. Thus, the results of this study clearly show that the ceria support strongly affects the overall desulfation mechanism. The intrinsic role of the ceria support during desulfation, and its effect on the overall NOx storage processes are discussed on the basis of the characterization results obtained here.

  2. Adsorption and Reaction of Acetone over CeOX(111) Thin Films

    SciTech Connect

    Mullins, David R; Senanayake, Sanjaya D; Gordon, Wesley O; Overbury, Steven {Steve} H

    2009-01-01

    This study reports the interaction of acetone (CH3COCH3), the simplest ketone, with well ordered CeO2(111) thin film surfaces. The fully oxidized CeO2(111) surface shows a weak interaction with acetone with the sole desorption product (TPD) being acetone at 210 K. The chemisorbed molecule binds to the surface as the ?1-acetone species rather than through a bridge-bonded dioxy-configuration. Exposure of a CeO2(111) surface to acetone at 600K removes oxygen as CO and results in the conversion of Ce4+ to Ce3+. Acetone chemisorbs strongly on reduced CeO2-x(111) with molecular acetone desorbing near 500 K. Decomposition also occurs with H2 desorbing between 450 and 600 K and C reacting with O in the ceria to desorb above 650 K. A stable species exists from 200 to 500 K on the reduced surface that has three unique types of C. High resolution C 1s XPS spectra indicate these are Ce-CH2, C-CH3 and C-O species. C k-edge NEXAFS indicates the presence of C{double_bond}C and C{double_bond}O bonds. It is postulated that the intermediate is a carbanion bonded through both O and C atoms to Ce cations.

  3. The role of charge transfer in the oxidation state change of Ce atoms in the TM13-CeO2(111) systems (TM = Pd, Ag, Pt, Au): a DFT + U investigation.

    PubMed

    Tereshchuk, Polina; Freire, Rafael L H; Ungureanu, Crina G; Seminovski, Yohanna; Kiejna, Adam; Da Silva, Juarez L F

    2015-05-28

    Despite extensive studies of transition metal (TM) clusters supported on ceria (CeO2), fundamental issues such as the role of the TM atoms in the change in the oxidation state of Ce atoms are still not well understood. In this work, we report a theoretical investigation based on static and ab initio molecular dynamics density functional theory calculations of the interaction of 13-atom TM clusters (TM = Pd, Ag, Pt, Au) with the unreduced CeO2(111) surface represented by a large surface unit cell and employing Hubbard corrections for the strong on-site Coulomb correlation in the Ce f-electrons. We found that the TM13 clusters form pyramidal-like structures on CeO2(111) in the lowest energy configurations with the following stacking sequence, TM/TM4/TM8/CeO2(111), while TM13 adopts two-dimensional structures at high energy structures. TM13 induces a change in the oxidation state of few Ce atoms (3 of 16) located in the topmost Ce layer from Ce(IV) (itinerant Ce f-states) to Ce(III) (localized Ce f-states). There is a charge flow from the TM atoms to the CeO2(111) surface, which can be explained by the electronegativity difference between the TM (Pd, Ag, Pt, Au) and O atoms, however, the charge is not uniformly distributed on the topmost O layer due to the pressure induced by the TM13 clusters on the underlying O ions, which yields a decrease in the ionic charge of the O ions located below the cluster and an increase in the remaining O ions. Due to the charge flow mainly from the TM8-layer to the topmost O-layer, the charge cannot flow from the Ce(IV) atoms to the O atoms with the same magnitude as in the clean CeO2(111) surface. Consequently, the effective cationic charge decreases mainly for the Ce atoms that have a bond with the O atoms not located below the cluster, and hence, those Ce atoms change their oxidation state from IV to III. This increases the size of the Ce(III) compared with the Ce(IV) cations, which builds-in a strain within the topmost Ce layer, and hence, also affecting the location of the Ce(III) cations and the structure of the TM13 clusters.

  4. Origins and implications of the ordering of oxygen vacancies and localized electrons on partially reduced CeO2(111)

    DOE PAGESBeta

    Sutton, Jonathan E.; Beste, Ariana; Steven H. Overbury

    2015-10-12

    In this study, we use density functional theory to explain the preferred structure of partially reduced CeO2(111). Low-energy ordered structures are formed when the vacancies are isolated (maximized intervacancy separation) and the size of the Ce3+ ions is minimized. Both conditions help minimize disruptions to the lattice around the vacancy. The stability of the ordered structures suggests that isolated vacancies are adequate for modeling more complex (e.g., catalytic) systems. Oxygen diffusion barriers are predicted to be low enough that O diffusion between vacancies is thermodynamically controlled at room temperature. The O-diffusion-reaction energies and barriers are decreased when one Ce fmore » electron hops from a nearest-neighbor Ce cation to a next-nearest-neighbor Ce cation, with a barrier that has been estimated to be slightly less than the barrier to O diffusion in the absence of polaron hopping. In conculsion, this indicates that polaron hopping plays a key role in facilitating the overall O diffusion process, and depending on the relative magnitudes of the polaron hopping and O diffusion barriers, polaron hopping may be the kinetically limiting process.« less

  5. High Catalytic Activity and Chemoselectivity of Sub-nanometric Pd Clusters on Porous Nanorods of CeO2 for Hydrogenation of Nitroarenes.

    PubMed

    Zhang, Sai; Chang, Chun-Ran; Huang, Zheng-Qing; Li, Jing; Wu, Zhemin; Ma, Yuanyuan; Zhang, Zhiyun; Wang, Yong; Qu, Yongquan

    2016-03-01

    Sub-nanometric Pd clusters on porous nanorods of CeO2 (PN-CeO2) with a high Pd dispersion of 73.6% exhibit the highest catalytic activity and best chemoselectivity for hydrogenation of nitroarenes to date. For hydrogenation of 4-nitrophenol, the catalysts yield a TOF of ∼44059 h(-1) and a chemoselectivity to 4-aminophenol of >99.9%. The superior catalytic performance can be attributed to a cooperative effect between the highly dispersed sub-nanometric Pd clusters for hydrogen activation and unique surface sites of PN-CeO2 with a high concentration of oxygen vacancy for an energetically and geometrically preferential adsorption of nitroarenes via nitro group. The high concentration of surface defects of PN-CeO2 and large Pd dispersion contribute to the enhanced catalytic activity for the hydrogenation reactions. The high chemoselectivity is mainly governed by the high Pd dispersion on the support. The catalysts also deliver high catalytic activity and selectivity for nitroaromatics with various reducible substituents into the corresponding aminoarenes.

  6. An ultrasensitive electrochemical sensor for simultaneous determination of xanthine, hypoxanthine and uric acid based on Co doped CeO2 nanoparticles.

    PubMed

    Lavanya, N; Sekar, C; Murugan, R; Ravi, G

    2016-08-01

    A novel electrochemical sensor has been fabricated using Co doped CeO2 nanoparticles for selective and simultaneous determination of xanthine (XA), hypoxanthine (HXA) and uric acid (UA) in a phosphate buffer solution (PBS, pH5.0) for the first time. The Co-CeO2 NPs have been prepared by microwave irradiation method and characterized by Powder XRD, Raman spectroscopy, HRTEM and VSM measurements. The electrochemical behaviours of XA, HXA and UA at the Co-CeO2 NPs modified glassy carbon electrode (GCE) were studied by cyclic voltammetry and square wave voltammetry methods. The modified electrode exhibited remarkably well-separated anodic peaks corresponding to the oxidation of XA, HXA and UA over the concentration range of 0.1-1000, 1-600 and 1-2200μM with detection limits of 0.096, 0.36, and 0.12μM (S/N=3), respectively. For simultaneous detection by synchronous change of the concentrations of XA, HXA and UA, the linear responses were in the range of 1-400μM each with the detection limits of 0.47, 0.26, and 0.43μM (S/N=3), respectively. The fabricated sensor was further applied to the detection of XA, HXA and UA in human urine samples with good selectivity and high reproducibility.

  7. Template-assisted formation of microsized nanocrystalline CeO2 tubes and their catalytic performance in the carboxylation of methanol

    PubMed Central

    Naumann, Meike; Schäfer, Christian; Brandner, Armin; Hofmann, Heiko J; Claus, Peter

    2011-01-01

    Summary Polymethylmethacrylate (PMMA)/ceria composite fibres were synthesized by using a sequential combination of polymer electrospinning, spray-coating with a sol, and a final calcination step to yield microstructured ceria tubes, which are composed of nanocrystalline ceria particles. The PMMA template is removed from the organic/inorganic hybrid material by radio frequency (rf) plasma etching followed by calcination of the ceramic green-body fibres. Microsized ceria (CeO2) tubes, with a diameter of ca. 0.75 µm, composed of nanocrystalline agglomerated ceria particles were thus obtained. The 1-D ceramic ceria material was characterized by X-ray diffraction, scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), UV–vis and photoluminescence spectroscopy (PL), as well as thermogravimetric analysis (TGA). Its catalytic performance was studied in the direct carboxylation of methanol with carbon dioxide leading to dimethyl carbonate [(CH3O)2CO, DMC], which is widely employed as a phosgene and dimethyl sulfate substitute, and as well as a fuel additive. PMID:22259761

  8. Influence of synthesis conditions on the crystal structure of the powder formed in the ZrO2 - Ce2O3/CeO2 system.

    NASA Astrophysics Data System (ADS)

    Popov, V. V.; Menushenkov, A. P.; Khubbutdinov, R. M.; Svetogorov, R. D.; Zubavichus, Ya V.; Sharapov, A. S.; Kurilkin, V. V.

    2016-09-01

    Influence of synthesis conditions (type of atmosphere, reduction and oxidation, annealing temperature) on the chemical composition and structure of the compounds formed in the “ZrO2 - Ce2O3 / CeO2” system has been investigated by X-ray absorption fine structure (XAFS) spectroscopy combined with X-ray diffraction (XRD) and thermogravimetric analysis (TGA). It is revealed that isothermal annealing of precursor at temperatures less than 1000 °C in air leads to formation of Ce0.5Zr0.5O2 powders with cubic fluorite-type structure (Fm-3m). Further increase of annealing temperatures above 1000 °C causes decomposition of formed crystal structure into two phases: cubic and tetragonal. Annealing in reduction hydrogen atmosphere causes formation of Ce4 + 2xCe3 + 2-2xZr2O7 + x compounds with intermediate valency of cerium, where value of x depends on the reducing conditions and treatment parameters of precursor. Annealing in vacuum at 1400 °C strongly reduces the content of Ce4+ in a powder samples and leads to formation of pyrochlore structure (space group Fd-3m) with practically Ce3+ valence state.

  9. Interplay of dopant, defects and electronic structure in driving ferromagnetism in Co-doped oxides: TiO(2), CeO(2) and ZnO.

    PubMed

    Ali, Bakhtyar; Shah, Lubna R; Ni, C; Xiao, J Q; Shah, S Ismat

    2009-11-11

    A comprehensive study of the defects and impurity (Co)-driven ferromagnetism is undertaken in the oxide semiconductors: TiO(2), ZnO and CeO(2). The effect of magnetic (Co(2+)) and non-magnetic (Cu(2+)) impurities in conjunction with defects, such as oxygen vacancies (V(o)), have been thoroughly investigated. Analyses of the x-ray diffraction (XRD) and x-ray photoelectron spectroscopy (XPS) data reveal the incorporation of cobalt in the lattice, with no signature of cobalt segregation. It is shown that oxygen vacancies are necessary for the ferromagnetic coupling in the Co-doped oxides mentioned above. The possible exchange mechanisms responsible for the ferromagnetism are discussed in light of the energy levels of dopants in the host oxides. In addition, Co and Cu co-doped TiO(2) samples are studied in order to understand the role of point defects in establishing room temperature ferromagnetism. The parameters calculated from the bound magnetic polaron (BMP) and Jorgensen's optical electronegativity models offer a satisfactory explanation of the defect-driven ferromagnetism in the doped/co-doped samples.

  10. Selective catalytic reduction of NO with NH3 over CeO2-ZrO2-WO3 catalysts prepared by different methods

    NASA Astrophysics Data System (ADS)

    Ning, Ping; Song, Zhongxian; Li, Hao; Zhang, Qiulin; Liu, Xin; Zhang, Jinhui; Tang, Xiaosu; Huang, Zhenzhen

    2015-03-01

    The selective catalytic reduction (SCR) of NO by NH3 has been investigated over the CeO2-ZrO2-WO3 (CZW) catalysts prepared by hydrothermal synthesis, incipient impregnation, co-precipitation and sol-gel methods. The results indicate that the CZW catalyst prepared by hydrothermal method shows the best SCR activity, and more than 90% NO conversion is obtained at 195-450 °C with a gas hourly space velocity of 50,000 h-1. The samples are characterized by XRD, N2 adsorption-desorption, SEM, EDS, XPS, H2-TPR, NH3-TPD and Pyridine-IR techniques. The results imply that the superior SCR activity of CZW catalyst is contributed to the excellent redox property, strong acidity and highest content of chemisorbed oxygen species. Furthermore, the larger surface area and greater total pore volume improve the redox ability and enhance NO conversion at low temperature, while the co-existence of Lewis and Brønsted acid sites enhance the SCR activity at high temperature.

  11. Origins and implications of the ordering of oxygen vacancies and localized electrons on partially reduced CeO2(111 )

    NASA Astrophysics Data System (ADS)

    Sutton, Jonathan E.; Beste, Ariana; Overbury, Steven H.

    2015-10-01

    We use density functional theory to explain the preferred structure of partially reduced CeO2(111 ). Low-energy ordered structures are formed when the vacancies are isolated (maximized intervacancy separation) and the size of the Ce3 + ions is minimized. Both conditions help minimize disruptions to the lattice around the vacancy. The stability of the ordered structures suggests that isolated vacancies are adequate for modeling more complex (e.g., catalytic) systems. Oxygen diffusion barriers are predicted to be low enough that O diffusion between vacancies is thermodynamically controlled at room temperature. The O-diffusion-reaction energies and barriers are decreased when one Ce f electron hops from a nearest-neighbor Ce cation to a next-nearest-neighbor Ce cation, with a barrier that has been estimated to be slightly less than the barrier to O diffusion in the absence of polaron hopping. This indicates that polaron hopping plays a key role in facilitating the overall O diffusion process, and depending on the relative magnitudes of the polaron hopping and O diffusion barriers, polaron hopping may be the kinetically limiting process.

  12. Alkali metal poisoning of a CeO2-WO3 catalyst used in the selective catalytic reduction of NOx with NH3: an experimental and theoretical study.

    PubMed

    Peng, Yue; Li, Junhua; Chen, Liang; Chen, Jinghuan; Han, Jian; Zhang, He; Han, Wei

    2012-03-01

    The alkali metal-induced deactivation of a novel CeO(2)-WO(3) (CeW) catalyst used for selective catalytic reduction (SCR) was investigated. The CeW catalyst could resist greater amounts of alkali metals than V(2)O(5)-WO(3)/TiO(2). At the same molar concentration, the K-poisoned catalyst exhibited a greater loss in activity compared with the Na-poisoned catalyst below 200 °C. A combination of experimental and theoretical methods, including NH(3)-TPD, DRIFTS, H(2)-TPR, and density functional theory (DFT) calculations, were used to elucidate the mechanism of the alkali metal deactivation of the CeW catalyst in SCR reaction. Experiments results indicated that decreases in the reduction activity and the quantity of Brønsted acid sites rather than the acid strength were responsible for the catalyst deactivation. The DFT calculations revealed that Na and K could easily adsorb on the CeW (110) surface and that the surface oxygen could migrate to cover the active tungsten, and then inhibit the SCR of NO(x) with ammonia. Hot water washing is a convenient and effective method to regenerate alkali metal-poisoned CeW catalysts, and the catalytic activity could be recovered 90% of the fresh catalyst.

  13. Chemical reaction mechanisms between Y2O3 stabilized ZrO2 and Gd doped CeO2 with PH3 in coal syngas

    NASA Astrophysics Data System (ADS)

    Chen, Gang; Kishimoto, Haruo; Yamaji, Katsuhiko; Kuramoto, Koji; Gong, Mingyang; Liu, Xingbo; Hackett, Gregory; Gerdes, Kirk; Horita, Teruhisa

    2014-12-01

    To clarify the chemical stability of the key materials exposed to coal syngas (CSG) containing PH3 contaminant atmosphere, exposure tests of Y2O3 8 mol.% stabilized ZrO2 (YSZ) and Gd doped CeO2 (GDC) are carried out in simulated CSG with different concentrations of PH3. Significant reaction between YSZ and 10 ppm PH3 in CSG atmosphere is confirmed, and no obvious reaction is detected on the surface of YSZ after exposed in CSG with 1 ppm PH3. YPO4, Zr2.25(PO4)3 and monoclinic Y partial stabilized ZrO2 (m-PSZ) are identified on the YSZ pellet surface after exposed in CSG with 10 ppm PH3. GDC reacted with PH3 even at 1 ppm concentration. A (Ce0.9Gd0.1)PO4 layer is formed on the surface of GDC pellet after exposure in CSG with 10 ppm PH3. Possible reaction mechanisms between YSZ and GDC with PH3 in CSG are clarified. Compared with GDC, YSZ exhibits sufficient phosphorus resistance for devices directly exposed to a coal syngas atmosphere containing low concentration of PH3.

  14. Effect of CeO2, MgO and Y2O3 additions on the sinterability of a milled Si3N4 with 14.5 wt% SiO2

    NASA Technical Reports Server (NTRS)

    Arias, A.

    1981-01-01

    The sinterability of alpha Si3N4 with 0-5.07 equivalent per cent of CeO2, MgO, or Y2O3 has been studied in the temperature range 1650-1820 C by density measurements and X-ray diffraction analysis. Maximum densities were obtained in the range 1765-1820 C and were 99.6% of theoretical with 2.5% CeO2; 98.5% of theoretical with 1.24 to 1.87% MgO, and 99.2% of theoretical with 2.5% Y2O3. Densities 94% or more of theoretical value were obtained with as little as 0.62 equivalent per cent additive.

  15. Dielectric and piezoelectric properties of CeO2-added nonstoichiometric (Na0.5K0.5)0.97(Nb0.96Sb0.04)O3 ceramics for piezoelectric energy harvesting device applications.

    PubMed

    Oh, Youngkwang; Noh, Jungrae; Yoo, Juhyun; Kang, Jinhee; Hwang, Larkhoon; Hong, Jaeil

    2011-09-01

    In this study, nonstoichiometric (Na(0.5)K(0.5))(0.97)(Nb(0.96)Sb(0.04))O(3) ceramics were fabricated and their dielectric and piezoelectric properties were investigated according to the CeO(2) addition. In this ceramic composition, CeO(2) addition improved sinterability, electromechanical coupling factor k(p), mechanical quality factor Q(m), piezoelectric constant d(33), and g(33). At the sintering temperature of 1100°C, for the 0.2wt% CeO(2) added specimen, the optimum values of density = 4.359 g/cm(3), k(p) = 0.443, Q(m) = 588, ε(r) = 444, d(33) = 159 pC/N, and g(33) = 35 × 10(-3) V·m/N, were obtained. A piezoelectric energy harvesting device using 0.2 wt% CeO(2)- added lead-free (K(0.5)Na(0.5))(0.97)(Nb(0.96)Sb(0.04))O(3) ceramics and a rectifying circuit for energy harvesting were fabricated and their electrical characteristics were investigated. Under an external vibration acceleration of 0.7 g, when the mass, the frequency of vibration generator, and matching load resistance were 2.4 g, 70 Hz, and 721 Ω, respectively, output voltage and power of piezoelectric harvesting device indicated the optimum values of 24.6 mV(rms) and 0.839 μW, respectively-suitable for application as the electric power source of a ubiquitous sensor network (USN) sensor node. PMID:21937318

  16. Preparation and crystalline qualities of SrTiO 3 and CeO 2 buffer layers fabricated on Ni substrates via a sol-gel method for YBCO coated conductors

    NASA Astrophysics Data System (ADS)

    Chen, S.; Sun, Z.; Shi, K.; Wang, S.; Meng, J.; Liu, Q.; Han, Z.

    2004-10-01

    High purity rolled Ni substrate was annealed at 1000 °C for 60 min to develop a cube texture with a full-width at half-maximum (FWHM) value of 5.26°. Strontium acetate, titanium (IV) butoxide, and inorganic cerium nitrite were used as the starting materials for fabrication of SrTiO 3 and CeO 2 buffer layers via a sol-gel method on the Ni substrate material. The results show that the heat treatment temperature and holding time affect both the surface morphology and the texture of the buffer layers. The SrTiO 3 and CeO 2 buffer layers grown on the Ni substrate show a sharp (2 0 0) orientation distribution. An intermediate layer was found between the SrTiO 3 layer and the Ni substrate. By optimizing the heat treatment parameters, the ω-scan FWHM values can reach 5.31° and 6.60° for the SrTiO 3 and CeO 2 buffer layers, respectively.

  17. Effect of Ce doping of TiO2 support on NH3-SCR activity over V2O5-WO3/CeO2-TiO2 catalyst.

    PubMed

    Cheng, Kai; Liu, Jian; Zhang, Tao; Li, Jianmei; Zhao, Zhen; Wei, Yuechang; Jiang, Guiyuan; Duan, Aijun

    2014-10-01

    CeO2-TiO2 composite supports with different Ce/Ti molar ratios were prepared by a homogeneous precipitation method, and V2O5-WO3/CeO2-TiO2 catalysts for the selective catalytic reduction (SCR) of NOx with NH3 were prepared by an incipient-wetness impregnation method. These catalysts were characterized by means of BET, XRD, UV-Vis, Raman and XPS techniques. The results showed that the catalytic activity of V2O5-WO3/TiO2 was greatly enhanced by Ce doping (molar ratio of Ce/Ti=1/10) in the TiO2 support. The catalysts that were predominantly anatase TiO2 showed better catalytic performance than the catalysts that were predominantly fluorite CeO2. The Ce additive could enhance the surface adsorbed oxygen and accelerate the SCR reaction. The effects of O2 concentration, ratio of NH3/NO, space velocity and SO2 on the catalytic activity were also investigated. The presence of oxygen played an important role in NO reduction. The optimal ratio of NH3/NO was 1/1 and the catalyst had good resistance to SO2 poisoning. PMID:25288555

  18. Effect of Ce doping of TiO2 support on NH3-SCR activity over V2O5-WO3/CeO2-TiO2 catalyst.

    PubMed

    Cheng, Kai; Liu, Jian; Zhang, Tao; Li, Jianmei; Zhao, Zhen; Wei, Yuechang; Jiang, Guiyuan; Duan, Aijun

    2014-10-01

    CeO2-TiO2 composite supports with different Ce/Ti molar ratios were prepared by a homogeneous precipitation method, and V2O5-WO3/CeO2-TiO2 catalysts for the selective catalytic reduction (SCR) of NOx with NH3 were prepared by an incipient-wetness impregnation method. These catalysts were characterized by means of BET, XRD, UV-Vis, Raman and XPS techniques. The results showed that the catalytic activity of V2O5-WO3/TiO2 was greatly enhanced by Ce doping (molar ratio of Ce/Ti=1/10) in the TiO2 support. The catalysts that were predominantly anatase TiO2 showed better catalytic performance than the catalysts that were predominantly fluorite CeO2. The Ce additive could enhance the surface adsorbed oxygen and accelerate the SCR reaction. The effects of O2 concentration, ratio of NH3/NO, space velocity and SO2 on the catalytic activity were also investigated. The presence of oxygen played an important role in NO reduction. The optimal ratio of NH3/NO was 1/1 and the catalyst had good resistance to SO2 poisoning.

  19. Variations in the structural, optical and electrochemical properties of CeO 2-TiO 2 films as a function of TiO 2 content

    NASA Astrophysics Data System (ADS)

    Verma, Amita; Joshi, Amish G.; Bakhshi, A. K.; Shivaprasad, S. M.; Agnihotry, S. A.

    2006-05-01

    Alcohol based sols of cerium chloride (CeCl 3·7H 2O) and titanium propoxide (Ti(OPr) 4) in ethanol mixed in different mole ratios have yielded mixed oxide films on densification at 500 °C. The reversibility of the intercalation/deintercalation reactions has shown electrochemical stability of the films. Addition of TiO 2 in an equivalent mole ratio manifests in producing highly transparent films with appreciable ion storage capacity. The electrochemical studies have revealed the significant role of TiO 2 in controlling the ion storage capacity of the films, as it tends to induce the disorder. In addition, the films prepared from an aged sol are observed to exhibit a much higher ion storage capacity than the films deposited using the as-prepared sol. The X-ray photoelectron spectroscopic studies have provided information on the variation of Ce 4+/Ce 3+ ratio as a function of increased TiO 2 content in the films. This study has led to a better understanding of the increased ion storage capacity with the increased TiO 2 proportion. The transmission electron microscopic study has demonstrated the presence of CeO 2 nanograins even in films, which are amorphous to X-rays. Elucidation of the structural, optical and electrochemical features of the films has yielded information on aspects relevant to their usage in transmissive electrochromic devices. The films have been found to exhibit properties that can find application as counter electrode in electrochromic smart windows in which they are able to retain their transparency under charge insertion, high enough for practical uses. Also, the fastest coloration-bleaching kinetics for the primary electrochromic electrode (WO 3) working in combination with Ce/Ti (1:1) electrode stimulates the use of latter in electrochromic windows (ECWs).

  20. Characterization of CeO2-Supported Cu-Pd Bimetallic Catalyst for the Oxygen-Assisted Water-Gas Shift Reaction

    SciTech Connect

    Fox, Elise; Velu, Subramani; Engelhard, Mark H.; Chin, Ya-Huei; Miller, Jeffrey T.; Kropf, Jeremy; Song, Chunshan

    2008-12-10

    This study was focused to investigate the roles of Cu and Pd in CuPd/CeO2 bimetallic catalysts containing 20-30 wt% Cu and 0.5-1 wt% Pd used in the oxygen-assisted water-gas shift (OWGS) reaction employing a combined bulk and surface characterization techniques such as XRD, TPR, CO chemisorption, and in-situ XPS. The catalytic activity for CO conversion and the stability of catalyst during on-stream operation increased by the addition of Cu to Pd/CeO2 or Pd to Cu/CeO2 monometallic catalysts, especially when the OWGS reaction was performed under low temperatures, below 200oC. The bimetallic catalyst after leaching with nitric acid retained about 60% of its original activity. The TPR of monometallic Cu/CeO2 showed reduction of CuO supported on CeO2 in two distinct regions, around 150 and 250oC. The high temperature peak disappeared and reduction occurred in a single step around 150oC upon Pd addition. The Pd dispersion decreased from 38.5% for Pd/CeO2 to below 1% for CuPd/CeO2 bimetallic catalyst. In-situ XPS studies showed a shift in Cu 2p peaks toward lower binding energy (BE) with concommitant shift in the Pd 3d peaks toward higher BE. Addition of Pd decreased the surface Cu concentration while the concentration of Pd remained unaltered. All these observations indicated the formation of Cu-Pd surface alloy. The valence band XP spectra collected below 10 eV corroborated the core level XP spectra and indicated that Cu is mainly involved in the catalytic reaction. The improved catalytic activity and stability of CuPd/CeO2 bimetallic catalyst was attributed to the alloy formation.

  1. Ultrasound-assisted reductive dissolution of CeO2 and PuO2 in the presence of Ti particles.

    PubMed

    Beaudoux, Xavier; Virot, Matthieu; Chave, Tony; Leturcq, Gilles; Jouan, Gauthier; Venault, Laurent; Moisy, Philippe; Nikitenko, Sergey I

    2016-06-01

    PuO2 is considered an important material for current and future nuclear fuel; however it is a very refractive compound towards dissolution. Among other techniques, its reprocessing can be performed via complexing dissolution in concentrated and boiling nitric acid containing hydrofluoric acid, or via oxidant dissolution in the presence of reagents with redox couples having high potentials such as Ce(iv)/Ce(iii), or Ag(ii)/Ag(i). Reductive dissolution can be performed under softer conditions and is considered an alternative to these methods which may suffer from several drawbacks (corrosion, effluent management, compatibility with nuclear waste disposal, etc.). In this study, a sonochemical and reductive approach is investigated for PuO2 dissolution under relatively mild conditions. At the first stage, the experiments are performed with CeO2 as an inactive surrogate for PuO2. The quantitative dissolution of both oxides can be achieved under ultrasound (20 kHz, 0.35-0.70 W mL(-1)) in 0.5 M HNO3/0.1 M [N2H5NO3]/2 M HCOOH sparged with Ar at 33-35 °C in the presence of Ti particles as a generating source of reductive species. Ultrasound enables the depassivation of the Ti surface (usually strongly passivated in nitric solutions) through acoustic cavitation which then allows further generation of the intermediate Ti(iii) reductive species. Dissolution rates and yields can be further increased with the injection of dilute fluoride aliquots (NH4F or HF) in the sonicated solution to favor Ti chemical depassivation. The rapid and complete dissolution of PuO2 under selected conditions is accompanied by Pu(iii) accumulation in solution. PMID:27145713

  2. On The Protection by The Combination of CeO2 Nanoparticles and Sodium Selenite on Human Lymphocytes against Chlorpyrifos-Induced Apoptosis In Vitro

    PubMed Central

    Pedram, Sahar; Mohammadirad, Azadeh; Rezvanfar, Mohammad Amin; Navaei-Nigjeh, Mona; Baeeri, Maryam; Abdollahi, Mohammad

    2015-01-01

    Objective Chlorpyrifos (CP) as an organophosphorus pesticide is thought to induce oxidative stress in human cells via producing reactive oxygen species (ROS) that leads to the presence of pathologic conditions due to apoptosis along with acetylcholinesterase (AChE) inhibition.This study aimed to evaluate the apoptotic effects of CP and to assess the protective potential of CeO2nanoparticle (CNP) and sodium selenite (SSe) by measuring cascades of apoptosis, oxidative stress, inflammation, and AChE inhibition in human isolated lymphocytes. Materials and Methods In the present experimental study, we examined the anti-oxidative and AChE activating potential of CNP and SSe in CP-treated human lymphocytes. Therefore, the lymphocytes were isolated and exposed to CP, CP+CNP, CP+SSe, and CP+CNP+SSe after a three-day incubation. Then tumor necrosis factor-alpha (TNF-α) release, myeloperoxidase (MPO) activity, thiobarbituric acid-reactive substances (TBARS) levels as inflammatory/oxidative stress indices along with AChE activity were assessed. In addition, the apoptotic process was measured by flow cytometry. Results Results showed a significant reduction in the mortality rate, TNF-α, MPO activity, TBARS, and apoptosis rate in cells treated with CNP, SSe and their combination. Interestingly, both CNP and SSe were able to activate AChE which is inhibited by CP. The results supported the synergistic effect of CNP/SSe combination in the prevention of apoptosis along with oxidative stress and inflammatory cascade. Conclusion CP induces apoptosis in isolated human lymphocytes via oxidative stress and inflammatory mediators. CP firstly produces ROS, which leads to membrane phospholipid damage. The beneficial effects of CNP and SSe in reduction of CP-induced apoptosis and restoring AChE inhibition relate to their anti-oxidative potentials. PMID:26199915

  3. DNA damage and oxidative stress induced by CeO2 nanoparticles in human dermal fibroblasts: Evidence of a clastogenic effect as a mechanism of genotoxicity.

    PubMed

    Benameur, Laila; Auffan, Mélanie; Cassien, Mathieu; Liu, Wei; Culcasi, Marcel; Rahmouni, Hidayat; Stocker, Pierre; Tassistro, Virginie; Bottero, Jean-Yves; Rose, Jérôme; Botta, Alain; Pietri, Sylvia

    2015-01-01

    The broad range of applications of cerium oxide (CeO2) nanoparticles (nano-CeO2) has attracted industrial interest, resulting in greater exposures to humans and environmental systems in the coming years. Their health effects and potential biological impacts need to be determined for risk assessment. The aims of this study were to gain insights into the molecular mechanisms underlying the genotoxic effects of nano-CeO2 in relation with their physicochemical properties. Primary human dermal fibroblasts were exposed to environmentally relevant doses of nano-CeO2 (mean diameter, 7 nm; dose range, 6 × 10(-5)-6 × 10(-3) g/l corresponding to a concentration range of 0.22-22 µM) and DNA damages at the chromosome level were evaluated by genetic toxicology tests and compared to that induced in cells exposed to micro-CeO2 particles (mean diameter, 320 nm) under the same conditions. For this purpose, cytokinesis-blocked micronucleus assay in association with immunofluorescence staining of centromere protein A in micronuclei were used to distinguish between induction of structural or numerical chromosome changes (i.e. clastogenicity or aneuploidy). The results provide the first evidence of a genotoxic effect of nano-CeO2, (while not significant with micro-CeO2) by a clastogenic mechanism. The implication of oxidative mechanisms in this genotoxic effect was investigated by (i) assessing the impact of catalase, a hydrogen peroxide inhibitor, and (ii) by measuring lipid peroxidation and glutathione status and their reversal by application of N-acetylcysteine, a precusor of glutathione synthesis in cells. The data are consistent with the implication of free radical-related mechanisms in the nano-CeO2-induced clastogenic effect, that can be modulated by inhibition of cellular hydrogen peroxide release. PMID:25325158

  4. DNA damage and oxidative stress induced by CeO2 nanoparticles in human dermal fibroblasts: Evidence of a clastogenic effect as a mechanism of genotoxicity.

    PubMed

    Benameur, Laila; Auffan, Mélanie; Cassien, Mathieu; Liu, Wei; Culcasi, Marcel; Rahmouni, Hidayat; Stocker, Pierre; Tassistro, Virginie; Bottero, Jean-Yves; Rose, Jérôme; Botta, Alain; Pietri, Sylvia

    2015-01-01

    The broad range of applications of cerium oxide (CeO2) nanoparticles (nano-CeO2) has attracted industrial interest, resulting in greater exposures to humans and environmental systems in the coming years. Their health effects and potential biological impacts need to be determined for risk assessment. The aims of this study were to gain insights into the molecular mechanisms underlying the genotoxic effects of nano-CeO2 in relation with their physicochemical properties. Primary human dermal fibroblasts were exposed to environmentally relevant doses of nano-CeO2 (mean diameter, 7 nm; dose range, 6 × 10(-5)-6 × 10(-3) g/l corresponding to a concentration range of 0.22-22 µM) and DNA damages at the chromosome level were evaluated by genetic toxicology tests and compared to that induced in cells exposed to micro-CeO2 particles (mean diameter, 320 nm) under the same conditions. For this purpose, cytokinesis-blocked micronucleus assay in association with immunofluorescence staining of centromere protein A in micronuclei were used to distinguish between induction of structural or numerical chromosome changes (i.e. clastogenicity or aneuploidy). The results provide the first evidence of a genotoxic effect of nano-CeO2, (while not significant with micro-CeO2) by a clastogenic mechanism. The implication of oxidative mechanisms in this genotoxic effect was investigated by (i) assessing the impact of catalase, a hydrogen peroxide inhibitor, and (ii) by measuring lipid peroxidation and glutathione status and their reversal by application of N-acetylcysteine, a precusor of glutathione synthesis in cells. The data are consistent with the implication of free radical-related mechanisms in the nano-CeO2-induced clastogenic effect, that can be modulated by inhibition of cellular hydrogen peroxide release.

  5. Contribution of energetically reactive surface features to the dissolution of CeO2 and ThO2 analogues for spent nuclear fuel microstructures.

    PubMed

    Corkhill, Claire L; Myllykylä, Emmi; Bailey, Daniel J; Thornber, Stephanie M; Qi, Jiahui; Maldonado, Pablo; Stennett, Martin C; Hamilton, Andrea; Hyatt, Neil C

    2014-08-13

    In the safety case for the geological disposal of nuclear waste, the release of radioactivity from the repository is controlled by the dissolution of the spent fuel in groundwater. There remain several uncertainties associated with understanding spent fuel dissolution, including the contribution of energetically reactive surface sites to the dissolution rate. In this study, we investigate how surface features influence the dissolution rate of synthetic CeO2 and ThO2, spent nuclear fuel analogues that approximate as closely as possible the microstructure characteristics of fuel-grade UO2 but are not sensitive to changes in oxidation state of the cation. The morphology of grain boundaries (natural features) and surface facets (specimen preparation-induced features) was investigated during dissolution. The effects of surface polishing on dissolution rate were also investigated. We show that preferential dissolution occurs at grain boundaries, resulting in grain boundary decohesion and enhanced dissolution rates. A strong crystallographic control was exerted, with high misorientation angle grain boundaries retreating more rapidly than those with low misorientation angles, which may be due to the accommodation of defects in the grain boundary structure. The data from these simplified analogue systems support the hypothesis that grain boundaries play a role in the so-called "instant release fraction" of spent fuel, and should be carefully considered, in conjunction with other chemical effects, in safety performance assessements for the geological disposal of spent fuel. Surface facets formed during the sample annealing process also exhibited a strong crystallographic control and were found to dissolve rapidly on initial contact with dissolution medium. Defects and strain induced during sample polishing caused an overestimation of the dissolution rate, by up to 3 orders of magnitude.

  6. Enhancement of the Power Conversion Efficiency in the Inverted Organic Solar Cells Fabricated Utilizing a CeO2 Interlayer Between the Poly(3-hexylthiophene) (P3HT):[6,6]-Phenyl C6 Butyric Acid Methyl Ester and the Cathode.

    PubMed

    Arul, N Sabari; Lee, Yong Hun; Lee, Dea Uk; Kim, Tae Whan

    2015-01-01

    CeO2 nanoparticles were synthesized by using a precipitation method. High-resolution transmission electron microscopy images, X-ray diffraction patterns, energy dispersive X-ray spectroscopy spectra, and UV-Visible absorption spectroscopy spectra showed that the formed samples were CeO2 polycrystalline nanoparticles. Inverted organic solar cells with a structure of indium-tin-oxide/CeO2/poly(3-hexylthiophene) (P3HT):[6,6]-phenyl C61 butyric acid methyl ester (PCBM)/MoO3/Ag were fabricated. Current density-voltage results showed that the power conversion efficiency of the device of the fabricated inverted OPV cells with a CeO2 interlayer between the P3HT:PCBM and the cathode was 0.39% larger than that without a CeO2 interlayer.

  7. Enhancement of Glycerol Steam Reforming Activity and Thermal Stability by Incorporating CeO2 and TiO2 in Ni- and Co-MCM-41 Catalysts

    NASA Astrophysics Data System (ADS)

    Dade, William N.

    Hydrogen (H2) has many applications in industry with current focus shifted to production of hydrocarbon fuels and valuable oxygenates using the Fischer-Tropsch technology and direct use in proton exchange membrane fuel cell (PEMFC). Hydrogen is generally produced via steam reforming of natural gas or alcohols like methanol and ethanol. Glycerol, a by-product of biodiesel production process, is currently considered to be one of the most attractive sources of sustainable H2 due to its high H/C ratio and bio-based origin. Ni and Co based catalysts have been reported to be active in glycerol steam reforming (GSR); however, deactivation of the catalysts by carbon deposition and sintering under GSR operating conditions is a major challenge. In this study, a series of catalysts containing Ni and Co nanoparticles incorporated in CeO2 and TiO2 modified high surface area MCM-41 have been synthesized using one-pot method. The catalysts are tested for GSR (at H2O/Glycerol mole ratio of 12 and GHSV of 2200 h-1) to study the effect of support modification and reaction temperature (450 - 700 °C) on the product selectivity and long term stability. GSR results revealed that all the catalysts performed significantly well exhibiting over 85% glycerol conversion at 650 °C except Ni catalysts that showed better low temperature activities. Deactivation studies of the catalysts conducted at 650 °C indicated that the Ni-TiO2-MCM-41 and Ni-CeO 2-MCM-41 were resistant to deactivation with ˜100% glycerol conversion for 40 h. In contrast, Co-TiO2-MCM-41 perform poorly as the catalyst rapidly deactivated after 12 h to yield ˜20% glycerol conversion after 40 h. The WAXRD and TGA-DSC analyses of spent catalysts showed a significant amount of coke deposition that might explain catalysts deactivation. The flattening shape of the original BET type IV isotherm with drastic reduction of catalyst surface area can also be responsible for observed drop in catalysts activities.

  8. Bioactivity of Y2O3 and CeO2 doped SiO2-SrO-Na2O glass-ceramics.

    PubMed

    Placek, L M; Keenan, T J; Wren, A W

    2016-08-01

    The bioactivity of yttrium and cerium are investigated when substituted for Sodium (Na) in a 0.52SiO2-0.24SrO-0.24-xNa2O-xMO glass-ceramics (where x = 0.08 and MO = Y2O3 or CeO2). Bioactivity is monitored through pH and inductively coupled plasma-optical emission spectrometry where pH of simulated body fluid ranged from 7.5 to 7.6 and increased between 8.2 and 10.0 after 14-day incubation with the glass-ceramic disks. Calcium (Ca) and phosphorus (P) levels in simulated body fluid after incubation with yttrium and cerium containing disks show a continual decline over the 14-day period. In contrast, Con disks (not containing yttrium or cerium) caused the elimination of Ca in solution after 1 day and throughout the incubation period, and initially showed a decline in P levels followed by an increase at 14 days. Scanning electron microscopy and energy dispersive spectroscopy confirmed the presence of Ca and P on the surface of the simulated body fluid-incubated disks and showed precipitates on Con and HCe (8 mol% cerium) samples. Cell viability of MC3T3 osteoblasts was not significantly affected at a 9% extract concentration. Optical microscopy after 24 h cell incubation with disks showed that Con samples do not support osteoblast or Schwann cell growth, while all yttrium and cerium containing disks have direct contact with osteoblasts spread across the wells. Schwann cells attached in all wells, but only showed spreading with the HY-S (8 mol% yttrium, heated to sintering temperature) and YCe (4 mol% yttrium and cerium) disks. Scanning electron microscopy of the compatible disks shows osteoblast and sNF96.2 Schwann cells attachment and spreading directly on the disk surfaces. PMID:27231265

  9. Green processing of metal oxide core-shell nanoparticles as low-temperature dielectrics in organic thin-film transistors.

    PubMed

    Portilla, Luis; Etschel, Sebastian H; Tykwinski, Rik R; Halik, Marcus

    2015-10-21

    TiO2 , Fe3 O4, AlOx , ITO (indium tin oxide), and CeO2 nanoparticles are tailored to exhibit excellent dispersability in deionized water and alcohols. The latter provides an ecofriendly solution for processing metal oxide nanoparticles at a neutral pH. Water-processed dielectrics from the metal oxide nanoparticles are incorporated into organic thin-film transistors fabricated on rigid and flexible substrates. PMID:26308740

  10. Green processing of metal oxide core-shell nanoparticles as low-temperature dielectrics in organic thin-film transistors.

    PubMed

    Portilla, Luis; Etschel, Sebastian H; Tykwinski, Rik R; Halik, Marcus

    2015-10-21

    TiO2 , Fe3 O4, AlOx , ITO (indium tin oxide), and CeO2 nanoparticles are tailored to exhibit excellent dispersability in deionized water and alcohols. The latter provides an ecofriendly solution for processing metal oxide nanoparticles at a neutral pH. Water-processed dielectrics from the metal oxide nanoparticles are incorporated into organic thin-film transistors fabricated on rigid and flexible substrates.

  11. Relative stability and reducibility of CeO2 and Rh/CeO2 species on the surface and in the cavities of γ-Al2O3: a periodic DFT study.

    PubMed

    Koleva, Iskra Z; Aleksandrov, Hristiyan A; Vayssilov, Georgi N; Duarte, Renata; van Bokhoven, Jeroen A

    2015-09-14

    We report the structure and stability of ceria units deposited on the surface of γ-Al2O3 or incorporated in its cavities, as determined by periodic density functional calculations. Ceria species are modeled as CeO2 or Ce2O4 moieties or as a small nanoparticle, Ce13O26, on the (100) and (001) surfaces of a γ-Al2O3 slab. Among the studied structures the incorporation of Ce(4+) ions in cavities of γ-Al2O3 is favored with respect to the ions on the surface only in subsurface cavities of the (100) surface. The calculations also suggested that formation of a surface layer of ceria on the (100) alumina surface is preferable compared to three-dimensional moieties. The deposition of a small ceria nanoparticle on (100) and (001) surfaces of γ-Al2O3 reduces the energy for oxygen vacancy formation to an essentially spontaneous process on the (100) surface, which may be the reason for the experimentally detected large fraction of Ce(3+) ions in the CeO2/γ-Al2O3 systems. The deposition of a single rhodium atom or RhO unit in some of the structures with a CeO2 unit and Ce13O26 showed that spontaneous electron transfer from rhodium to cerium ion occurs, which results in reduction of Ce(4+) to Ce(3+) and the oxidation of rhodium. Only in the presence of deposited rhodium atoms, the incorporated cerium ions can be reduced to Ce(3+).

  12. Development of Xe and Kr empirical potentials for CeO2, ThO2, UO2 and PuO2, combining DFT with high temperature MD.

    PubMed

    Cooper, M W D; Kuganathan, N; Burr, P A; Rushton, M J D; Grimes, R W; Stanek, C R; Andersson, D A

    2016-10-12

    The development of embedded atom method (EAM) many-body potentials for actinide oxides and associated mixed oxide (MOX) systems has motivated the development of a complementary parameter set for gas-actinide and gas-oxygen interactions. A comprehensive set of density functional theory (DFT) calculations were used to study Xe and Kr incorporation at a number of sites in CeO2, ThO2, UO2 and PuO2. These structures were used to fit a potential, which was used to generate molecular dynamics (MD) configurations incorporating Xe and Kr at 300 K, 1500 K, 3000 K and 5000 K. Subsequent matching to the forces predicted by DFT for these MD configurations was used to refine the potential set. This fitting approach ensured weighted fitting to configurations that are thermodynamically significant over a broad temperature range, while avoiding computationally expensive DFT-MD calculations. The resultant gas potentials were validated against DFT trapping energies and are suitable for simulating combinations of Xe and Kr in solid solutions of CeO2, ThO2, UO2 and PuO2, providing a powerful tool for the atomistic simulation of conventional nuclear reactor fuel UO2 as well as advanced MOX fuels. PMID:27549186

  13. Development of Xe and Kr empirical potentials for CeO2, ThO2, UO2 and PuO2, combining DFT with high temperature MD

    NASA Astrophysics Data System (ADS)

    Cooper, M. W. D.; Kuganathan, N.; Burr, P. A.; Rushton, M. J. D.; Grimes, R. W.; Stanek, C. R.; Andersson, D. A.

    2016-10-01

    The development of embedded atom method (EAM) many-body potentials for actinide oxides and associated mixed oxide (MOX) systems has motivated the development of a complementary parameter set for gas-actinide and gas-oxygen interactions. A comprehensive set of density functional theory (DFT) calculations were used to study Xe and Kr incorporation at a number of sites in CeO2, ThO2, UO2 and PuO2. These structures were used to fit a potential, which was used to generate molecular dynamics (MD) configurations incorporating Xe and Kr at 300 K, 1500 K, 3000 K and 5000 K. Subsequent matching to the forces predicted by DFT for these MD configurations was used to refine the potential set. This fitting approach ensured weighted fitting to configurations that are thermodynamically significant over a broad temperature range, while avoiding computationally expensive DFT-MD calculations. The resultant gas potentials were validated against DFT trapping energies and are suitable for simulating combinations of Xe and Kr in solid solutions of CeO2, ThO2, UO2 and PuO2, providing a powerful tool for the atomistic simulation of conventional nuclear reactor fuel UO2 as well as advanced MOX fuels.

  14. Development of Xe and Kr empirical potentials for CeO2, ThO2, UO2 and PuO2, combining DFT with high temperature MD

    DOE PAGESBeta

    Cooper, M. W. D.; Kuganathan, N.; Burr, P. A.; Rushton, M. J. D.; Grimes, R. W.; Stanek, C. R.; Andersson, D. A.

    2016-08-23

    In this study, the development of embedded atom method (EAM) many-body potentials for actinide oxides and associated mixed oxide (MOX) systems has motivated the development of a complementary parameter set for gas-actinide and gas-oxygen interactions. A comprehensive set of density functional theory (DFT) calculations were used to study Xe and Kr incorporation at a number of sites in CeO2, ThO2, UO2 and PuO2. These structures were used to fit a potential, which was used to generate molecular dynamics (MD) configurations incorporating Xe and Kr at 300 K, 1500 K, 3000 K and 5000 K. Subsequent matching to the forces predictedmore » by DFT for these MD configurations was used to refine the potential set. This fitting approach ensured weighted fitting to configurations that are thermodynamically significant over a broad temperature range, while avoiding computationally expensive DFT-MD calculations. The resultant gas potentials were validated against DFT trapping energies and are suitable for simulating combinations of Xe and Kr in solid solutions of CeO2, ThO2, UO2 and PuO2, providing a powerful tool for the atomistic simulation of conventional nuclear reactor fuel UO2 as well as advanced MOX fuels.« less

  15. Development of Xe and Kr empirical potentials for CeO2, ThO2, UO2 and PuO2, combining DFT with high temperature MD.

    PubMed

    Cooper, M W D; Kuganathan, N; Burr, P A; Rushton, M J D; Grimes, R W; Stanek, C R; Andersson, D A

    2016-10-12

    The development of embedded atom method (EAM) many-body potentials for actinide oxides and associated mixed oxide (MOX) systems has motivated the development of a complementary parameter set for gas-actinide and gas-oxygen interactions. A comprehensive set of density functional theory (DFT) calculations were used to study Xe and Kr incorporation at a number of sites in CeO2, ThO2, UO2 and PuO2. These structures were used to fit a potential, which was used to generate molecular dynamics (MD) configurations incorporating Xe and Kr at 300 K, 1500 K, 3000 K and 5000 K. Subsequent matching to the forces predicted by DFT for these MD configurations was used to refine the potential set. This fitting approach ensured weighted fitting to configurations that are thermodynamically significant over a broad temperature range, while avoiding computationally expensive DFT-MD calculations. The resultant gas potentials were validated against DFT trapping energies and are suitable for simulating combinations of Xe and Kr in solid solutions of CeO2, ThO2, UO2 and PuO2, providing a powerful tool for the atomistic simulation of conventional nuclear reactor fuel UO2 as well as advanced MOX fuels.

  16. The model case of an oxygen storage catalyst - non-stoichiometry, point defects and electrical conductivity of single crystalline CeO2-ZrO2-Y2O3 solid solutions.

    PubMed

    Eufinger, Jens-Peter; Daniels, Maximilian; Schmale, Kerstin; Berendts, Stefan; Ulbrich, Gregor; Lerch, Martin; Wiemhöfer, Hans-Dieter; Janek, Jürgen

    2014-12-14

    The ternary solid solution CeO2-ZrO2 is known for its superior performance as an oxygen storage catalyst in exhaust gas catalysis (e.g. TWC), although the defect chemical background of these outstanding properties is not fully understood quantitatively. Here, a comprehensive experimental study is reported regarding defects and defect-related transport properties of cubic stabilized single crystalline (CexZr1-x)0.8Y0.2O1.9-δ (0 ≤x≤ 1) solid solutions as a model system for CeO2-ZrO2. The constant fraction of yttria was chosen in order to fix a defined concentration of oxygen vacancies and to stabilize the cubic fluorite-type lattice for all Ce/Zr ratios. Measurements of the total electrical conductivity, the partial electronic conductivity, the ionic transference number and the non-stoichiometry (oxygen deficiency, oxygen storage capacity) were performed in the oxygen partial pressure range -25 < lg pO2/bar < 0 and for temperatures between 500 °C and 750 °C. The total conductivity at low pO2 is dominated by electronic transport. A strong deviation from the widely accepted ideal solution based point defect model was observed. An extended point defect model was developed using defect activities rather than concentrations in order to describe the point defect reactions in CeO2-ZrO2-Y2O3 properly. It served to obtain good quantitative agreement with the measured data. By a combination of values for non-stoichiometries and for electronic conductivities, the electron mobility could be calculated as a function of pO2, ranging between 10(-2) cm(2) V(-1) s(-1) and 10(-5) cm(2) V(-1) s(-1). Finally, the origin of the high oxygen storage capacity and superior catalytic promotion performance at a specific ratio of n(Ce)/n(Zr) ≈ 1 was attributed to two main factors: (1) a strongly enhanced electronic conductivity in the high and medium pO2 range qualifies the material to be a good mixed conductor, which is essential for a fast oxygen exchange and (2) the equilibrium constant for the reduction exhibits a maximum, which means that the reduction is thermodynamically most favoured just at this composition.

  17. All-solid-state electric-double-layer transistor based on oxide ion migration in Gd-doped CeO2 on SrTiO3 single crystal

    NASA Astrophysics Data System (ADS)

    Tsuchiya, Takashi; Terabe, Kazuya; Aono, Masakazu

    2013-08-01

    An all-solid-state electric-double-layer transistor (EDLT) with a Gd-doped CeO2 (GDC) oxide ion conductor/SrTiO3 (STO) insulator structure has been developed. At 473 K, the drain current of the EDLT was well controlled, from less than nA order to μA order, by electrostatic carrier doping at the GDC/STO interface due to oxide ion (O2-) migration in the GDC, in contrast to an inactiveness at room temperature. The EDL capacitance at the interface, measured with an ac impedance spectroscopy, was 14 μF cm-2, higher than that reported for a microporous-SiO2 EDLT and comparable to that of an ionic-liquid-gated EDLT.

  18. Nanoparticulate cerium dioxide and cerium dioxide-titanium dioxide composite thin films on glass by aerosol assisted chemical vapour deposition

    NASA Astrophysics Data System (ADS)

    Qureshi, Uzma; Dunnill, Charles W.; Parkin, Ivan P.

    2009-11-01

    Two series of composite thin films were deposited on glass by aerosol assisted chemical vapour deposition (AACVD)—nanoparticulate cerium dioxide and nanoparticulate cerium dioxide embedded in a titanium dioxide matrix. The films were analysed by a range of techniques including UV-visible absorption spectroscopy, X-ray diffraction, scanning electron microscopy and energy dispersive analysis by X-rays. The AACVD prepared films showed the functional properties of photocatalysis and super-hydrophilicity. The CeO 2 nanoparticle thin films displaying photocatalysis and photo-induced hydrophilicity almost comparable to that of anatase titania.

  19. Anomalous grain growth in the surface region of a nanocrystalline CeO2 film under low-temperature heavy ion irradiation

    SciTech Connect

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

    2012-06-15

    Grain growth and phase stability of nanocrystalline ceria are investigated under ion irradiation at different temperatures. Irradiations at temperatures of 300 and 400 K result in uniform grain growth throughout the film. Anomalous grain growth is observed in thin films of nanocrystalline ceria under 3 MeV Au+ irradiation at 160 K. At this low temperature, significant grain growth is observed within 100 nm from the surface, no obvious growth is detected in the rest of the films. While the grain growth is attributed to a defect-stimulated mechanism at room temperature and above, a defect diffusion-limited mechanism is significant at low temperature with the primary defect responsible being the oxygen vacancy. The nanocrystalline grains remain in the cubic phase regardless of defect kinetics.

  20. Anomalous grain growth in the surface region of a nanocrystalline CeO2 film under low-temperature heavy ion irradiation

    SciTech Connect

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

    2012-01-01

    Grain growth and phase stability of nanocrystalline ceria are investigated under ion irradiation at different temperatures. Irradiations at temperatures of 300 and 400 K result in uniform grain growth throughout the film. Anomalous grain growth is observed in thin films of nanocrystalline ceria under 3 MeV Au+ irradiation at 160 K. At this low temperature, significant grain growth is observed within 100 nm from the surface, no obvious growth is detected in the rest of the films. While the grain growth is attributed to a defect-stimulated mechanism at room temperature and above, a defect diffusion-limited mechanism is significant at low temperature with the primary defect responsible being the oxygen vacancy.

  1. 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.

  2. Performance enhancement of solution impregnated nanostructured La0.8Sr0.2Co0.8Ni0.2O3-δ oxygen electrode for intermediate temperature solid oxide electrolysis cells

    NASA Astrophysics Data System (ADS)

    Tan, Yuan; Duan, Nanqi; Wang, Ao; Yan, Dong; Chi, Bo; Wang, Ning; Pu, Jian; Li, Jian

    2016-02-01

    Nanostructured La0.8Sr0.2Co0.8Ni0.2O3-δ (LSCN) based Gd2O3-doped CeO2 (GDC) oxygen electrodes are prepared by impregnation method for intermediate temperature solid oxide electrolysis cell (SOEC) for efficient hydrogen production. The microstructure features and the electrochemical performance of the impregnated LSCN-GDC oxygen electrodes with various LSCN loadings are evaluated and investigated. Electrochemical tests show that the impregnated LSCN-GDC oxygen electrodes present great enhancement of oxygen evolution performance, due to the good nanoparticle LSCN dispersion on the GDC scaffold surface to maximize the active reaction sites. The cell with 30 wt% LSCN loaded LSCN-GDC as the oxygen electrode presents a polarization resistance of 0.072 Ω cm2 at 800 °C with 60 vol% absolute humidity (AH), only about half of that for the screen-printed LSCN electrode. The hydrogen production rate is 484 mL cm-2 h-1 at 750 °C at 1.5 V with 60 vol%AH. For stability test in galvanostatic SOEC operation up to 100 h, the solution impregnated cell shows a very stable performance without obvious degradation.

  3. Enhancement of the chemical stability in confined δ-Bi2O3

    NASA Astrophysics Data System (ADS)

    Sanna, Simone; Esposito, Vincenzo; Andreasen, Jens Wenzel; Hjelm, Johan; Zhang, Wei; Kasama, Takeshi; Simonsen, Søren Bredmose; Christensen, Mogens; Linderoth, Søren; Pryds, Nini

    2015-05-01

    Bismuth-oxide-based materials are the building blocks for modern ferroelectrics, multiferroics, gas sensors, light photocatalysts and fuel cells. Although the cubic fluorite δ-phase of bismuth oxide (δ-Bi2O3) exhibits the highest conductivity of known solid-state oxygen ion conductors, its instability prevents use at low temperature. Here we demonstrate the possibility of stabilizing δ-Bi2O3 using highly coherent interfaces of alternating layers of Er2O3-stabilized δ-Bi2O3 and Gd2O3-doped CeO2. Remarkably, an exceptionally high chemical stability in reducing conditions and redox cycles at high temperature, usually unattainable for Bi2O3-based materials, is achieved. Even more interestingly, at low oxygen partial pressure the layered material shows anomalous high conductivity, equal or superior to pure δ-Bi2O3 in air. This suggests a strategy to design and stabilize new materials that are comprised of intrinsically unstable but high-performing component materials.

  4. Effects of Lithium Oxide Addition on Sintering Behavior and Electrical Conductivity of Ce0.8Gd0.2O1.9 Ceramics Prepared by Commercial Powders.

    PubMed

    Seo, Seung-Woo; Park, Min-Woo; Lee, Joo-Sin

    2016-05-01

    The densification behavior and electrical conductivity of Ce0.8Gd0.2O1.9 ceramics with lithium oxide concentrations ranging from 0 to 7 mol% were investigated. The sintered density was found to increase with increasing Li2O content up to 2 mol% and then to decrease somewhat upon further Li20 addition. Dense Ce0.8Gd0.2O1.9 ceramics with 97% of the theoretical density could be obtained by sintering the milled mixture with 2 mol% Li2O addition at 1250 degrees C for 5 h. The conductivity of the 2 mol% Li2O-added specimen showed a maximum value of 4.99 x 10(-3) Ω(-1) x cm(-1) at 700 degrees C. Pure Ce0.8Gd0.2O1.9 ceramics needed to be sintered at 1550 degrees C in order to obtain an equivalent theoretical density and conductivity. The addition of Li2O was found to promote the sintering properties and electrical conductivities of Gd2O3-doped CeO2.

  5. Effects of Lithium Oxide Addition on Sintering Behavior and Electrical Conductivity of Ce0.8Gd0.2O1.9 Ceramics Prepared by Commercial Powders.

    PubMed

    Seo, Seung-Woo; Park, Min-Woo; Lee, Joo-Sin

    2016-05-01

    The densification behavior and electrical conductivity of Ce0.8Gd0.2O1.9 ceramics with lithium oxide concentrations ranging from 0 to 7 mol% were investigated. The sintered density was found to increase with increasing Li2O content up to 2 mol% and then to decrease somewhat upon further Li20 addition. Dense Ce0.8Gd0.2O1.9 ceramics with 97% of the theoretical density could be obtained by sintering the milled mixture with 2 mol% Li2O addition at 1250 degrees C for 5 h. The conductivity of the 2 mol% Li2O-added specimen showed a maximum value of 4.99 x 10(-3) Ω(-1) x cm(-1) at 700 degrees C. Pure Ce0.8Gd0.2O1.9 ceramics needed to be sintered at 1550 degrees C in order to obtain an equivalent theoretical density and conductivity. The addition of Li2O was found to promote the sintering properties and electrical conductivities of Gd2O3-doped CeO2. PMID:27483925

  6. DFT+U Study on the Localized Electronic States and Their Potential Role During H2O Dissociation and CO Oxidation Processes on CeO2(111) Surface

    SciTech Connect

    Wang, Yanggang; Mei, Donghai; Li, Jun; Rousseau, Roger J.

    2013-10-14

    We present the results of an extensive density functional theory based electronic structure study of the role of 4f-state localized electron states in the surface chemistry of a partially reduced CeO2(111) surface. These electrons exist as polaronic states, residing of Ce3+ sites, which can be created by either the formation of oxygen vacancies, OV, or other surface defects. Via ab initio molecular dynamics these localized electrons are found to be able to move freely within the upper surface layer but penetration into the bulk is prohibited as a result of the higher elastic strain induced by creating a subsurface Ce3+ defect. We found that water molecules can be easily dissociated into two surface bound hydroxyls at the Ce4+ site associated with OV sites and the dissociation process does not significantly affect the electronic structure of the reduced surface. In the presence of water, a proton-mediated Mars-van Krevelen mechanism for CO oxidation via the formation of bicarbonate species is identified. Overall we find that surface hydroxyls formed via water dissociation at CeO2 surface lead to inhabitation of the CO oxidation reaction. This is consistent with the experimental observation of requisite elevated temperatures, on the order of 600K, for this reaction to occur. Part of this work was supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences and performed at the Pacific Northwest National Laboratory (PNNL). PNNL is a multi-program national laboratory operated for DOE by Battelle. J. Li and Y.-G. Wang were also financially supported by NKBRSF (2011CB932400) and NSFC (91026003, 21101098) of China. Y.-G. Wang acknowledges the fellowship from China Scholarship Council and the PNNL-ASF fellowship program. Computational resources were provided at W. R. Wiley Environmental Molecular Science Laboratory (EMSL), a national scientific user facility sponsored by the Department of Energy’s Office of Biological and Environmental Research located at PNNL and the National Energy Research Scientific Computing Center (NERSC) at Lawrence Berkeley National Laboratory.

  7. Evaluation of chemical stability, thermal expansion coefficient, and electrical properties of solid state and wet-chemical synthesized Y and Mn-codoped CeO2 for solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Handal, Hala T.; Thangadurai, Venkataraman

    2013-12-01

    Chemical stability and high electrical conductivity under the operating conditions of solid oxide fuel cell (SOFC) are considered as the momentum for innovating solid electrolytes and electrodes. In this paper, we report synthesis, structure, chemical stability and electrical conductivity of novel co-doped Ce0.9-xY0.1MnxO2-δ (x = 0-15 mol%) (CYMO). X-ray diffraction of Mn and Y-doped CeO2 shows the formation of fluorite-type structure with a space group Fm-3m. A few weak peaks corresponding to a tetragonal Mn3O4 phase has been detected in some samples. Solubility of Mn in ceria is explained by considering the influence of the ionic radius, the crystal structure and its electronic structure. Thermal analysis shows dissimilarity between the reduction behavior of Ce0.9Mn0.1O2-δ and Ce0.9-xY0.1MnxO2-δ. Ce0.8Y0.1Mn0.1O2-δ exhibited the highest conductivity of ˜6 × 10-2 S cm-1 and 0.15 S cm-1 at 700 °C in air and H2, respectively. Surface studies have confirmed the formation of S species upon exposure to 30 ppm H2S in H2 and a mechanism for S poisoning is presented.

  8. Y0.08Sr0.88TiO3-CeO2 composite as a diffusion barrier layer for stainless-steel supported solid oxide fuel cell

    NASA Astrophysics Data System (ADS)

    Kim, Kun Joong; Kim, Sun Jae; Choi, Gyeong Man

    2016-03-01

    A new diffusion barrier layer (DBL) is proposed for solid oxide fuel cells (SOFCs) supported on stainless-steel where DBL prevents inter-diffusion of atoms between anode and stainless steel (STS) support during fabrication and operation of STS-supported SOFCs. Half cells consisting of dense yttria-stabilized zirconia (YSZ) electrolyte, porous Ni-YSZ anode layer, and ferritic STS support, with or without Y0.08Sr0.88TiO3-CeO2 (YST-CeO2) composite DBL, are prepared by tape casting and co-firing at 1250 and 1350 °C, respectively, in reducing (H2) atmosphere. The porous YST-CeO2 layer (t ∼ 60 μm) blocks inter-diffusion of Fe and Ni, and captures the evaporated Cr during cell fabrication (1350 °C). The cell with DBL and La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) cathode achieved a maximum power density of ∼220 mW cm-2 which is stable at 700 °C. In order to further improve the power performance, Ni coarsening in anode during co-firing must be prevented or alternative anode which is resistive to coarsening is suggested. This study demonstrates that the new YST-CeO2 layer is a promising as a DBL for stainless-steel-supported SOFCs fabricated with co-firing process.

  9. Promotion effects of SiO2 or/and Al2O3 doped CeO2/TiO2 catalysts for selective catalytic reduction of NO by NH3.

    PubMed

    Zhao, Wenru; Tang, Yu; Wan, Yaping; Li, Liang; Yao, Si; Li, Xiaowei; Gu, Jinlou; Li, Yongsheng; Shi, Jianlin

    2014-08-15

    A series of the CeO2-based catalysts loaded on TiO2, TiO2-SiO2, TiO2-Al2O3, and TiO2-SiO2-Al2O3 supports were prepared by incipient impregnation method for the selective catalytic reduction (SCR) of NO by NH3 in the presence of oxygen. The SCR activities of the catalysts with different supports increases in the order of Ce/TiO2 < Ce/TiO2-20SiO2 ≈ Ce/TiO2-3.5Al2O3 < Ce/TiO2-20SiO2-3.5Al2O3. The Ce/TiO2-20SiO2-3.5Al2O3 catalyst showed 100% NO conversion in the temperature range of 250-425°C and 100% N2 selectivity in the whole temperature range. The catalytic activity of Ce/TiO2-20SiO2-3.5Al2O3 exhibited good stability and strong resistance to SO2 and H2O poisoning. The co-introduction of SiO2 and Al2O3 into TiO2 could increase the amount of chemisorbed oxygen and Lewis acid sites on the surface of catalyst, which should be responsible for the excellent SCR activity.

  10. Effect of scanning speeds on microstructure and wear behavior of laser-processed NiCr-Cr3C2-MoS2-CeO2 on 38CrMoAl steel

    NASA Astrophysics Data System (ADS)

    Sun, Guifang; Tong, Zhaopeng; Fang, Xiaoyu; Liu, Xiaojun; Ni, Zhonghua; Zhang, Wei

    2016-03-01

    Self-lubricating wear-resistant NiCr-Cr3C2-MoS2-CeO2 layers were fabricated on 38CrMoAl extruder screws by laser processing. The effect of scanning speeds on microstructure, phases, microhardness, and wear behavior was investigated. The obtained results indicate that the laser-processed layers had fine and nonuniform microstructures with undissolved MoS2 particles distributed on the matrix. With an increase of the laser-scanning speeds, the microstructures changed from hypoeutectic to hypereutectic, volume fraction of martensite increased, microhardness increased, and thickness and friction coefficients of the layers decreased. Wear resistance of the optimized layer was increased by 29.76 times compared with that of the substrate. The undissolved MoS2 was separated from the matrix on loading. In addition to the grain-refining and solution-strengthening effects, oxide films formed on the surface of the layers shielded them and enhanced their wear resistance. The crack or fracture behavior of the laser-processed layers on loading was determined by its toughness, which also had an important effect on the wear behavior of the processed layers.

  11. Nanoscale Thin Film Electrolytes for Clean Energy Applications

    SciTech Connect

    Nandasiri, Manjula I.; Sanghavi, Rahul P.; Kuchibhatla, Satyanarayana V N T; Thevuthasan, Suntharampillai

    2012-02-01

    Ceria and zirconia based systems can be used as electrolytes to develop solid oxide fuel cells for clean energy production and to prevent air pollution by developing efficient, reliable oxygen sensors. In this study, we have used oxygen plasma assisted molecular beam epitaxy (OPA-MBE) to grow samaria doped ceria (SDC), to understand the role of dopant concentration and geometry of the films towards the ionic conduction in these thin films. We have also discussed the Gd doped CeO2 (GDC) and Gd stabilized ZrO2 (GSZ) multi-layer thin films to investigate the effect of interfacial phenomena on the ionic conductivity of these hetero-structures. We found the optimum concentration to be 15 mol % SmO1.5, for achieving lowest electrical resistance in SDC thin films. The electrical resistance decreases with the increase in film thickness up to 200 nm. The results demonstrate the usefulness of this study towards establishing an optimum dopant concentration and choosing an appropriate thin film thickness to ameliorate the conductance of the SDC material system. Furthermore, we have explored the conductivity of highly oriented GDC and GSZ multi-layer thin films, wherein the conductivity increased with an increase in the number of layers. The extended defects and lattice strain near the interfaces increase the density of oxygen vacancies, which leads to enhanced ionic conductivity in multi-layer thin films.

  12. Reduced microwave losses of YBa2Cu3O7-δ thin films on electro-optic LiNbO3 crystals

    NASA Astrophysics Data System (ADS)

    Fàbrega, L.; Rubí, R.; Fontcuberta, J.; Sánchez, F.; Ferrater, C.; García-Cuenca, M. V.; Varela, M.; Collado, C.; Mateu, J.; Menendez, O.; O'Callaghan, J. M.

    2002-11-01

    We report on the growth of epitaxial YBa2Cu3O7 thin films on X-cut LiNbO3 single crystals. The use of double CeO2/YSZ buffer layers allows a single in-plane orientation of YBa2Cu3O7, and results in superior superconducting properties. In particular, surface resistance Rs values of 1.4 mΩ have been measured at 8 GHz and 65 K. The attainment of such low values of Rs constitutes a key step toward the incorporation of high Tc materials as electrodes in photonic and acoustic devices.

  13. Pulsed laser deposition of YBCO thin films on IBAD-YSZ substrates

    NASA Astrophysics Data System (ADS)

    Li, M.; Ma, B.; Koritala, R. E.; Fisher, B. L.; Venkataraman, K.; Balachandran, U.

    2003-01-01

    High-quality YBa2Cu3O7-x (YBCO) films were fabricated on yttria-stabilized zirconia (YSZ)-buffered Hastelloy C276 substrates by pulsed laser deposition. YSZ was grown by ion-beam-assisted deposition. A thin (approx10 nm) CeO2 layer was deposited before the deposition of YBCO. The crystalline structure and biaxial texture of the YBCO film and the buffer layer were examined by x-ray diffraction 2theta-scan, phi-scan and pole-figure analysis. Epitaxial growth of the YBCO film on the buffer layer was observed. Full width at half maximum (FWHM) value of 7.4° was measured from the phi-scan of YBCO(103). Raman spectroscopy showed compositional uniformity and phase integrity in the YBCO films. Surface morphologies of the YBCO films were examined by scanning electron microscopy. Comparative studies indicated that the CeO2 buffer layer significantly improves the structural alignment and superconducting properties of YBCO films. Tc = 90 K, with sharp transition, and transport Jc = 2.2 × 106 A cm-2 at 77 K in zero-external field were obtained on the 0.5 mum thick YBCO films. The dependence of Jc on the FWHM of the YBCO(103) phi-scan indicated that high Jc is associated with low FWHM.

  14. Chemiluminescent Diagnostics of Free-Radical Processes in an Abiotic System and in Liver Cells in the Presence of Nanoparticles Based on Rare-Earth Elements nReVO4:Eu3+ (Re = Gd, Y, La) and CeO2

    NASA Astrophysics Data System (ADS)

    Averchenko, E. A.; Kavok, N. S.; Klochkov, V. K.; Malyukin, Yu. V.

    2014-11-01

    We have used luminol-dependent chemiluminescence with Fenton's reagent to study the effect of nanoparticles based on rare-earth elements of different sizes and shapes on free-radical processes in abiotic and biotic cell-free systems, and also in isolated cells in vitro. We have estimated the effects of rare-earth orthovanadate nanoparticles of spherical (GdYVO4:Eu3+, 1-2 nm), spindle-shaped (GdVO4:Eu3+, 25 ×8 nm), and rod-shaped (LaVO4:Eu3+, 57 × (6-8) nm) nanoparticles and spherical CeO2 nanoparticles (sizes 1-2 nm and 8-10 nm). We have shown that in contrast to the abiotic system, in which all types of nanoparticles exhibit antiradical activity, in the presence of biological material, extra-small spherical (1-2 nm) nanoparticles of both types exhibit pro-oxidant activity, and also enhance pro-oxidant induced oxidative stress (for the pro-oxidants hydrogen peroxide and tert-butyl hydroperoxide). The effect of rare-earth orthovanadate spindle and rod shaped nanoparticles in this system was neutral; a moderate antioxidant effect was exhibited by 8-10 nm CeO2 nanoparticles.

  15. Thermal measurements and computational simulations of three-phase (CeO2-MgAl2O4-CeMgAl11O19) and four-phase (3Y-TZP-Al2O3-MgAl2O4-LaPO4) composites as surrogate inert matrix nuclear fuel

    NASA Astrophysics Data System (ADS)

    Angle, Jesse P.; Nelson, Andrew T.; Men, Danju; Mecartney, Martha L.

    2014-11-01

    This study investigates the temperature dependent thermal conductivity of multiphase ceramic composites for simulated inert matrix nuclear fuel. Fine grained composites were made of CeO2-MgAl2O4-CeMgAl11O19 or 3Y-TZP-Al2O3-MgAl2O4-LaPO4. CeO2 and 3Y-TZP are used as UO2 surrogates due to their similar structures and low thermal conductivities. Laser flash analysis from room temperature to 1273 K (1000 °C) was used to determine the temperature dependent thermal conductivity. A computational approach using Object Oriented Finite Element Analysis Version 2 (OOF2) was employed to simulate the composite thermal conductivity based on the microstructure. Observed discrepancies between experimental and simulated thermal conductivities at low temperature may be due to Kapitza resistance; however, there is less than 3% deviation between models and experiments above 673 K (400 °C) for both compositions. When the surrogate phase was replaced with UO2 in the computational model for the four-phase composite, a 12-16% increase in thermal conductivity resulted compared to single phase UO2, in the range of 673-1273 K (400-1000 °C). This computational approach may be potentially viable for the high-throughput evaluation of composite systems and the strategic selection of inert phases without extensive sample fabrication during the initial development stages of composite nuclear fuel design.

  16. Thin Clouds

    Atmospheric Science Data Center

    2013-04-18

    ... their delicate appearance, thin, feathery clouds of ice crystals called cirrus may contribute to global warming. Some scientists ... July 9, 2002 - Thin, feathery clouds of ice crystals over the Caribbean Sea. project:  MISR ...

  17. Ultra-thin Oxide Membranes: Synthesis and Carrier Transport

    NASA Astrophysics Data System (ADS)

    Sim, Jai Sung

    Self-supported freestanding membranes are films that are devoid of any underlying supporting layers. The key advantage of such structures is that, due to the lack of substrate effects - both mechanical and chemical, the true native properties of the material can be probed. This is crucial since many of the studies done on materials that are used as freestanding membranes are done as films clamped to substrates or in the bulk form. This thesis focuses on the synthesis and fabrication as well as electrical studies of free standing ultrathin < 40nm oxide membranes. It also is one of the first demonstrations for electrically probing nanoscale freestanding oxide membranes. Fabrication of such membranes is non-trivial as oxide materials are often brittle and difficult to handle. Therefore, it requires an understanding of thin plate mechanics coupled with controllable thin film deposition process. Taking things a step further, to electrically probe these membranes required design of complex device architecture and extensive optimization of nano-fabrication processes. The challenges and optimized fabrication method of such membranes are demonstrated. Three materials are probed in this study, VO2, TiO2, and CeO2. VO2 for understanding structural considerations for electronic phase change and nature of ionic liquid gating, TiO2 and CeO2 for understanding surface conduction properties and surface chemistry. The VO2 study shows shift in metal-insulator transition (MIT) temperature arising from stress relaxation and opening of the hysteresis. The ionic liquid gating studies showed reversible modulation of channel resistance and allowed distinguishing bulk process from the surface effects. Comparing the ionic liquid gating experiments to hydrogen doping experiments illustrated that ionic liquid gating can be a surface limited electrostatic effect, if the critical voltage threshold is not exceeded. TiO2 study shows creation of non-stoichiometric forms under ion milling. Utilizing

  18. Synthesis of UO2 and ThO2 doped with Gd2O3

    NASA Astrophysics Data System (ADS)

    Baena, Angela; Cardinaels, Thomas; Vos, Benedict; Binnemans, Koen; Verwerft, Marc

    2015-06-01

    Uranium dioxide (urania, UO2) and thorium dioxide (thoria, ThO2) doped with gadolinium oxide (gadolinia, Gd2O3) were prepared via solid-state synthesis. For Gd2O3-doped ThO2, also an alternative, semi-dry process ("suspension coating") was applied in which Gd2O3-coated ThO2 powder was produced via suspension drying followed by calcination. The microstructure and homogeneity of the materials were investigated by ceramography, EPMA and XRD. Solid-state synthesis is a convenient method to produce Gd2O3-doped UO2. However, this route was found to be inappropriate to obtain Gd2O3-doped ThO2 with an acceptable microstructure and homogeneity. The suspension coating process reported in this work is a simple and practical method to overcome these issues.

  19. Thermal stability of NdBCO/YBCO/MgO thin film seeds

    NASA Astrophysics Data System (ADS)

    Volochová, D.; Kavečanský, V.; Antal, V.; Diko, P.; Yao, X.

    2016-04-01

    Thermal stability of the Nd1+x Ba2-x Cu3O7-δ (Nd-123 or NdBCO) thin films deposited on MgO substrate, with YBa2Cu3O7-δ (Y-123 or YBCO) buffer layer (NdBCO/YBCO/MgO thin film), has been experimentally studied in order to determine the optimal film thickness acting as seed for bulk YBCO growth. YBCO bulk superconductors with Y2BaCuO5 (Y-211) and CeO2 addition were prepared by the top seeded melt growth process in a chamber furnace using NdBCO/YBCO/MgO thin film seeds of different thicknesses (200-700 nm with 20 nm YBCO buffer layer) and different maximum temperatures, T max. The maximum temperatures varied in the range of 1040 °C-1125 °C. The highest thermal stability 1118 °C was observed in the case of NdBCO/YBCO/MgO thin film of 300 nm thickness. These results are corroborated with differential scanning calorimetry and high temperature x-ray diffraction measurements, as well as microstructure observations.

  20. Stable BaCe 0.5Zr 0.3Y 0.16Zn 0.04O 3- δ thin membrane prepared by in situ tape casting for proton-conducting solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Zhang, Shangquan; Bi, Lei; Zhang, Lei; Tao, Zetian; Sun, Wenping; Wang, Haiqian; Liu, Wei

    Stable BaCe 0.5Zr 0.3Y 0.16Zn 0.04O 3- δ (BCZYZ) thin membrane was successfully prepared by in situ tape casting/co-firing method for proton-conducting solid oxide fuel cells. The starting powders were BaCO 3, CeO 2, ZrO 2, Y 2O 3, ZnO for electrolyte and BaCO 3, CeO 2, ZrO 2, Y 2O 3, ZnO, NiO, graphite for anode. The anode/electrolyte bi-layers were prepared by a simple multi-layer tape casting/co-firing method. The phase characterizations and microstructures were studied by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The anode-electrolyte bi-layers were sintered at 1450 °C. The electrolytes were extremely dense with pure perovskite phase and the thickness was about 25 μm. The anodes were porous and no obvious reaction was found between NiO and BCZYZ. With LaSr 3Co 1.5Fe 1.5O 10- δ (LSCF)/BCZYZ as cathode, the open current voltage and maximum power density respectively, reached 1.00 V and 247 mW cm -2 at 650 °C.

  1. Thin Film?

    NASA Astrophysics Data System (ADS)

    Kariper, İ. Afşin

    2014-09-01

    This study focuses on the critical surface tension of lead sulfite (PbSO3) crystalline thin film produced with chemical bath deposition on substrates (commercial glass).The PbSO3 thin films were deposited at room temperature at different deposition times. The structural properties of the films were defined and examined according to X-ray diffraction (XRD) and the XRD results such as dislocation density, average grain size, and no. of crystallites per unit area. Atomic force microscopy was used to measure the film thickness and the surface properties. The critical surface tension of the PbSO3 thin films was measured with an optical tensiometer instrument and calculated using the Zisman method. The results indicated that the critical surface tension of films changed in accordance with the average grain size and film thickness. The film thickness increased with deposition time and was inversely correlated with surface tension. The average grain size increased according to deposition time and was inversely correlated with surface tension.

  2. NdBaCo2/3Fe2/3Cu2/3O5+δ double perovskite as a novel cathode material for CeO2- and LaGaO3-based solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Jin, Fangjun; Li, Lei; He, Tianmin

    2015-01-01

    Double perovskites LnBaCo2O5+δ (Ln = rare earth) are explored as cathode materials for intermediate-temperature solid oxide fuel cell. Barriers to the applicability of double perovskite cathodes include high thermal expansion coefficient (TEC) and poor chemical compatibility with common electrolytes. In this paper, we report the characteristics and applicability of a double perovskite NdBaCo2/3Fe2/3Cu2/3O5+δ (NBCFC) cathode on CeO2- and LaGaO3-based electrolytes. NBCFC is found to crystallize in a tetragonal structure. Partial substitution of Fe and Cu for cobalt in NBCFC demonstrates significantly decreased TEC and good chemical compatibility with both Gd0.1Ce0.9O1.95 (GDC) and La0.9Sr0.1Ga0.8Mg0.2O3-δ (LSGM) electrolytes, while maintaining its good electrochemical performance. The oxidation states of transition metal cations are Co3+/Co4+, Fe3+/Fe4+, and Cu+/Cu2+, respectively. The average TEC of NBCFC is 15.7 × 10-6 K-1 between 30 and 850 °C, and the polarization resistance values are 0.056 and 0.023 Ω cm2 at 800 °C with GDC and LSGM electrolytes, respectively. The absence of spin-state transition in copper contributes to the TEC reduction. Addition of appropriate amounts of GDC into NBCFC to form NBCFC-GDC composite cathodes further reduce the TEC and improve cathode performance. These results can be used to improve and develop novel double perovskite cathode materials.

  3. Adsorption and Reaction of Acetone over CeOx(111) Thin Films

    SciTech Connect

    Senanayake, S.; Gordon, W; Overbury, S; Mullins, D

    2009-01-01

    This study reports the interaction of acetone (CH{sub 3}COCH{sub 3}), the simplest ketone, with well ordered CeO2(111) thin film surfaces. The fully oxidized CeO{sub 2}(111) surface shows a weak interaction with acetone with the sole desorption product (TPD) being acetone at 210 K. The chemisorbed molecule binds to the surface as the 1-acetone species rather than through a bridge-bonded dioxy-configuration. Exposure of a CeO{sub 2}(111) surface to acetone at 600K removes oxygen as CO and results in the conversion of Ce{sup 4+} to Ce{sup 3+}. Acetone chemisorbs strongly on reduced CeO{sub 2-x}(111) with molecular acetone desorbing near 500 K. Decomposition also occurs with H{sub 2} desorbing between 450 and 600 K and C reacting with O in the ceria to desorb above 650 K. A stable species exists from 200 to 500 K on the reduced surface that has three unique types of C. High resolution C 1s XPS spectra indicate these are Ce-CH{sub 2}, C-CH{sub 3} and C-O species. C k-edge NEXAFS indicates the presence of C{double_bond}C and C{double_bond}O bonds. It is postulated that the intermediate is a carbanion bonded through both O and C atoms to Ce cations.

  4. Effect of inductors to mitigate the hot-spot problem in parallel-connected superconducting thin-film fault current limiting elements

    NASA Astrophysics Data System (ADS)

    Yamasaki, H.; Furuse, M.; Kaiho, K.

    2015-06-01

    We have been developing superconducting thin-film fault current limiter (FCL) elements, in which high-resistivity Au-Ag alloy shunt layers are used to protect YBa2Cu3O7 (YBCO) thin films deposited on CeO2-buffered sapphire substrates. The high resistance of the thin films enables the element to withstand high electric fields of more than 40 Vpeak cm-1 during the current-limiting period after quenching, thus greatly reducing the amount of YBCO thin film needed and, consequently, the cost of an FCL. We have succeeded in fabricating and testing 500 V/200 A FCL modules using two 20 cm long YBCO films connected in parallel. In the present study, we performed extensive switching experiments on FCL elements, in which two YBCO films are connected in parallel to achieve higher rated currents, and confirmed the previously observed phenomenon that the hot-spot problem causing film damage just after quench initiation becomes more severe when the total critical current of the thin films is higher. We have investigated the origin of this phenomenon and found that a rapid current transfer from the first-quenched film with lower critical current to the other film causes higher current in the secondly-quenched film that sometimes leads to hot spots. It is demonstrated that the serious hot-spot problem can be mitigated by the use of inductors when the high-resistance FCL elements are connected in parallel. Based on these findings we propose an appropriate architecture of a high electric-field superconducting thin-film FCL that can be used in a real power grid.

  5. Nonlinear behavior of thin film SrTiO3 capacitors at microwave frequencies

    NASA Astrophysics Data System (ADS)

    Kozyrev, A. B.; Samoilova, T. B.; Golovkov, A. A.; Hollmann, E. K.; Kalinikos, D. A.; Loginov, V. E.; Prudan, A. M.; Soldatenkov, O. I.; Galt, D.; Mueller, C. H.; Rivkin, T. V.; Koepf, G. A.

    1998-09-01

    The voltage-dependent dielectric constant (ɛ) of SrTiO3 (STO) thin films is the basis for developing cryogenic capacitors for tunable microwave applications. In this study, the effect of microwave signal level on nonlinear response at 1.7-1.9 GHz was examined by measuring the level of the third order intermodulation distortion (IMD) signal relative to the input signal level. Small signal dielectric properties such as capacitance, tuning, and loss (tan δ) were also measured at 1 MHz, 3 GHz, and 10 GHz, at temperatures from 4.2 to 300 K. Planar capacitors were comprised of highly (100)-oriented, 1 μm thick STO films deposited via magnetron sputtering onto CeO2-buffered (11_02)-oriented sapphire substrates, with 10 μm gaps between the electrodes. Deviations from the anticipated cubic dependence of the third order IMD product on incident power, for incident power ranges from -10 to 22 dBm, were attributed to conductivity nonlinearity. At incident power levels of 22 dBm and with no dc bias applied to the capacitor, the level of the third order IMD product was 21 dB below the fundamental signal level. Application of a 107 V/m dc electric field bias across the capacitor suppressed the third order IMD by an additional 10 dB. The nonlinear properties of thin film STO capacitors as a function of microwave voltage were determined by comparing the experimental and theoretical dependencies of the IMD products.

  6. Pyrolyzed thin film carbon

    NASA Technical Reports Server (NTRS)

    Tai, Yu-Chong (Inventor); Liger, Matthieu (Inventor); Harder, Theodore (Inventor); Konishi, Satoshi (Inventor); Miserendino, Scott (Inventor)

    2010-01-01

    A method of making carbon thin films comprises depositing a catalyst on a substrate, depositing a hydrocarbon in contact with the catalyst and pyrolyzing the hydrocarbon. A method of controlling a carbon thin film density comprises etching a cavity into a substrate, depositing a hydrocarbon into the cavity, and pyrolyzing the hydrocarbon while in the cavity to form a carbon thin film. Controlling a carbon thin film density is achieved by changing the volume of the cavity. Methods of making carbon containing patterned structures are also provided. Carbon thin films and carbon containing patterned structures can be used in NEMS, MEMS, liquid chromatography, and sensor devices.

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

    SciTech Connect

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

    2006-01-01

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

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

    NASA Astrophysics Data System (ADS)

    Edleman, Nikki Lynn

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

  9. Plasmonic Based Sensing Using an Array of Au-Metal Oxide Thin Films

    SciTech Connect

    Joy, N.; Rogers, Phillip H.; Nandasiri, Manjula I.; Thevuthasan, Suntharampillai; Carpenter, Michael A.

    2012-12-04

    An optical plasmonic-based sensing array has been developed and tested for the selective and sensitive detection of H2, CO, and NO2 at a temperature of 500°C in an oxygen-containing background. The three element sensing array used Au nanoparticles embedded in separate thin films of yttria stabilized zirconia (YSZ), CeO2, and TiO2. A peak in the absorbance spectrum due to a localized surface plasmon resonance (LSPR) on the Au nanoparticles was monitored for each film during gas exposures and showed a blue shift in the peak positions for the reducing gases, H2 and CO, and a red shift for the oxidizing gas NO2. A more in-depth look at the sensing response was performed using the multivariate methods of principal component analysis (PCA) analysis and linear discriminant analysis (LDA) on data from across the entire absorbance spectrum range. Qualitative results from both methods showed good separation between the three analytes for both the full array and the Au-TiO2 sample. Quantification of LDA cluster separation using the Mahalanobis distance showed better cluster separation for the array, but there were some instances with the lowest concentrations where the single Au-TiO2 film had better separation than the array. A second method to quantify cluster separation in LDA space was developed using multidimensional volume analysis of the individual cluster volume, overlapped cluster volume and empty volume between clusters. Compared to the individual sensing elements, the array showed less cluster overlap, smaller cluster volumes, and more space between clusters, all of which were expected for improved separability between the analytes.

  10. Thin film hydrogen sensor

    DOEpatents

    Cheng, Y.T.; Poli, A.A.; Meltser, M.A.

    1999-03-23

    A thin film hydrogen sensor includes a substantially flat ceramic substrate with first and second planar sides and a first substrate end opposite a second substrate end; a thin film temperature responsive resistor on the first planar side of the substrate proximate to the first substrate end; a thin film hydrogen responsive metal resistor on the first planar side of the substrate proximate to the fist substrate end and proximate to the temperature responsive resistor; and a heater on the second planar side of the substrate proximate to the first end. 5 figs.

  11. Premelting of thin wires

    NASA Astrophysics Data System (ADS)

    Gülseren, O.; Ercolessi, F.; Tosatti, E.

    1995-03-01

    We have investigated the melting behavior of thin lead wires using molecular dynamics. We find that-in analogy with cluster melting-the melting temperature Tm(R) of a wire with radius R is lower than that of a bulk solid Tbm by Tm(R)=Tbm-c/R. Surface melting effects, with formation of a thin skin of highly diffusive atoms at the wire surface, are observed. The diffusivity is lower over (111)-oriented faces, and higher at (110) and (100) rounded areas. The possible relevance to recent results on nonrupturing thin necks between a scanning tunnel microscope tip and a warm surface is addressed.

  12. Thin film hydrogen sensor

    DOEpatents

    Cheng, Yang-Tse; Poli, Andrea A.; Meltser, Mark Alexander

    1999-01-01

    A thin film hydrogen sensor, includes: a substantially flat ceramic substrate with first and second planar sides and a first substrate end opposite a second substrate end; a thin film temperature responsive resistor on the first planar side of the substrate proximate to the first substrate end; a thin film hydrogen responsive metal resistor on the first planar side of the substrate proximate to the fist substrate end and proximate to the temperature responsive resistor; and a heater on the second planar side of the substrate proximate to the first end.

  13. Electrochemical thinning of silicon

    DOEpatents

    Medernach, John W.

    1994-01-01

    Porous semiconducting material, e.g. silicon, is formed by electrochemical treatment of a specimen in hydrofluoric acid, using the specimen as anode. Before the treatment, the specimen can be masked. The porous material is then etched with a caustic solution or is oxidized, depending of the kind of structure desired, e.g. a thinned specimen, a specimen, a patterned thinned specimen, a specimen with insulated electrical conduits, and so on. Thinned silicon specimen can be subjected to tests, such as measurement of interstitial oxygen by Fourier transform infra-red spectroscopy (FTIR).

  14. Electrochemical thinning of silicon

    DOEpatents

    Medernach, J.W.

    1994-01-11

    Porous semiconducting material, e.g. silicon, is formed by electrochemical treatment of a specimen in hydrofluoric acid, using the specimen as anode. Before the treatment, the specimen can be masked. The porous material is then etched with a caustic solution or is oxidized, depending of the kind of structure desired, e.g. a thinned specimen, a specimen, a patterned thinned specimen, a specimen with insulated electrical conduits, and so on. Thinned silicon specimen can be subjected to tests, such as measurement of interstitial oxygen by Fourier transform infra-red spectroscopy (FTIR). 14 figures.

  15. Biomimetic thin film synthesis

    SciTech Connect

    Graff, G.L.; Campbell, A.A.; Gordon, N.R.

    1995-05-01

    The purpose of this program is to develop a new process for forming thin film coatings and to demonstrate that the biomimetic thin film technology developed at PNL is useful for industrial applications. In the biomimetic process, mineral deposition from aqueous solution is controlled by organic functional groups attached to the underlying substrate surface. The coatings process is simple, benign, inexpensive, energy efficient, and particularly suited for temperature sensitive substrate materials (such as polymers). In addition, biomimetic thin films can be deposited uniformly on complex shaped and porous substrates providing a unique capability over more traditional line-of-sight methods.

  16. Ceramic Composite Thin Films

    NASA Technical Reports Server (NTRS)

    Ruoff, Rodney S. (Inventor); Stankovich, Sasha (Inventor); Dikin, Dmitriy A. (Inventor); Nguyen, SonBinh T. (Inventor)

    2013-01-01

    A ceramic composite thin film or layer includes individual graphene oxide and/or electrically conductive graphene sheets dispersed in a ceramic (e.g. silica) matrix. The thin film or layer can be electrically conductive film or layer depending the amount of graphene sheets present. The composite films or layers are transparent, chemically inert and compatible with both glass and hydrophilic SiOx/silicon substrates. The composite film or layer can be produced by making a suspension of graphene oxide sheet fragments, introducing a silica-precursor or silica to the suspension to form a sol, depositing the sol on a substrate as thin film or layer, at least partially reducing the graphene oxide sheets to conductive graphene sheets, and thermally consolidating the thin film or layer to form a silica matrix in which the graphene oxide and/or graphene sheets are dispersed.

  17. Super Thin Ceramic Coatings

    NASA Video Gallery

    New technology being developed at NASA's Glenn Research Center creates super thin ceramic coatings on engine components. The Plasma Spray – Physical Vapor Deposition (PS-PVD) rig uses a powerful ...

  18. Thin silicon solar cells

    NASA Astrophysics Data System (ADS)

    Hall, R. B.; Bacon, C.; Direda, V.; Ford, D. H.; Ingram, A. E.; Cotter, J.; Hughes-Lampros, T.; Rand, J. A.; Ruffins, T. R.; Barnett, A. M.

    1992-12-01

    The silicon-film design achieves high performance by using a dun silicon layer and incorporating light trapping. Optimally designed thin crystalline solar cells (less than 50 microns thick) have performance advantages over conventional thick devices. The high-performance silicon-film design employs a metallurgical barrier between the low-cost substrate and the thin silicon layer. Light trapping properties of silicon-film on ceramic solar cells are presented and analyzed. Recent advances in process development are described here.

  19. Multifunctional thin film surface

    DOEpatents

    Brozik, Susan M.; Harper, Jason C.; Polsky, Ronen; Wheeler, David R.; Arango, Dulce C.; Dirk, Shawn M.

    2015-10-13

    A thin film with multiple binding functionality can be prepared on an electrode surface via consecutive electroreduction of two or more aryl-onium salts with different functional groups. This versatile and simple method for forming multifunctional surfaces provides an effective means for immobilization of diverse molecules at close proximities. The multifunctional thin film has applications in bioelectronics, molecular electronics, clinical diagnostics, and chemical and biological sensing.

  20. Thin silicon solar cells

    SciTech Connect

    Hall, R.B.; Bacon, C.; DiReda, V.; Ford, D.H.; Ingram, A.E.; Cotter, J.; Hughes-Lampros, T.; Rand, J.A.; Ruffins, T.R.; Barnett, A.M.

    1992-12-01

    The silicon-film design achieves high performance by using a dun silicon layer and incorporating light trapping. Optimally designed thin crystalline solar cells (<50 microns thick) have performance advantages over conventional thick devices. The high-performance silicon-film design employs a metallurgical barrier between the low-cost substrate and the thin silicon layer. Light trapping properties of silicon-film on ceramic solar cells are presented and analyzed. Recent advances in process development are described here.

  1. A Model Approach to Flux-Pinning Properties of YBa2Cu 3O7-delta Thin Film Vortex States via Non-Superconducting Impurities

    NASA Astrophysics Data System (ADS)

    Gamble, Ronald S., Jr.

    Thin film YBa2Cu3O7--delta (YBCO) samples with added non-superconducting nanodot defects of CeO 2 and BaSnO2 are the focus of recent high-temperature superconductor studies. These nanodots allow magnetic flux to penetrate at these sites of the superconducting lattice thus creating a magnetic flux vortex state. Examining the structure shows that these quantized magnetic flux vortices arrange themselves in a self-assembled lattice. The nanodots, with non-superconducting properties, serve to present structural properties to restrict motion of these vorticies under a pinning-force and to enhance the critical current density. A formulation of a new model for the system by a variation in the electron pair velocity via the virtual work from the nanodot defects in accordance to the well-known Superconductivity theories is tested. A solution to the expression for the magnetic flux, zero net force and pair velocity will generate a setting for the optimal deposition parameters of number density, growth geometry and mass density of these nanodot structures. With a calculation of pair velocities from a similar work, a comparison is made between experimental and theoretical velocity calculations using growth geometry and chemical potential. This will yield insight into how the current density for a doped high-temperature superconductor will be modified and tuned based on the dynamics and density of the nanodots themselves.

  2. CeO2 and CuOx Interactions and the Controlled Assembly of CeO2(111) and CeO2(100) Nanoparticles on an Oxidized Cu(111)Substrate

    SciTech Connect

    Rodriguez J. A.; Yang F.; Choi Y.M.; Agnoli S.; Liu P.; Stacchiola D.; Hrbek J.

    2011-11-24

    The catalytic performance of ceria-based heterogeneous catalysts in many chemical transformations (water-gas shift reaction, CO oxidation, alcohol synthesis from CO/CO{sub 2} hydrogenation, etc.) is affected by the surface structure of the ceria. To control the performance of ceria-containing inverse catalysts, we devised a method to grow ceria nanoparticles (NPs) exposing exclusively either (111) or (100) surfaces and characterized their surface structures by scanning tunneling microscopy. When cerium is vapor-deposited on Cu(111) in a background of molecular O{sub 2}, only CeO{sub 2}(111) NPs grow. However, if the surface of Cu(111) is preoxidized with O{sub 2} or NO{sub 2} to form a rectangular copper oxide phase, probably Cu{sub 4}O{sub 3}(001), CeO{sub 2}(100) NPs grow on the oxide template instead. These experimental findings are interpreted using results of density functional calculations. The (100) surface of bulk ceria reconstructs to preserve charge neutrality. This is not necessary for CeO{sub 2}(100) NPs grown on Cu{sub 4}O{sub 3}(001), where the topmost oxygen layer of Cu{sub 4}O{sub 3} is shared with the interfacial layer of cerium. After the CeO{sub 2}(100)/CuO{sub x}/Cu(111) surfaces were exposed to CO, the copper oxide was reduced but the shape of the CeO{sub 2}(100) NPs remained intact. This opens the door for diverse applications in catalysis.

  3. Lithospheric and crustal thinning

    NASA Technical Reports Server (NTRS)

    Moretti, I.

    1985-01-01

    In rift zones, both the crust and the lithosphere get thinner. The amplitude and the mechanism of these two thinning situations are different. The lithospheric thinning is a thermal phenomenon produced by an asthenospherical uprising under the rift zone. In some regions its amplitude can exceed 200%. This is observed under the Baikal rift where the crust is directly underlaid by the mantellic asthenosphere. The presence of hot material under rift zones induces a large negative gravity anomaly. A low seismic velocity zone linked to this thermal anomaly is also observed. During the rifting, the magmatic chambers get progressively closer from the ground surface. Simultaneously, the Moho reflector is found at shallow depth under rift zones. This crustal thinning does not exceed 50%. Tectonic stresses and vertical movements result from the two competing effects of the lithospheric and crustal thinning. On the one hand, the deep thermal anomaly induces a large doming and is associated with extensive deviatoric stresses. On the other hand, the crustal thinning involves the formation of a central valley. This subsidence is increased by the sediment loading. The purpose here is to quantify these two phenomena in order to explain the morphological and thermal evolution of rift zones.

  4. Thin film photovoltaics

    SciTech Connect

    Zweibel, K; Ullal, H S

    1989-05-01

    Thin films are considered a potentially attractive technological approach to making cost-effective electricity by photovoltaics. Over the last twenty years, many have been investigated and some (cadmium telluride, copper indium diselenide, amorphous silicon) have become leading candidates for future large-scale commercialization. This paper surveys the past development of these key thin films and gives their status and future prospects. In all cases, significant progress toward cost-effective PV electricity has been made. If this progress continues, it appears that thin film PV could provide electricity that is competitive for summer daytime peaking power requirements by the middle of the 1990s; and electricity in a range that is competitive with fossil fuel costs (i.e., 6 cents/kilowatt-hour) should be available from PV around the turn of the century. 22 refs., 9 figs.

  5. Thin film temperature sensor

    NASA Technical Reports Server (NTRS)

    Grant, H. P.; Przybyszewski, J. S.

    1980-01-01

    Thin film surface temperature sensors were developed. The sensors were made of platinum-platinum/10 percent rhodium thermocouples with associated thin film-to-lead wire connections and sputtered on aluminum oxide coated simulated turbine blades for testing. Tests included exposure to vibration, low velocity hydrocarbon hot gas flow to 1250 K, and furnace calibrations. Thermal electromotive force was typically two percent below standard type S thermocouples. Mean time to failure was 42 hours at a hot gas flow temperature of 1250 K and an average of 15 cycles to room temperature. Failures were mainly due to separation of the platinum thin film from the aluminum oxide surface. Several techniques to improve the adhesion of the platinum are discussed.

  6. Thin film ceramic thermocouples

    NASA Technical Reports Server (NTRS)

    Gregory, Otto (Inventor); Fralick, Gustave (Inventor); Wrbanek, John (Inventor); You, Tao (Inventor)

    2011-01-01

    A thin film ceramic thermocouple (10) having two ceramic thermocouple (12, 14) that are in contact with each other in at least on point to form a junction, and wherein each element was prepared in a different oxygen/nitrogen/argon plasma. Since each element is prepared under different plasma conditions, they have different electrical conductivity and different charge carrier concentration. The thin film thermocouple (10) can be transparent. A versatile ceramic sensor system having an RTD heat flux sensor can be combined with a thermocouple and a strain sensor to yield a multifunctional ceramic sensor array. The transparent ceramic temperature sensor that could ultimately be used for calibration of optical sensors.

  7. Thin film photovoltaic device

    DOEpatents

    Catalano, Anthony W.; Bhushan, Manjul

    1982-01-01

    A thin film photovoltaic solar cell which utilizes a zinc phosphide semiconductor is of the homojunction type comprising an n-type conductivity region forming an electrical junction with a p-type region, both regions consisting essentially of the same semiconductor material. The n-type region is formed by treating zinc phosphide with an extrinsic dopant such as magnesium. The semiconductor is formed on a multilayer substrate which acts as an opaque contact. Various transparent contacts may be used, including a thin metal film of the same chemical composition as the n-type dopant or conductive oxides or metal grids.

  8. Shear Thinning in Xenon

    NASA Technical Reports Server (NTRS)

    Bergm Robert F.; Moldover, Michael R.; Yao, Minwu; Zimmerli, Gregory A.

    2009-01-01

    We measured shear thinning, a viscosity decrease ordinarily associated with complex liquids such as molten plastics or ketchup, near the critical point of xenon. The data span a wide range of dimensionless shear rate: the product of the shear rate and the relaxation time of critical fluctuations was greater than 0.001 and was less than 700. As predicted by theory, shear thinning occurred when this product was greater than 1. The measurements were conducted aboard the Space Shuttle Columbia to avoid the density stratification caused by Earth's gravity.

  9. Thin-film optical initiator

    DOEpatents

    Erickson, Kenneth L.

    2001-01-01

    A thin-film optical initiator having an inert, transparent substrate, a reactive thin film, which can be either an explosive or a pyrotechnic, and a reflective thin film. The resultant thin-film optical initiator system also comprises a fiber-optic cable connected to a low-energy laser source, an output charge, and an initiator housing. The reactive thin film, which may contain very thin embedded layers or be a co-deposit of a light-absorbing material such as carbon, absorbs the incident laser light, is volumetrically heated, and explodes against the output charge, imparting about 5 to 20 times more energy than in the incident laser pulse.

  10. Thin-film coatings

    NASA Technical Reports Server (NTRS)

    Buckley, D. H.

    1980-01-01

    Thin, adherent, high density films are discussed with respect to their application in two plasma physics techniques (ion plating and sputtering). The operation of each technique is described as well as what surfaces can be coated, and what kind of materials can be applied. The effects of these films on the mechanical properties of solid surfaces are also discussed.

  11. Thin Lens Ray Tracing.

    ERIC Educational Resources Information Center

    Gatland, Ian R.

    2002-01-01

    Proposes a ray tracing approach to thin lens analysis based on a vector form of Snell's law for paraxial rays as an alternative to the usual approach in introductory physics courses. The ray tracing approach accommodates skew rays and thus provides a complete analysis. (Author/KHR)

  12. Treading on Thin Water.

    ERIC Educational Resources Information Center

    Haley, Richard D.

    1985-01-01

    Provides a simple introduction to animals whose habitat is the thin surface film of water. Describes adaptive mechanisms of water striders, whirlygigs and riffle bugs and suggests ways to observe them in the wild or as aquarium animals. Includes basic demonstrations of the nature of surface tension. (JHZ)

  13. Thin film photovoltaic cell

    DOEpatents

    Meakin, John D.; Bragagnolo, Julio

    1982-01-01

    A thin film photovoltaic cell having a transparent electrical contact and an opaque electrical contact with a pair of semiconductors therebetween includes utilizing one of the electrical contacts as a substrate and wherein the inner surface thereof is modified by microroughening while being macro-planar.

  14. Epitaxial thin films

    DOEpatents

    Hunt, Andrew Tye; Deshpande, Girish; Lin, Wen-Yi; Jan, Tzyy-Jiuan

    2006-04-25

    Epitatial thin films for use as buffer layers for high temperature superconductors, electrolytes in solid oxide fuel cells (SOFC), gas separation membranes or dielectric material in electronic devices, are disclosed. By using CCVD, CACVD or any other suitable deposition process, epitaxial films having pore-free, ideal grain boundaries, and dense structure can be formed. Several different types of materials are disclosed for use as buffer layers in high temperature superconductors. In addition, the use of epitaxial thin films for electrolytes and electrode formation in SOFCs results in densification for pore-free and ideal gain boundary/interface microstructure. Gas separation membranes for the production of oxygen and hydrogen are also disclosed. These semipermeable membranes are formed by high-quality, dense, gas-tight, pinhole free sub-micro scale layers of mixed-conducting oxides on porous ceramic substrates. Epitaxial thin films as dielectric material in capacitors are also taught herein. Capacitors are utilized according to their capacitance values which are dependent on their physical structure and dielectric permittivity. The epitaxial thin films of the current invention form low-loss dielectric layers with extremely high permittivity. This high permittivity allows for the formation of capacitors that can have their capacitance adjusted by applying a DC bias between their electrodes.

  15. Thin Wall Iron Castings

    SciTech Connect

    J.F. Cuttino; D.M. Stefanescu; T.S. Piwonka

    2001-10-31

    Results of an investigation made to develop methods of making iron castings having wall thicknesses as small as 2.5 mm in green sand molds are presented. It was found that thin wall ductile and compacted graphite iron castings can be made and have properties consistent with heavier castings. Green sand molding variables that affect casting dimensions were also identified.

  16. 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.

  17. Thin films for material engineering

    NASA Astrophysics Data System (ADS)

    Wasa, Kiyotaka

    2016-07-01

    Thin films are defined as two-dimensional materials formed by condensing one by one atomic/molecular/ionic species of matter in contrast to bulk three-dimensional sintered ceramics. They are grown through atomic collisional chemical reaction on a substrate surface. Thin film growth processes are fascinating for developing innovative exotic materials. On the basis of my long research on sputtering deposition, this paper firstly describes the kinetic energy effect of sputtered adatoms on thin film growth and discusses on a possibility of room-temperature growth of cubic diamond crystallites and the perovskite thin films of binary compound PbTiO3. Secondly, high-performance sputtered ferroelectric thin films with extraordinary excellent crystallinity compatible with MBE deposited thin films are described in relation to a possible application for thin-film MEMS. Finally, the present thin-film technologies are discussed in terms of a future material science and engineering.

  18. Modern Thin-Layer Chromatography.

    ERIC Educational Resources Information Center

    Poole, Colin F.; Poole, Salwa K.

    1989-01-01

    Some of the important modern developments of thin-layer chromatography are introduced. Discussed are the theory and instrumentation of thin-layer chromatography including multidimensional and multimodal techniques. Lists 53 references. (CW)

  19. Thin film solar cell workshop

    NASA Technical Reports Server (NTRS)

    Armstrong, Joe; Jeffrey, Frank

    1993-01-01

    A summation of responses to questions posed to the thin-film solar cell workshop and the ensuing discussion is provided. Participants in the workshop included photovoltaic manufacturers (both thin film and crystalline), cell performance investigators, and consumers.

  20. NMR characterization of thin films

    DOEpatents

    Gerald II, Rex E.; Klingler, Robert J.; Rathke, Jerome W.; Diaz, Rocio; Vukovic, Lela

    2010-06-15

    A method, apparatus, and system for characterizing thin film materials. The method, apparatus, and system includes a container for receiving a starting material, applying a gravitational force, a magnetic force, and an electric force or combinations thereof to at least the starting material, forming a thin film material, sensing an NMR signal from the thin film material and analyzing the NMR signal to characterize the thin film of material.

  1. NMR characterization of thin films

    DOEpatents

    Gerald, II, Rex E.; Klingler, Robert J.; Rathke, Jerome W.; Diaz, Rocio; Vukovic, Lela

    2008-11-25

    A method, apparatus, and system for characterizing thin film materials. The method, apparatus, and system includes a container for receiving a starting material, applying a gravitational force, a magnetic force, and an electric force or combinations thereof to at least the starting material, forming a thin film material, sensing an NMR signal from the thin film material and analyzing the NMR signal to characterize the thin film of material.

  2. [Spectral emissivity of thin films].

    PubMed

    Zhong, D

    2001-02-01

    In this paper, the contribution of multiple reflections in thin film to the spectral emissivity of thin films of low absorption is discussed. The expression of emissivity of thin films derived here is related to the thin film thickness d and the optical constants n(lambda) and k(lambda). It is shown that in the special case d-->infinity the emissivity of thin films is equivalent to that of the bulk material. Realistic numerical and more precise general numerical results for the dependence of the emissivity on d, n(lambda) and k(lambda) are given.

  3. Biomimetic thin film deposition

    SciTech Connect

    Rieke, P.R.; Graff, G.E.; Campbell, A.A.; Bunker, B.C.; Baskaran, S.; Song, L.; Tarasevich, B.J.; Fryxell, G.E.

    1995-09-01

    Biological mineral deposition for the formation of bone, mollusk shell and other hard tissues provides materials scientists with illustrative materials processing strategies. This presentation will review the key features of biomineralization and how these features can be of technical importance. We have adapted existing knowledge of biomineralization to develop a unique method of depositing inorganic thin films and coating. Our approach to thin film deposition is to modify substrate surfaces to imitate the proteins found in nature that are responsible for controlling mineral deposition. These biomimetic surfaces control the nucleation and growth of the mineral from a supersaturated aqueous solution. This has many processing advantages including simple processing equipment, environmentally benign reagents, uniform coating of highly complex shapes, and enhanced adherence of coating. Many different types of metal oxide, hydroxide, sulfide and phosphate materials with useful mechanical, optical, electronic and biomedical properties can be deposited.

  4. Shear-thinning Fluid

    NASA Technical Reports Server (NTRS)

    2001-01-01

    Whipped cream and the filling for pumpkin pie are two familiar materials that exhibit the shear-thinning effect seen in a range of industrial applications. It is thick enough to stand on its own atop a piece of pie, yet flows readily when pushed through a tube. This demonstrates the shear-thinning effect that was studied with the Critical Viscosity of Xenon Experiment (CVX-2) on the STS-107 Research 1 mission in 2002. CVX observed the behavior of xenon, a heavy inert gas used in flash lamps and ion rocket engines, at its critical point. The principal investigator was Dr. Robert Berg of the National Institutes of Standards and Technology in Gaithersburg, MD.

  5. Advanced thin film thermocouples

    NASA Technical Reports Server (NTRS)

    Kreider, K. G.; Semancik, S.; Olson, C.

    1984-01-01

    The fabrication, materials characterization, and performance of thin film platinum rhodium thermocouples on gas turbine alloys was investigated. The materials chosen for the study were the turbine blade alloy systems MAR M200+Hf with NiCoCrAlY and FeCrAlY coatings, and vane alloy systems MAR M509 with FeCrAlY. Research was focussed on making improvements in the problem areas of coating substrate stability, adhesion, and insulation reliability and durability. Diffusion profiles between the substrate and coating with and without barrier coatings of Al2O3 are reported. The relationships between fabrication parameters of thermal oxidation and sputtering of the insulator and its characterization and performance are described. The best thin film thermocouples were fabricated with the NiCoCrAlY coatings which were thermally oxidized and sputter coated with Al2O3.

  6. Thin, Lightweight Solar Cell

    NASA Technical Reports Server (NTRS)

    Brandhorst, Henry W., Jr.; Weinberg, Irving

    1991-01-01

    Improved design for thin, lightweight solar photovoltaic cells with front contacts reduces degradation of electrical output under exposure to energetic charged particles (protons and electrons). Increases ability of cells to maintain structural integrity under exposure to ultraviolet radiation by eliminating ultraviolet-degradable adhesives used to retain cover glasses. Interdigitated front contacts and front junctions formed on semiconductor substrate. Mating contacts formed on back surface of cover glass. Cover glass and substrate electrostatically bonded together.

  7. Ultra-Thin, Flexible Electronics

    NASA Technical Reports Server (NTRS)

    Holland, Brian; McPherson, Ryan; Zhang, Tan; Hou, Zhenwei; Dean, Robert; Johnson, R. Wayne; DelCastillo, Linda; Moussessian, Alina

    2008-01-01

    Thinned die can be used to realize ultra-thin flexible electronics for applications such as conformal and wearable electronics. Three techniques have been developed to achieve this goal using thinned die: die flip chip bonded onto flexible substrates, die laminated onto LCP films, and die embedded in polyimide. A key to achieving each of these techniques is the thinning of die to a thickness of 50 microns or thinner. Conventional CMP processing can be used to thin to 50 microns. At 50 microns, the active die become flexible and must be handled by temporarily bonding them to a holder die, for further processing. Once bonded face down to the holder die, the active die can be further thinned by DRIE etching the exposed backside. The thinned die can then been packaged in or on the flexible substrate.

  8. Thin film superconductor magnetic bearings

    DOEpatents

    Weinberger, Bernard R.

    1995-12-26

    A superconductor magnetic bearing includes a shaft (10) that is subject to a load (L) and rotatable around an axis of rotation, a magnet (12) mounted to the shaft, and a stator (14) in proximity to the shaft. The stator (14) has a superconductor thin film assembly (16) positioned to interact with the magnet (12) to produce a levitation force on the shaft (10) that supports the load (L). The thin film assembly (16) includes at least two superconductor thin films (18) and at least one substrate (20). Each thin film (18) is positioned on a substrate (20) and all the thin films are positioned such that an applied magnetic field from the magnet (12) passes through all the thin films. A similar bearing in which the thin film assembly (16) is mounted on the shaft (10) and the magnet (12) is part of the stator (14) also can be constructed.

  9. On the theory of thin and thin-walled rods

    NASA Technical Reports Server (NTRS)

    Dzhanelidze, G Y

    1951-01-01

    Through the work of V. Z. Vlasov a theory of thin-walled rods has been established that is widely applicable in practice. This theory was extended by A. A. Umanski to thin-walled rods of closed profile section. The authors based their work on the concepts of the modern theory of shells. An attempt is made herein to construct a theory of thin-walled rods including the classical theory of deformation of thin rods by making use of a kinematic assumption.

  10. Carbon thin film thermometry

    NASA Technical Reports Server (NTRS)

    Collier, R. S.; Sparks, L. L.; Strobridge, T. R.

    1973-01-01

    The work concerning carbon thin film thermometry is reported. Optimum film deposition parameters were sought on an empirical basis for maximum stability of the films. One hundred films were fabricated for use at the Marshall Space Flight Center; 10 of these films were given a precise quasi-continuous calibration of temperature vs. resistance with 22 intervals between 5 and 80 K using primary platinum and germanium thermometers. Sensitivity curves were established and the remaining 90 films were given a three point calibration and fitted to the established sensitivity curves. Hydrogen gas-liquid discrimination set points are given for each film.

  11. Thin film hydrogen sensor

    DOEpatents

    Lauf, Robert J.; Hoffheins, Barbara S.; Fleming, Pamela H.

    1994-01-01

    A hydrogen sensor element comprises an essentially inert, electrically-insulating substrate having a thin-film metallization deposited thereon which forms at least two resistors on the substrate. The metallization comprises a layer of Pd or a Pd alloy for sensing hydrogen and an underlying intermediate metal layer for providing enhanced adhesion of the metallization to the substrate. An essentially inert, electrically insulating, hydrogen impermeable passivation layer covers at least one of the resistors, and at least one of the resistors is left uncovered. The difference in electrical resistances of the covered resistor and the uncovered resistor is related to hydrogen concentration in a gas to which the sensor element is exposed.

  12. Method for thinning specimen

    DOEpatents

    Follstaedt, David M.; Moran, Michael P.

    2005-03-15

    A method for thinning (such as in grinding and polishing) a material surface using an instrument means for moving an article with a discontinuous surface with an abrasive material dispersed between the material surface and the discontinuous surface where the discontinuous surface of the moving article provides an efficient means for maintaining contact of the abrasive with the material surface. When used to dimple specimens for microscopy analysis, a wheel with a surface that has been modified to produce a uniform or random discontinuous surface significantly improves the speed of the dimpling process without loss of quality of finish.

  13. Thin film magnetism

    SciTech Connect

    Bader, S.D. )

    1990-06-01

    New developments in thin-film magnetism are reviewed with an emphasis on the ultrathin regime. The scope includes relatively simple metallic systems in overlayer, sandwich, and superlattice configurations. Sample fabrication, characterization, and magnetic measurement techniques are outlined by highlighting some of the more modern experimental innovations. Current issues and advances that demonstrate the symbiotic relationship between experiment and theory are then examined, including the surface magnetic anisotropy, the two-dimensional critical behavior, the creation of metastable phases via epitaxy, and phenomena associated with coupled magnetic layers. The review ends with a brief account of the impact of the various contemporary developments on the applications area.

  14. Polycrystalline thin film photovoltaic technology

    SciTech Connect

    Ullal, H.S.; Zweibel, K.; Mitchell, R.L.; Noufi, R.

    1991-03-01

    Low-cost, high-efficiency thin-film modules are an exciting photovoltaic technology option for generating cost-effective electricity in 1995 and beyond. In this paper we review the significant technical progress made in the following thin films: copper indium diselenide, cadmium telluride, and polycrystalline thin silicon films. Also, the recent US DOE/SERI initiative to commercialize these emerging technologies is discussed. 6 refs., 9 figs.

  15. Thin-Film Power Transformers

    NASA Technical Reports Server (NTRS)

    Katti, Romney R.

    1995-01-01

    Transformer core made of thin layers of insulating material interspersed with thin layers of ferromagnetic material. Flux-linking conductors made of thinner nonferromagnetic-conductor/insulator multilayers wrapped around core. Transformers have geometric features finer than those of transformers made in customary way by machining and mechanical pressing. In addition, some thin-film materials exhibit magnetic-flux-carrying capabilities superior to those of customary bulk transformer materials. Suitable for low-cost, high-yield mass production.

  16. Cortical thinning in psychopathy

    PubMed Central

    Ly, Martina; Motzkin, Julian C.; Philippi, Carissa L.; Kirk, Gregory R.; Newman, Joseph P.; Kiehl, Kent A.; Koenigs, Michael

    2013-01-01

    Objective Psychopathy is a personality disorder associated with severely antisocial behavior and a host of cognitive and affective deficits. The neuropathological basis of the disorder has not been clearly established. Cortical thickness is a sensitive measure of brain structure that has been used to identify neurobiological abnormalities in a number of psychiatric disorders. The purpose of this study is to evaluate cortical thickness and corresponding functional connectivity in criminal psychopaths. Method Using T1 MRI data, we computed cortical thickness maps in a sample of adult male prison inmates selected based on psychopathy diagnosis (n=21 psychopathic inmates, n=31 non-psychopathic inmates). Using rest-fMRI data from a subset of these inmates (n=20 psychopathic inmates, n=20 non-psychopathic inmates), we then computed functional connectivity within networks exhibiting significant thinning among psychopaths. Results Relative to non-psychopaths, psychopaths exhibited significantly thinner cortex in a number of regions, including left insula and dorsal anterior cingulate cortex, bilateral precentral gyrus, bilateral anterior temporal cortex, and right inferior frontal gyrus. These neurostructural differences were not due to differences in age, IQ, or substance abuse. Psychopaths also exhibited a corresponding reduction in functional connectivity between left insula and left dorsal anterior cingulate cortex. Conclusions Psychopathy is associated with a distinct pattern of cortical thinning and reduced functional connectivity. PMID:22581200

  17. Thin film mechanics

    NASA Astrophysics Data System (ADS)

    Cooper, Ryan C.

    This doctoral thesis details the methods of determining mechanical properties of two classes of novel thin films suspended two-dimensional crystals and electron beam irradiated microfilms of polydimethylsiloxane (PDMS). Thin films are used in a variety of surface coatings to alter the opto-electronic properties or increase the wear or corrosion resistance and are ideal for micro- and nanoelectromechanical system fabrication. One of the challenges in fabricating thin films is the introduction of strains which can arise due to application techniques, geometrical conformation, or other spurious conditions. Chapters 2-4 focus on two dimensional materials. This is the intrinsic limit of thin films-being constrained to one atomic or molecular unit of thickness. These materials have mechanical, electrical, and optical properties ideal for micro- and nanoelectromechanical systems with truly novel device functionality. As such, the breadth of applications that can benefit from a treatise on two dimensional film mechanics is reason enough for exploration. This study explores the anomylously high strength of two dimensional materials. Furthermore, this work also aims to bridge four main gaps in the understanding of material science: bridging the gap between ab initio calculations and finite element analysis, bridging the gap between ab initio calculations and experimental results, nanoscale to microscale, and microscale to mesoscale. A nonlinear elasticity model is used to determine the necessary elastic constants to define the strain-energy density function for finite strain. Then, ab initio calculations-density functional theory-is used to calculate the nonlinear elastic response. Chapter 2 focuses on validating this methodology with atomic force microscope nanoindentation on molybdenum disulfide. Chapter 3 explores the convergence criteria of three density functional theory solvers to further verify the numerical calculations. Chapter 4 then uses this model to investigate

  18. Plasmonic-Based High Temperature Chemical Sensing Using Gold Nanoparticles Embedded in Metal Oxide Thin Films

    NASA Astrophysics Data System (ADS)

    Joy, Nicholas

    Thin metal oxide films embedded with Au nanoparticles (AuNPs) have been investigated as high temperature localized surface plasmon resonance (LSPR) based sensing materials to monitor H2, CO, and NO2 at a temperature of 500°C. Applications for this technology include turbine engines as well as other combustion environments where it is important to monitor emission gases for both regulatory purposes as well as combustion control. These high temperature applications, which may be oxidizing or reducing in nature, present challenges to sensor reliability and selectivity, and have therefore necessitated the development of novel sensing devices. While there has been work on developing semiconductor-based electrical sensing methods, this work examines the optical response of AuNPs in yttria-stabilized zirconia (YSZ), TiO2, and CeO2. The main challenge with this technique is to achieve a selective response to the target gases. As a means of addressing this issue, both materials and data analysis techniques have been investigated. From the materials aspect, a sensor array was developed for a direct comparison of Au-YSZ, Au-TiO2, and Au-CeO2. In order to analyze the data, the multivariate method of principle component analysis was applied. The result of this analysis showed that a unique response was seen for each of the three target gases during separate exposures, which is an initial step towards selective detection in a gas mixture. Additional material control has also been achieved with the use of electron beam lithography to pattern Au nanoparticles for size and shape control. A particular emphasis has been placed on the nanorod geometry due to its tunable longitudinal LSPR peak; however, thermal stability of this geometry has been a challenge. Encapsulating the Au nanorods with YSZ was shown to help stabilize the nanorods for sensing tests performed at 500°C. Apart from material control, a kinetics analysis has also been performed for H2 reactions with Au-YSZ in an

  19. Thin film atomic hydrogen detectors

    NASA Technical Reports Server (NTRS)

    Gruber, C. L.

    1977-01-01

    Thin film and bead thermistor atomic surface recombination hydrogen detectors were investigated both experimentally and theoretically. Devices were constructed on a thin Mylar film substrate. Using suitable Wheatstone bridge techniques sensitivities of 80 microvolts/2x10 to the 13th power atoms/sec are attainable with response time constants on the order of 5 seconds.

  20. Thin films: Past, present, future

    SciTech Connect

    Zweibel, K

    1995-04-01

    This report describes the characteristics of the thin film photovoltaic modules necessary for an acceptable rate of return for rural areas and underdeveloped countries. The topics of the paper include a development of goals of cost and performance for an acceptable PV system, a review of current technologies for meeting these goals, issues and opportunities in thin film technologies.

  1. Thin film ion conducting coating

    DOEpatents

    Goldner, Ronald B.; Haas, Terry; Wong, Kwok-Keung; Seward, George

    1989-01-01

    Durable thin film ion conducting coatings are formed on a transparent glass substrate by the controlled deposition of the mixed oxides of lithium:tantalum or lithium:niobium. The coatings provide durable ion transport sources for thin film solid state storage batteries and electrochromic energy conservation devices.

  2. 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.

  3. Polyimide Aerogel Thin Films

    NASA Technical Reports Server (NTRS)

    Meador, Mary Ann; Guo, Haiquan

    2012-01-01

    Polyimide aerogels have been crosslinked through multifunctional amines. This invention builds on "Polyimide Aerogels With Three-Dimensional Cross-Linked Structure," and may be considered as a continuation of that invention, which results in a polyimide aerogel with a flexible, formable form. Gels formed from polyamic acid solutions, end-capped with anhydrides, and cross-linked with the multifunctional amines, are chemically imidized and dried using supercritical CO2 extraction to give aerogels having density around 0.1 to 0.3 g/cubic cm. The aerogels are 80 to 95% porous, and have high surface areas (200 to 600 sq m/g) and low thermal conductivity (as low as 14 mW/m-K at room temperature). Notably, the cross-linked polyimide aerogels have higher modulus than polymer-reinforced silica aerogels of similar density, and can be fabricated as both monoliths and thin films.

  4. Thin film interconnect processes

    NASA Astrophysics Data System (ADS)

    Malik, Farid

    Interconnects and associated photolithography and etching processes play a dominant role in the feature shrinkage of electronic devices. Most interconnects are fabricated by use of thin film processing techniques. Planarization of dielectrics and novel metal deposition methods are the focus of current investigations. Spin-on glass, polyimides, etch-back, bias-sputtered quartz, and plasma-enhanced conformal films are being used to obtain planarized dielectrics over which metal films can be reliably deposited. Recent trends have been towards chemical vapor depositions of metals and refractory metal silicides. Interconnects of the future will be used in conjunction with planarized dielectric layers. Reliability of devices will depend to a large extent on the quality of the interconnects.

  5. Selective inorganic thin films

    SciTech Connect

    Phillips, M.L.F.; Weisenbach, L.A.; Anderson, M.T.

    1995-05-01

    This project is developing inorganic thin films as membranes for gas separation applications, and as discriminating coatings for liquid-phase chemical sensors. Our goal is to synthesize these coatings with tailored porosity and surface chemistry on porous substrates and on acoustic and optical sensors. Molecular sieve films offer the possibility of performing separations involving hydrogen, air, and natural gas constituents at elevated temperatures with very high separation factors. We are focusing on improving permeability and molecular sieve properties of crystalline zeolitic membranes made by hydrothermally reacting layered multicomponent sol-gel films deposited on mesoporous substrates. We also used acoustic plate mode (APM) oscillator and surface plasmon resonance (SPR) sensor elements as substrates for sol-gel films, and have both used these modified sensors to determine physical properties of the films and have determined the sensitivity and selectivity of these sensors to aqueous chemical species.

  6. Ferromagnetic thin films

    DOEpatents

    Krishnan, Kannan M.

    1994-01-01

    A ferromagnetic .delta.-Mn.sub.1-x Ga.sub.x thin film having perpendicular anisotropy is described which comprises: (a) a GaAs substrate, (b) a layer of undoped GaAs overlying said substrate and bonded thereto having a thickness ranging from about 50 to about 100 nanometers, (c) a layer of .delta.-Mn.sub.1-x Ga.sub.x overlying said layer of undoped GaAs and bonded thereto having a thickness ranging from about 20 to about 30 nanometers, and (d) a layer of GaAs overlying said layer of .delta.-Mn.sub.1-x Ga.sub.x and bonded thereto having a thickness ranging from about 2 to about 5 nanometers, wherein x is 0.4 .+-.0.05.

  7. Ferromagnetic thin films

    DOEpatents

    Krishnan, K.M.

    1994-12-20

    A ferromagnetic [delta]-Mn[sub 1[minus]x]Ga[sub x] thin film having perpendicular anisotropy is described which comprises: (a) a GaAs substrate, (b) a layer of undoped GaAs overlying said substrate and bonded thereto having a thickness ranging from about 50 to about 100 nanometers, (c) a layer of [delta]-Mn[sub 1[minus]x]Ga[sub x] overlying said layer of undoped GaAs and bonded thereto having a thickness ranging from about 20 to about 30 nanometers, and (d) a layer of GaAs overlying said layer of [delta]-Mn[sub 1[minus]x]Ga[sub x] and bonded thereto having a thickness ranging from about 2 to about 5 nanometers, wherein x is 0.4[+-]0.05. 7 figures.

  8. Thin film hydrogen sensor

    DOEpatents

    Lauf, R.J.; Hoffheins, B.S.; Fleming, P.H.

    1994-11-22

    A hydrogen sensor element comprises an essentially inert, electrically-insulating substrate having a thin-film metallization deposited thereon which forms at least two resistors on the substrate. The metallization comprises a layer of Pd or a Pd alloy for sensing hydrogen and an underlying intermediate metal layer for providing enhanced adhesion of the metallization to the substrate. An essentially inert, electrically insulating, hydrogen impermeable passivation layer covers at least one of the resistors, and at least one of the resistors is left uncovered. The difference in electrical resistances of the covered resistor and the uncovered resistor is related to hydrogen concentration in a gas to which the sensor element is exposed. 6 figs.

  9. Nonlinear optical thin films

    NASA Technical Reports Server (NTRS)

    Leslie, Thomas M.

    1993-01-01

    A focused approach to development and evaluation of organic polymer films for use in optoelectronics is presented. The issues and challenges that are addressed include: (1) material synthesis, purification, and the tailoring of the material properties; (2) deposition of uniform thin films by a variety of methods; (3) characterization of material physical properties (thermal, electrical, optical, and electro-optical); and (4) device fabrication and testing. Photonic materials, devices, and systems were identified as critical technology areas by the Department of Commerce and the Department of Defense. This approach offers strong integration of basic material issues through engineering applications by the development of materials that can be exploited as the active unit in a variety of polymeric thin film devices. Improved materials were developed with unprecedented purity and stability. The absorptive properties can be tailored and controlled to provide significant improvement in propagation losses and nonlinear performance. Furthermore, the materials were incorporated into polymers that are highly compatible with fabrication and patterning processes for integrated optical devices and circuits. By simultaneously addressing the issues of materials development and characterization, keeping device design and fabrication in mind, many obstacles were overcome for implementation of these polymeric materials and devices into systems. We intend to considerably improve the upper use temperature, poling stability, and compatibility with silicon based devices. The principal device application that was targeted is a linear electro-optic modulation etalon. Organic polymers need to be properly designed and coupled with existing integrated circuit technology to create new photonic devices for optical communication, image processing, other laser applications such as harmonic generation, and eventually optical computing. The progression from microscopic sample to a suitable film

  10. Materials Data on CeO2 (SG:225) by Materials Project

    DOE Data Explorer

    Kristin Persson

    2014-11-02

    Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations

  11. Structure and Reactivity of Alkyl Ethers Adsorbed on CeO(2)(111) Model Catalysts

    SciTech Connect

    Calaza, Florencia C; Chen, Tsung-Liang; Mullins, David R; Overbury, Steven {Steve} H

    2011-01-01

    The effect of surface hydroxyls on the adsorption of ether on ceria was explored. Adsorption of dimethyl ether (DME) and diethyl ether (DEE) on oxidized and reduced CeO{sub 2}(111) films was studied and compared with Ru(0001) using RAIRS and sXPS within a UHV environment. On Ru(0001) the ethers adsorb weakly with the molecular plane close to parallel to the surface plane. On the ceria films, the adsorption of the ethers was stronger than on the metal surface, presumably due to stronger interaction of the ether oxygen lone pair electrons with a cerium cation. This interaction causes the ethers to tilt away from the surface plane compared to the Ru(0001) surface. No pronounced differences were found between oxidized (CeO{sub 2}) and reduced (CeOx) films. The adsorption of the ethers was found to be perturbed by the presence of OH groups on hydroxylated CeOx. In the case of DEE, the geometry of adsorption resembles that found on Ru, and in the case of dimethyl ether DME is in between that one found on clean CeOx and the metal surface. Decomposition of the DEE was observed on the OH/CeOx surface following high DEE exposure at 300 K and higher temperatures. Ethoxides and acetates were identified as adsorbed species on the surface by means of RAIRS and ethoxides and formates by s-XPS. No decomposition of dimethyl ether was observed on the OH/CeOx at these higher temperatures, implying that the dissociation of the C-O bond from ethers requires the presence of {beta}-hydrogen.

  12. Structure and Reactivity of Alkyl Ethers Adsorbed on CeO2(111) Model Catalysts

    SciTech Connect

    F Calaza; T Chen; D Mullins; S Overbury

    2011-12-31

    The effect of surface hydroxyls on the adsorption of ether on ceria was explored. Adsorption of dimethyl ether (DME) and diethyl ether (DEE) on oxidized and reduced CeO{sub 2}(111) films was studied and compared with Ru(0001) using RAIRS and sXPS within a UHV environment. On Ru(0001) the ethers adsorb weakly with the molecular plane close to parallel to the surface plane. On the ceria films, the adsorption of the ethers was stronger than on the metal surface, presumably due to stronger interaction of the ether oxygen lone pair electrons with a cerium cation. This interaction causes the ethers to tilt away from the surface plane compared to the Ru(0001) surface. No pronounced differences were found between oxidized (CeO{sub 2}) and reduced (CeOx) films. The adsorption of the ethers was found to be perturbed by the presence of OH groups on hydroxylated CeOx. In the case of DEE, the geometry of adsorption resembles that found on Ru, and in the case of dimethyl ether DME is in between that one found on clean CeOx and the metal surface. Decomposition of the DEE was observed on the OH/CeOx surface following high DEE exposure at 300 K and higher temperatures. Ethoxides and acetates were identified as adsorbed species on the surface by means of RAIRS and ethoxides and formates by s-XPS. No decomposition of dimethyl ether was observed on the OH/CeOx at these higher temperatures, implying that the dissociation of the C-O bond from ethers requires the presence of {beta}-hydrogen.

  13. SESAME 96170, a solid-liquid equation of state for CeO2

    SciTech Connect

    Chisolm, Eric D.

    2014-05-02

    I describe an equation of state (EOS) for the low-pressure solid phase and liquid phase of cerium (IV) oxide, CeO2. The models and parameters used to calculate the EOS are presented in detail, and I compare with data for the full-density crystal. Hugoniot data are available only for high-porosity powders, and I discuss difficulties in comparing with such data. I have constructed SESAME 96170, an EOS for cerium (IV) oxide that includes the ambient solid and liquid phases. The EOS extends over the full standard SESAME range, but should not be used at low temperatures and high densities because of the lack of a high-pressure solid phase. I have described the models used to compute the three terms of the EOS (cold curve, nuclear, and thermal electronic), and I have given the parameters used in the models. They were determined by comparison with experimental data at P = 1 atm, including the constant-pressure specific heat, coefficient of thermal expansion, and melting and boiling points. The EOS compares well with data in its intended range of validity, but the presence of high-frequency optical modes in its phonon spectrum limits the agreement of our models with thermal data. The next step is to construct a multiphase EOS that includes the low- and high-pressure solid phases and the liquid. The DAC data from Duclos will most strongly constrain the parameters of the high-pressure solid. A remaining issue is the comparison of the crystal-density EOS with experimental Hugoniot data, which are taken at much lower initial data because the samples are porous powders. A satisfactory means of modeling porosity, allowing comparison of theory and experiment, has not yet been produced.

  14. Influence of defect distribution on the reducibility of CeO2-x nanoparticles

    NASA Astrophysics Data System (ADS)

    Chiara Spadaro, Maria; Luches, Paola; Bertoni, Giovanni; Grillo, Vincenzo; Turner, Stuart; Van Tendeloo, Gustaaf; Valeri, Sergio; D'Addato, Sergio

    2016-10-01

    Ceria nanoparticles (NPs) are fundamental in heterogeneous catalysis because of their ability to store or release oxygen depending on the ambient conditions. Their oxygen storage capacity is strictly related to the exposed planes, crystallinity, density and distribution of defects. In this work a study of ceria NPs produced with a ligand-free, physical synthesis method is presented. The NP films were grown by a magnetron sputtering based gas aggregation source and studied by high resolution- and scanning-transmission electron microscopy and x-ray photoelectron spectroscopy. In particular, the influence of the oxidation procedure on the NP reducibility has been investigated. The different reducibility has been correlated to the exposed planes, crystallinity and density and distribution of structural defects. The results obtained in this work represent a basis to obtain cerium oxide NP with desired oxygen transport properties.

  15. SESAME 96171, a three-phase equation of state for CeO2

    SciTech Connect

    Chisolm, Eric D.; Day, Christy M.

    2014-06-25

    We describe an equation of state (EOS) for cerium (IV) oxide, CeO2, that includes two solid phases and the liquid. The models and parameters used to calculate the EOS are presented in detail, and we compare with data for both crystal phases and ambient melt. We discuss complications that arise when making multiphase EOS.

  16. Ferromagnetism in diluted magnetic Zn-Co-doped CeO2-δ

    NASA Astrophysics Data System (ADS)

    Santos, T. S.; Folly, W. S. D.; Macêdo, M. A.

    2012-08-01

    Several oxides doped with transition metals can be used in spintronics devices due to their conductive and magnetic properties at room temperature. In this work, samples of Ce1-2xZnxCoxO2-δ were obtained by an alternative sol-gel proteic process for x=0.01, 0.05 and 0.1. The structural properties of samples were analyzed by XRD and Raman spectroscopy. Magnetization measurements revealed a ferromagnetic behavior at room temperature probably induced by oxygen vacancies.

  17. Trapping and diffusion of fission products in ThO2 and CeO2

    SciTech Connect

    Xiao, Haiyan; Zhang, Yanwen; Weber, William J

    2011-01-01

    The trapping and diffusion of Br, Rb, Cs and Xe in ThO2 and CeO{sub 2} have been studied using an Ab Initio total energy method in the local-density approximation of density functional theory. Fission products incorporated in cation mono-vacancy, cation-anion di-vacancy and Schottky defect sites are found to be stable, with the cation mono-vacancy being the preferred site in most cases. In both oxides, Rb and Cs are the most likely to be trapped, and Xe is more difficult to incorporate than other fission products. The energy barriers for migration of each species in ThO{sub 2} and CeO{sub 2} are also calculated. Alkali metals are relatively more mobile than other fission products, and bromine is the least mobile.

  18. Influence of defect distribution on the reducibility of CeO2-x nanoparticles.

    PubMed

    Spadaro, Maria Chiara; Luches, Paola; Bertoni, Giovanni; Grillo, Vincenzo; Turner, Stuart; Van Tendeloo, Gustaaf; Valeri, Sergio; D'Addato, Sergio

    2016-10-21

    Ceria nanoparticles (NPs) are fundamental in heterogeneous catalysis because of their ability to store or release oxygen depending on the ambient conditions. Their oxygen storage capacity is strictly related to the exposed planes, crystallinity, density and distribution of defects. In this work a study of ceria NPs produced with a ligand-free, physical synthesis method is presented. The NP films were grown by a magnetron sputtering based gas aggregation source and studied by high resolution- and scanning-transmission electron microscopy and x-ray photoelectron spectroscopy. In particular, the influence of the oxidation procedure on the NP reducibility has been investigated. The different reducibility has been correlated to the exposed planes, crystallinity and density and distribution of structural defects. The results obtained in this work represent a basis to obtain cerium oxide NP with desired oxygen transport properties. PMID:27631569

  19. Influence of defect distribution on the reducibility of CeO2-x nanoparticles.

    PubMed

    Spadaro, Maria Chiara; Luches, Paola; Bertoni, Giovanni; Grillo, Vincenzo; Turner, Stuart; Van Tendeloo, Gustaaf; Valeri, Sergio; D'Addato, Sergio

    2016-10-21

    Ceria nanoparticles (NPs) are fundamental in heterogeneous catalysis because of their ability to store or release oxygen depending on the ambient conditions. Their oxygen storage capacity is strictly related to the exposed planes, crystallinity, density and distribution of defects. In this work a study of ceria NPs produced with a ligand-free, physical synthesis method is presented. The NP films were grown by a magnetron sputtering based gas aggregation source and studied by high resolution- and scanning-transmission electron microscopy and x-ray photoelectron spectroscopy. In particular, the influence of the oxidation procedure on the NP reducibility has been investigated. The different reducibility has been correlated to the exposed planes, crystallinity and density and distribution of structural defects. The results obtained in this work represent a basis to obtain cerium oxide NP with desired oxygen transport properties.

  20. Characterization and ecological risk assessment of nanoparticulate CeO2 as a diesel fuel catalyst.

    PubMed

    Batley, Graeme E; Halliburton, Brendan; Kirby, Jason K; Doolette, Casey L; Navarro, Divina; McLaughlin, Mike J; Veitch, Colin

    2013-08-01

    Nanoparticulate cerium dioxide (nano-CeO2 ), when combusted as an additive to diesel fuel, was transformed from 6 nm to 14 nm sizes into particles near 43 nm, with no obvious change in the unit cell dimensions or crystalline form. Cerium sulfate, if formed during combustion, was below detection limits. Ceria nanoparticles were agglomerated within the soot matrix, with a mean aerodynamic diameter near 100 nm. The dissolution of cerium from the dried ceria catalyst in synthetic soft water was extremely small (<0.0006% or <0.2 µg Ce/L), with particles being highly agglomerated (<450 nm). Agglomeration was reduced in the presence of humic acid. In the combusted samples, soot was dominant, and the solubility of cerium in soft water showed an almost 100-fold increase in the <1 nm fraction compared to that before combustion. It appeared that the nano-CeO2 remained agglomerated within the soot matrix and would not be present as dispersed nanoparticles in aquatic or soil environments. Despite the increased dissolution, the solubility was not sufficient for the combusted ceria to represent a risk in aquatic ecosystems. The predicted environmental concentrations were still orders of magnitude below the predicted no effects concentration of near 1 mg/L. In the soil environment, any cerium released from soot materials would interact with natural colloids, decreasing cerium concentrations in soil solutions and further minimizing the potential risk to soil organisms.

  1. Host thin films incorporating nanoparticles

    NASA Astrophysics Data System (ADS)

    Qureshi, Uzma

    The focus of this research project was the investigation of the functional properties of thin films that incorporate a secondary nanoparticulate phase. In particular to assess if the secondary nanoparticulate material enhanced a functional property of the coating on glass. In order to achieve this, new thin film deposition methods were developed, namely use of nanopowder precursors, an aerosol assisted transport technique and an aerosol into atmospheric pressure chemical vapour deposition system. Aerosol assisted chemical vapour deposition (AACVD) was used to deposit 8 series of thin films on glass. Five different nanoparticles silver, gold, ceria, tungsten oxide and zinc oxide were tested and shown to successfully deposit thin films incorporating nanoparticles within a host matrix. Silver nanoparticles were synthesised and doped within a titania film by AACVD. This improved solar control properties. A unique aerosol assisted chemical vapour deposition (AACVD) into atmospheric pressure chemical vapour deposition (APCVD) system was used to deposit films of Au nanoparticles and thin films of gold nanoparticles incorporated within a host titania matrix. Incorporation of high refractive index contrast metal oxide particles within a host film altered the film colour. The key goal was to test the potential of nanopowder forms and transfer the suspended nanopowder via an aerosol to a substrate in order to deposit a thin film. Discrete tungsten oxide nanoparticles or ceria nanoparticles within a titanium dioxide thin film enhanced the self-cleaning and photo-induced super-hydrophilicity. The nanopowder precursor study was extended by deposition of zinc oxide thin films incorporating Au nanoparticles and also ZnO films deposited from a ZnO nanopowder precursor. Incorporation of Au nanoparticles within a VO: host matrix improved the thermochromic response, optical and colour properties. Composite VC/TiC and Au nanoparticle/V02/Ti02 thin films displayed three useful

  2. Learning unit: Thin lenses

    NASA Astrophysics Data System (ADS)

    Nita, L.-S.

    2012-04-01

    Learning unit: Thin lenses "Why objects seen through lenses are sometimes upright and sometimes reversed" Nita Laura Simona National College of Arts and Crafts "Constantin Brancusi", Craiova, Romania 1. GEOMETRIC OPTICS. 13 hours Introduction (models, axioms, principles, conventions) 1. Thin lenses (Types of lenses. Defining elements. Path of light rays through lenses. Image formation. Required physical quantities. Lens formulas). 2. Lens systems (Non-collated lenses. Focalless systems). 3. Human eye (Functioning as an optical system. Sight defects and their corrections). 4. Optical instruments (Characteristics exemplified by a magnifying glass. Paths of light rays through a simplified photo camera. Path of light rays through a classical microscope) (Physics curriculum for the IXth grade/ 2011). This scenario exposes a learning unit based on experimental sequences (defining specific competencies), as a succession of lessons started by noticing a problem whose solution assumes the setup of an experiment under laboratory conditions. Progressive learning of theme objectives are realised with sequential experimental steps. The central cognitive process is the induction or the generalization (development of new knowledge based on observation of examples or counterexamples of the concept to be learnt). Pupil interest in theme objectives is triggered by problem-situations, for example: "In order to better see small objects I need a magnifying glass. But when using a magnifier, small object images are sometimes seen upright and sometimes seen reversed!" Along the way, pupils' reasoning will converge to the idea: "The image of an object through a lens depends on the relative distances among object, lens, and observer". Associated learning model: EXPERIMENT Specific competencies: derived from the experiment model, in agreement with the following learning unit steps I. Evoking - Anticipation: Size of the problem, formulation of hypotheses and planning of experiment. II

  3. Chiral atomically thin films

    NASA Astrophysics Data System (ADS)

    Kim, Cheol-Joo; Sánchez-Castillo, A.; Ziegler, Zack; Ogawa, Yui; Noguez, Cecilia; Park, Jiwoong

    2016-06-01

    Chiral materials possess left- and right-handed counterparts linked by mirror symmetry. These materials are useful for advanced applications in polarization optics, stereochemistry and spintronics. In particular, the realization of spatially uniform chiral films with atomic-scale control of their handedness could provide a powerful means for developing nanodevices with novel chiral properties. However, previous approaches based on natural or grown films, or arrays of fabricated building blocks, could not offer a direct means to program intrinsic chiral properties of the film on the atomic scale. Here, we report a chiral stacking approach, where two-dimensional materials are positioned layer-by-layer with precise control of the interlayer rotation (θ) and polarity, resulting in tunable chiral properties of the final stack. Using this method, we produce left- and right-handed bilayer graphene, that is, a two-atom-thick chiral film. The film displays one of the highest intrinsic ellipticity values (6.5 deg μm–1) ever reported, and a remarkably strong circular dichroism (CD) with the peak energy and sign tuned by θ and polarity. We show that these chiral properties originate from the large in-plane magnetic moment associated with the interlayer optical transition. Furthermore, we show that we can program the chiral properties of atomically thin films layer-by-layer by producing three-layer graphene films with structurally controlled CD spectra.

  4. Thin film composite actuators

    NASA Astrophysics Data System (ADS)

    Su, Quanmin; Kim, Taesung; Zheng, Yun; Wuttig, Manfred R.

    1995-05-01

    The mechanical properties of Ni50Ti50 deposited on Si substrates were studied focussing on the interaction of the film and substrate. This interaction determines the transformation characteristics through interface accommodation and mechanical constraints exerted by the substrate stiffness. Substrate stiffness, controlled by the film/substrate thickness ratio, was found to have a substantial influence on the output energy of the film/substrate composite. A switch type composite based on this knowledge was fabricated and tested. The thermo-mechanical properties of Terfenol-D thin films deposited on Si substrates were studied by static and dynamic measurements of film/substrate composite cantilevers. The Curie transition, (Delta) E effect and mechanical damping of the film were measured simultaneously. The stress in the film was controlled by annealing below the recrystallization temperature and determined to vary from -500 MPa, compression, in as deposited films to +480 MPa, tension, in annealed films. The Curie temperature shifts from 80 degree(s)C to 140 degree(s)C as the tension increases while the structure of the film remains amorphous. The stress change induced by annealing also drastically effects the film's damping characteristics. The (Delta) E effect of the amorphous material, about 20%, was used to estimate the magnetostriction, (lambda) s approximately equals 4 (DOT) 10-3.

  5. Chiral atomically thin films

    NASA Astrophysics Data System (ADS)

    Kim, Cheol-Joo; Sánchez-Castillo, A.; Ziegler, Zack; Ogawa, Yui; Noguez, Cecilia; Park, Jiwoong

    2016-06-01

    Chiral materials possess left- and right-handed counterparts linked by mirror symmetry. These materials are useful for advanced applications in polarization optics, stereochemistry and spintronics. In particular, the realization of spatially uniform chiral films with atomic-scale control of their handedness could provide a powerful means for developing nanodevices with novel chiral properties. However, previous approaches based on natural or grown films, or arrays of fabricated building blocks, could not offer a direct means to program intrinsic chiral properties of the film on the atomic scale. Here, we report a chiral stacking approach, where two-dimensional materials are positioned layer-by-layer with precise control of the interlayer rotation (θ) and polarity, resulting in tunable chiral properties of the final stack. Using this method, we produce left- and right-handed bilayer graphene, that is, a two-atom-thick chiral film. The film displays one of the highest intrinsic ellipticity values (6.5 deg μm-1) ever reported, and a remarkably strong circular dichroism (CD) with the peak energy and sign tuned by θ and polarity. We show that these chiral properties originate from the large in-plane magnetic moment associated with the interlayer optical transition. Furthermore, we show that we can program the chiral properties of atomically thin films layer-by-layer by producing three-layer graphene films with structurally controlled CD spectra.

  6. Microwave resonant technique in studies of photodielectric properties of bulk, thin film and nanoparticle materials

    NASA Astrophysics Data System (ADS)

    Pavlov, V. V.; Rakhmatullin, R. M.; Cefalas, A. C.; Semashko, V. V.

    2016-06-01

    An enhanced contactless microwave technique allows us to study the photoconductivity of materials. The transient response of the complex permittivity of matter (ε ={ε1}-j{ε2} ) under optical irradiation is measured with nanosecond time resolution. The main advantage of the novel methodology is the elimination of the polarization effect in evaluating photoconductivity. The potential of the methodology was demonstrated by photoconductivity measurements in Si [1 0 0] crystal, CeO2 nanocrystalline powder and Ce-doped LiYF4 single crystal. The variations of complex permittivity (δ {ε1} and δ {ε2} ) of Si [1 0 0] crystal, CeO2 nanocrystalline powder and Ce-doped LiYF4 single crystal under optical irradiation was measured and accurate values for crystalline band gaps were extracted. Finally, quantum confinement effects were observed in nano-size crystalline powders.

  7. Thin, Flexible IMM Solar Array

    NASA Technical Reports Server (NTRS)

    Walmsley, Nicholas

    2015-01-01

    NASA needs solar arrays that are thin, flexible, and highly efficient; package compactly for launch; and deploy into large, structurally stable high-power generators. Inverted metamorphic multijunction (IMM) solar cells can enable these arrays, but integration of this thin crystalline cell technology presents certain challenges. The Thin Hybrid Interconnected Solar Array (THINS) technology allows robust and reliable integration of IMM cells into a flexible blanket comprising standardized modules engineered for easy production. The modules support the IMM cell by using multifunctional materials for structural stability, shielding, coefficient of thermal expansion (CTE) stress relief, and integrated thermal and electrical functions. The design approach includes total encapsulation, which benefits high voltage as well as electrostatic performance.

  8. Ultra thin gage plastic film

    NASA Technical Reports Server (NTRS)

    Cox, D. W., Jr.; Struble, A. D.

    1971-01-01

    Process utilizing specially modified conventional equipment, with changes in process temperature, pressure, and cooling requirements produces ultra thin 1.56 micron /0.0614 mil/ thick polyethylene film.

  9. Interference Colors in Thin Films.

    ERIC Educational Resources Information Center

    Armstrong, H. L.

    1979-01-01

    Explains interference colors in thin films as being due to the removal, or considerable reduction, of a certain color by destructive inteference that results in the complementary color being seen. (GA)

  10. Slowly rotating thin shell gravastars

    NASA Astrophysics Data System (ADS)

    Uchikata, Nami; Yoshida, Shijun

    2016-01-01

    We construct the solutions of slowly rotating gravastars with a thin shell. In the zero-rotation limit, we consider the gravastar composed of a de Sitter core, a thin shell, and Schwarzschild exterior spacetime. The rotational effects are treated as small axisymmetric and stationary perturbations. The perturbed internal and external spacetimes are matched with a uniformly rotating thin shell. We assume that the angular velocity of the thin shell, Ω, is much smaller than the Keplerian frequency of the nonrotating gravastar, {{{Ω }}}{{k}}. The solutions within an accuracy up to the second order of {{Ω }}/{{{Ω }}}{{k}} are obtained. The thin shell matter is assumed to be described by a perfect fluid and to satisfy the dominant energy condition in the zero-rotation limit. In this study, we assume that the equation of state for perturbations is the same as that of the unperturbed solution. The spherically symmetric component of the energy density perturbations, δ {σ }0, is assumed to vanish independently of the rotation rate. Based on these assumptions, we obtain many numerical solutions and investigate properties of the rotational corrections to the structure of the thin shell gravastar.

  11. Thin EFG octagons

    NASA Astrophysics Data System (ADS)

    Kalejs, J. P.

    1994-01-01

    Mobil Solar Energy Corporation currently practices a unique crystal growth technology for producing crystalline silicon sheet, which is then cut with lasers into wafers. The wafers are processed into solar cells and incorporated into modules for photovoltaic applications. The silicon sheet is produced using a method known as Edge-defined Film-fed growth (EFG), in the form of hollow eight-sided polygons (octagons) with 10 cm faces. These are grown to lengths of 5 meters and thickness of 300 microns, with continuous melt replenishment, in compact furnaces designed to operate at a high sheet area production area of 135 sq cm/min. The present Photovoltaic Manufacturing Technology (PVMaT) three-year program seeks to advance the manufacturing line capabilities of the Mobil Solar crystal growth and cutting technologies. If successful, these advancements will provide significant reductions in already low silicon raw material usage, improve process productivity, laser cutting throughput and yield, and so lower both individual wafer cost and the cost of module production. This report summarizes the significant technical improvements in EFG technology achieved in Phase 1 of this program. Technical results are reported for each of the three main program areas: (1) thin octagon growth (crystal growth) -- to reduce the thickness of the octagon to an interim goal of 250 microns during Phase 1, with an ultimate goal of achieving 200 micron thicknesses; (2) laser cutting -- to improve the laser cutting process, so as to produce wafers with decreased laser cutting damage at increased wafer throughput rates; and (3) process control and product specification -- to implement advanced strategies in crystal growth process control and productivity designed to increase wafer yields.

  12. Thin film cell development workshop report

    NASA Technical Reports Server (NTRS)

    Woodyard, James R.

    1991-01-01

    The Thin Film Development Workshop provided an opportunity for those interested in space applications of thin film cells to debate several topics. The unique characteristics of thin film cells as well as a number of other issues were covered during the discussions. The potential of thin film cells, key research and development issues, manufacturing issues, radiation damage, substrates, and space qualification of thin film cells were discussed.

  13. Shear Thinning of Noncolloidal Suspensions.

    PubMed

    Vázquez-Quesada, Adolfo; Tanner, Roger I; Ellero, Marco

    2016-09-01

    Shear thinning-a reduction in suspension viscosity with increasing shear rates-is understood to arise in colloidal systems from a decrease in the relative contribution of entropic forces. The shear-thinning phenomenon has also been often reported in experiments with noncolloidal systems at high volume fractions. However its origin is an open theoretical question and the behavior is difficult to reproduce in numerical simulations where shear thickening is typically observed instead. In this letter we propose a non-Newtonian model of interparticle lubrication forces to explain shear thinning in noncolloidal suspensions. We show that hidden shear-thinning effects of the suspending medium, which occur at shear rates orders of magnitude larger than the range investigated experimentally, lead to significant shear thinning of the overall suspension at much smaller shear rates. At high particle volume fractions the local shear rates experienced by the fluid situated in the narrow gaps between particles are much larger than the averaged shear rate of the whole suspension. This allows the suspending medium to probe its high-shear non-Newtonian regime and it means that the matrix fluid rheology must be considered over a wide range of shear rates. PMID:27636496

  14. Thin-film metal hydrides.

    PubMed

    Remhof, Arndt; Borgschulte, Andreas

    2008-12-01

    The goal of the medieval alchemist, the chemical transformation of common metals into nobel metals, will forever be a dream. However, key characteristics of metals, such as their electronic band structure and, consequently, their electric, magnetic and optical properties, can be tailored by controlled hydrogen doping. Due to their morphology and well-defined geometry with flat, coplanar surfaces/interfaces, novel phenomena may be observed in thin films. Prominent examples are the eye-catching hydrogen switchable mirror effect, the visualization of solid-state diffusion and the formation of complex surface morphologies. Thin films do not suffer as much from embrittlement and/or decrepitation as bulk materials, allowing the study of cyclic absorption and desorption. Therefore, thin-metal hydride films are used as model systems to study metal-insulator transitions, for high throughput combinatorial research or they may be used as indicator layers to study hydrogen diffusion. They can be found in technological applications as hydrogen sensors, in electrochromic and thermochromic devices. In this review, we discuss the effect of hydrogen loading of thin niobium and yttrium films as archetypical examples of a transition metal and a rare earth metal, respectively. Our focus thereby lies on the hydrogen induced changes of the electronic structure and the morphology of the thin films, their optical properties, the visualization and the control of hydrogen diffusion and on the study of surface phenomena and catalysis.

  15. Obese people's perceptions of the thin ideal.

    PubMed

    Couch, Danielle; Thomas, Samantha L; Lewis, Sophie; Blood, R Warwick; Holland, Kate; Komesaroff, Paul

    2016-01-01

    The media play a key role in promoting the thin ideal. A qualitative study, in which we used in depth interviews and thematic analysis, was undertaken to explore the attitudes of 142 obese individuals toward media portrayals of the thin ideal. Participants discussed the thin ideal as a social norm that is also supported through the exclusion of positive media portrayals of obese people. They perceived the thin ideal as an 'unhealthy' mode of social control, reflecting on their personal experiences and their concerns for others. Participants' perceptions highlighted the intersections between the thin ideal and gender, grooming and consumerism. Participants' personal responses to the thin ideal were nuanced--some were in support of the thin ideal and some were able to critically reflect and reject the thin ideal. We consider how the thin ideal may act as a form of synoptical social control, working in tandem with wider public health panoptical surveillance of body weight. PMID:26685706

  16. Obese people's perceptions of the thin ideal.

    PubMed

    Couch, Danielle; Thomas, Samantha L; Lewis, Sophie; Blood, R Warwick; Holland, Kate; Komesaroff, Paul

    2016-01-01

    The media play a key role in promoting the thin ideal. A qualitative study, in which we used in depth interviews and thematic analysis, was undertaken to explore the attitudes of 142 obese individuals toward media portrayals of the thin ideal. Participants discussed the thin ideal as a social norm that is also supported through the exclusion of positive media portrayals of obese people. They perceived the thin ideal as an 'unhealthy' mode of social control, reflecting on their personal experiences and their concerns for others. Participants' perceptions highlighted the intersections between the thin ideal and gender, grooming and consumerism. Participants' personal responses to the thin ideal were nuanced--some were in support of the thin ideal and some were able to critically reflect and reject the thin ideal. We consider how the thin ideal may act as a form of synoptical social control, working in tandem with wider public health panoptical surveillance of body weight.

  17. Recovery Act : Near-Single-Crystalline Photovoltaic Thin Films on Polycrystalline, Flexible Substrates

    SciTech Connect

    Venkat Selvamanickam; Alex Freundlich

    2010-11-29

    III-V photovoltaics have exhibited efficiencies above 40%, but have found only a limited use because of the high cost of single crystal substrates. At the other end of the spectrum, polycrystalline and amorphous thin film solar cells offer the advantage of low-cost fabrication, but have not yielded high efficiencies. Our program is based on single-crystalline-like thin film photovoltaics on polycrystalline substrates using biaxially-textured templates made by Ion Beam-Assisted Deposition (IBAD). MgO templates made by IBAD on flexible metal substrate have been successfully used for epitaxial growth of germanium films. In spite of a 4.5% lattice mismatch, heteroepitaxial growth of Ge was achieved on CeO2 that was grown on IBAD MgO template. Room temperature optical bandgap of the Ge films was identified at 0.67 eV indicating minimal residual strain. Refraction index and extinction coefficient values of the Ge films were found to match well with that measured from a reference Ge single crystal. GaAs has been successfully grown epitaxially on Ge on metal substrate by molecular beam epitaxy. RHEED patterns indicate self annihilation of antiphase boundaries and the growth of a single domain GaAs. The GaAs is found to exhibit strong photoluminescence signal and, an existence of a relatively narrow (FWHM~20 meV) band-edge excitons measured in this film indicates a good optoelectronic quality of deposited GaAs. While excellent epitaxial growth has been achieved in GaAs on flexible metal substrates, the defect density of the films as measured by High Resolution X-ray Diffraction and etch pit experiments showed a high value of 5 * 10^8 per cm^2. Cross sectional transmission electron microscopy of the multilayer architecture showed concentration of threading dislocations near the germanium-ceria interface. The defect density was found decrease as the Ge films were made thicker. The defects appear to originate from the MgO layer presumably because of large lattice mismatches

  18. Thin metal electrode for AMTEC

    NASA Technical Reports Server (NTRS)

    Williams, Roger M. (Inventor); Wheeler, Bob L. (Inventor); Jefferies-Nakamura, Barbara (Inventor); Lamb, James L. (Inventor); Bankston, C. Perry (Inventor); Cole, Terry (Inventor)

    1989-01-01

    An electrode having higher power output is formed of a thin, porous film (less than 1 micrometer) applied to a beta-alumina solid electrolyte (BASE). The electrode includes an open grid, current collector such as a series of thin, parallel, grid lines applied to the thin film and a plurality of cross-members such as loop of metal wire surrounding the BASE tube. The loops are electrically connected by a bus wire. The overall impedance of the electrode considering both the contributions from the bulk BASE and the porous electrode BASE interface is low, about 0.5 OHM/cm.sup.2 and power densities of over 0.3 watt/cm.sup.2 for extended periods.

  19. Squirming through shear thinning fluids

    NASA Astrophysics Data System (ADS)

    Datt, Charu; Zhu, Lailai; Elfring, Gwynn J.; Pak, On Shun

    2015-11-01

    Many microorganisms find themselves surrounded by fluids which are non-Newtonian in nature; human spermatozoa in female reproductive tract and motile bacteria in mucosa of animals are common examples. These biological fluids can display shear-thinning rheology whose effects on the locomotion of microorganisms remain largely unexplored. Here we study the self-propulsion of a squirmer in shear-thinning fluids described by the Carreau-Yasuda model. The squirmer undergoes surface distortions and utilizes apparent slip-velocities around its surface to swim through a fluid medium. In this talk, we will discuss how the nonlinear rheological properties of a shear-thinning fluid affect the propulsion of a swimmer compared with swimming in Newtonian fluids.

  20. Vapor deposition of thin films

    DOEpatents

    Smith, David C.; Pattillo, Stevan G.; Laia, Jr., Joseph R.; Sattelberger, Alfred P.

    1992-01-01

    A highly pure thin metal film having a nanocrystalline structure and a process of preparing such highly pure thin metal films of, e.g., rhodium, iridium, molybdenum, tungsten, rhenium, platinum, or palladium by plasma assisted chemical vapor deposition of, e.g., rhodium(allyl).sub.3, iridium(allyl).sub.3, molybdenum(allyl).sub.4, tungsten(allyl).sub.4, rhenium(allyl).sub.4, platinum(allyl).sub.2, or palladium(allyl).sub.2 are disclosed. Additionally, a general process of reducing the carbon content of a metallic film prepared from one or more organometallic precursor compounds by plasma assisted chemical vapor deposition is disclosed.