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Sample records for gd2o3-doped ceo2 thin

  1. Enhancement of ferromagnetism in C ion implanted CeO2 thin films

    NASA Astrophysics Data System (ADS)

    Kumar, Pawan; Chand, F.; Asokan, K.

    2017-03-01

    This investigation reports on room temperature ferromagnetism in pristine and C ion implanted CeO2 thin films deposited on Si (111) substrates by the radio frequency (RF)-sputtering method. X-ray diffraction analysis shows that the face-centered cubic (FCC) structure corresponds to CeO2. The Raman spectra further confirm the formation of phase and also indicate the presence of defects, mainly oxygen vacancies, in these films. The presence of C is evident from Rutherford backscattering studies. Atomic force microscopy images indicate that the surface roughness values of the films reduce after C ion implantation. It is observed that the magnetic properties in CeO2 thin films are enhanced by C ion implantation. The saturation magnetization of the pristine film increases from ∼7 emu cm‑3 to ∼27 emu cm‑3 for a fluence of 6 × 1016 ions cm‑2. It is also observed that the coercivity values change after C ion implantation and reduce for a film with an ion fluence of 6 × 1016 ions cm‑2 compared with other films. Mechanisms such as the F-center exchange (FCE) model are considered when attempting to understand the enhanced ferromagnetism of C ion implanted CeO2 thin films.

  2. 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.

  3. 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.

  4. 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.

  5. Synthesis of CeO2@SiO2 core-shell nanoparticles by water-in-oil microemulsion. Preparation of functional thin film.

    PubMed

    Grasset, F; Marchand, R; Marie, A-M; Fauchadour, D; Fajardie, F

    2006-07-15

    Synthesis of nanoparticles under restricted environment offered by water-in-oil (W/O) microemulsions provides excellent control over particle size and shape, and inter-particle spacing. Such an environment has been involved to synthesize silica nanoparticles with a CeO2 core, so-called CeO2@SiO2. Aqueous fluids made up of ceria nanoparticles with a size close to 5 nm have been used as the water phase component. The starting CeO2 sols and obtained CeO2@SiO2 nanoparticles have been characterized by dynamic light scattering (DLS), X-ray diffraction, scanning and transmission electron microscopy, and specific surface area measurements. The microemulsion process has been characterized by DLS. Preliminary results on CeO2@SiO2 thin films are presented.

  6. Effect of surface modification of CeO2 buffer layers on Jc and defect microstructures of large-area YBCO thin films

    NASA Astrophysics Data System (ADS)

    Develos-Bagarinao, K.; Yamasaki, H.; Nakagawa, Y.

    2006-08-01

    High-quality CeO2 buffer layers are requisite for the successful growth of YBCO thin films with excellent properties on sapphire substrates. In this study, we evaluated the effect of surface modification of the CeO2 layers on the properties of the YBCO thin films prepared by large-area pulsed laser deposition (PLD), in particular the critical current density Jc and defect microstructure. High-temperature annealing (1050 °C) has been found to significantly smoothen the very rough and granular surfaces of the as-grown CeO2 layers (surface roughness rms~5-10 nm) to atomic flatness (rms~0.5 nm). However, a rather unique characteristic of the CeO2 layers deposited by large-area PLD is the development of pores when subjected to prolonged high-temperature annealing. For very short annealing periods (10-20 min), the surface morphology becomes atomically flat, along with the appearance of a high density of 'nanopores' that are ~40-100 nm in diameter and ~3-5 nm in depth. Extending the annealing period to 60 min or more results in the development of a surface subtended with enlarged pores ~0.2-0.5 µm in diameter. Compared with the YBCO thin films deposited on as-grown CeO2, YBCO thin films on annealed CeO2 exhibited better homogeneity of Jc and better crystalline texture. Among the YBCO thin films deposited on annealed CeO2, higher self-field and in-field Jc was obtained for YBCO thin films deposited on CeO2 with smooth surfaces but interspersed with nanopores. Investigation of the defect microstructure via the etch pit method in conjunction with atomic force microscopy (AFM) of the YBCO thin films revealed a high density of linear defects in the form of screw and edge dislocations, which correlated well with a high density of nanopores on annealed CeO2. Transmission electron microscopy (TEM) further confirmed the presence of threading dislocations clearly emanating from the nanopore sites. Angular dependence of Jc revealed enhanced flux pinning for YBCO thin films

  7. Growth of YBCO Thin Films on TiN(001) and CeO2-Coated TiN Surfaces

    DTIC Science & Technology

    2012-02-01

    substrates. Thin CeO2 (~200 nm thick) and YBCO (~300 nm thick) layers were grown on TiN-coated MgO substrates, using pulsed laser deposition. While YBCO ...and YBCO (300 nm thick) layers were grown on TiN-coated MgO substrates, using pulsed laser deposition. While YBCO grown directly on TiN was of poor...grown on the TiN-coated MgO and then an 300 nm thick YBCO layers was subsequently depos- ited. For other samples, YBCO deposition directly on the

  8. Photoluminescence and electrochemical properties of transparent CeO2-ZnO nanocomposite thin films prepared by Pechini method

    NASA Astrophysics Data System (ADS)

    Sani, Z. Khosousi; Ghodsi, F. E.; Mazloom, J.

    2017-02-01

    Nanocomposite thin films of CeO2-ZnO with different molar ratios of Zn/Ce (=0, 0.25, 0.5, 0.75 and 1) were prepared by the Pechini sol-gel route. Various spectroscopic and electrochemical techniques were applied to investigate the films. XRD patterns of all the samples exhibited the peaks corresponding to cubic fluorite structure of ceria and the (101) and (103) peaks of ZnO with hexagonal structure was just observed in the sample with molar ratio of 1. EDS confirmed the presence of constituent of element in the samples. FESEM images of the films showed a surface composed of nanograins. AFM analysis revealed that root mean square roughness was enhanced as molar ratio of Zn/Ce increased. Moreover, fractal dimension of surfaces were calculated by cube counting approach. Optical measurements indicated that the film with molar ratio of 1 has the highest transmission and lowest reflectivity. The optical band gap values varied between 2.95 and 3.42 eV. The compositional dependence of refractive index and extinction coefficient were reported. The UV and blue emission appeared in PL spectra. The highest photoluminescence emission intensity was observed in the 1:1 molar ratio sample. The cyclic voltammetry measurements indicated the highest charge density (9.75 mC cm-2) and diffusion coefficient (3.507 × 10-17 cm2 s-1) belonged to the Ce/Zn (1:1) thin film.

  9. 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.

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

    DOE PAGES

    Yang, Nan; Belianinov, Alex; Strelcov, Evgheni; ...

    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

  11. 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.

  12. 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.

  13. Angular properties of pure and Ca-substituted YBa2Cu3O7-δ superconducting thin films grown on SrTiO3 and CeO2 buffered Al2O3 substrates

    NASA Astrophysics Data System (ADS)

    Augieri, A.; Celentano, G.; Ciontea, L.; Galluzzi, V.; Gambardella, U.; Halbritter, J.; Petrisor, T.; Rufoloni, A.; Vannozzi, A.

    2007-09-01

    In this work transport properties of superconducting 10 at.% Ca-substituted YBCO thin films grown on (1 0 0)-SrTiO 3 single crystal substrate (STO) and superconducting pure and 10 at.% Ca-substituted YBCO thin films grown on CeO 2 buffered Al 2O 3 substrates (CAO) have been analyzed as a function of the temperature, applied magnetic field and angle between magnetic field direction and the direction normal to the film surfaces. Particularly, the angular analysis provides an easy way to discriminate between isotropic point defects and correlated pinning sites. Despite the intragrain pinning mechanisms remained unaffected by Ca substitution, a detrimental effect on grain boundary properties clearly emerged for 10 at.% Ca concentration. This effect is enhanced in sample grown on CeO 2 buffered sapphire where a more disturbed grain boundary is expected resulting in an enhancement of the correlated pinning, already observed in pure YBCO films grown on CAO, and in a reduction of the intrinsic pinning efficiency.

  14. Characterization of sol-gel thin films of TiO2-PbO, TiO2-Bi2O3 and TiO2-CeO2 compositions

    NASA Astrophysics Data System (ADS)

    Aegerter, Michel A.; La Serra, Eliane R.; Martins Rodrigues, Ana C.; Kordas, George; Moore, Glenn A.

    1990-11-01

    Single and multilayer sol-gel thin films of Ti02-PbO, Ti02-Bi203 and Ti02-CeO2 composition were deposited on glasses using the dip coating technique. The precursors included Ti(OPri)4 chemically modified by acetyl acetone and diluted in PriOH and sols of Pb(OAc)2, Bi(NO3)3 5H20 diluted in acetic acid. The Ti02-Ce02 sol was prepared by mixing Ce NH2 (NO3 )6 in ethanol and then adding Ti (O-iso-C3H7 )4. Structure texture and homogeneity of their main constituants was established by XRD, XPS,SIMS and SEM-EDX techniques as a function of heat treatments.

  15. 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.

  16. 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.

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

    DOE PAGES

    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

  18. Growth of highly strained CeO2 ultrathin films

    DOE PAGES

    Shi, Yezhou; Lee, Sang Chul; Monti, Matteo; ...

    2016-11-07

    Large biaxial strain is a promising route to tune the functionalities of oxide thin films. However, large strain is often not fully realized due to the formation of misfit dislocations at the film/substrate interface. In this work, we examine the growth of strained ceria (CeO2) thin films on (001)-oriented single crystal yttria-stabilized zirconia (YSZ) via pulsed-laser deposition. By varying the film thickness systematically between 1 and 430 nm, we demonstrate that ultrathin ceria films are coherently strained to the YSZ substrate for thicknesses up to 2.7 nm, despite the large lattice mismatch (~5%). The coherency is confirmed by both X-raymore » diffraction and high-resolution transmission electron microscopy. This thickness is several times greater than the predicted equilibrium critical thickness. Partial strain relaxation is achieved by forming semirelaxed surface islands rather than by directly nucleating dislocations. In situ reflective high-energy electron diffraction during growth confirms the transition from 2-D (layer-by-layer) to 3-D (island) at a film thickness of ~1 nm, which is further supported by atomic force microscopy. We propose that dislocations likely nucleate near the surface islands and glide to the film/substrate interface, as evidenced by the presence of 60° dislocations. Finally, an improved understanding of growing oxide thin films with a large misfit lays the foundation to systematically explore the impact of strain and dislocations on properties such as ionic transport and redox chemistry.« less

  19. Raman, dielectric and variable range hopping nature of Gd2O3-doped K0.5N0.5NbO3 piezoelectric ceramics

    NASA Astrophysics Data System (ADS)

    Peddigari, Mahesh; Dobbidi, Pamu

    2015-10-01

    (K0.5Na0.5)NbO3 (KNN) + x wt% Gd2O3 (x = 0 -1.5) ceramics have been prepared by conventional solid state reaction method. The effect of Gd2O3 on the structural, microstructural and dielectric properties of KNN ceramics were studied systematically. The effect of Gd2O3 on phase transformation from orthorhombic to psuedocubic structure is explained interms of changes in the internal vibration modes of NbO6 octahedra. The Raman intensity of the stretching mode v1 enhanced and shifted toward higher wavenumber with Gd2O3 concentration, which is attributed to the increase in polarizability and change in the O-Nb-O bond angles. Microstructural analysis revealed that the grain size of the KNN ceramics decreases from 2.26 ± 1.07 μm to 0.35 ± 0.13 μm and becomes homogenous with an increase in Gd2O3 concentration. The frequency dependent dielectric spectra are analyzed by using Havriliak-Negami function. The fitted symmetry parameter and relaxation time (τ) are found to be 0.914 and 8.78 × 10-10 ± 5.5 × 10-11 s, respectively for the sample doped with x = 1.0. The addition of Gd2O3 to the KNN shifted the polymorphic phase transition orthorhombic to tetragonal transition temperature (TO-T) from 199oC to 85oC with enhanced dielectric permittivity (ɛ' = 1139 at 1 MHz). The sample with x = 1.0, shown a high dielectric permittivity (ɛ' = 879) and low dielectric loss (<5%) in the broad temperature range (-140oC - 150oC) with the Curie temperature 307 oC can have the potential for high temperature piezoelectric and tunable RF circuit applications. The temperature dependent AC-conductivity follows the variable range hopping conduction mechanism by obtaining the slope -0.25 from the ln[ln(ρac)] versus ln(T) graph in the temperature range of 133 K-308 K. The effect of Gd2O3 on the Mott's parameters such as density of states (N(EF)), hopping length (RH), and hopping energy (WH) have been discussed.

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

    DOE PAGES

    Sanghavi, Shail; Wang, Weina; Nandasiri, Manjula I.; ...

    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

  1. Oxygen vacancy-assisted coupling and enolization of acetaldehyde on CeO2(111).

    PubMed

    Calaza, Florencia C; Xu, Ye; Mullins, David R; Overbury, Steven H

    2012-10-31

    The temperature-dependent adsorption and reaction of acetaldehyde (CH(3)CHO) on a fully oxidized and a highly reduced thin-film CeO(2)(111) surface have been investigated using a combination of reflection-absorption infrared spectroscopy (RAIRS) and periodic density functional theory (DFT+U) calculations. On the fully oxidized surface, acetaldehyde adsorbs weakly through its carbonyl O interacting with a lattice Ce(4+) cation in the η(1)-O configuration. This state desorbs at 210 K without reaction. On the highly reduced surface, new vibrational signatures appear below 220 K. They are identified by RAIRS and DFT as a dimer state formed from the coupling of the carbonyl O and the acyl C of two acetaldehyde molecules. This dimer state remains up to 400 K before decomposing to produce another distinct set of vibrational signatures, which are identified as the enolate form of acetaldehyde (CH(2)CHO¯). Furthermore, the calculated activation barriers for the coupling of acetaldehyde, the decomposition of the dimer state, and the recombinative desorption of enolate and H as acetaldehyde are in good agreement with previously reported TPD results for acetaldehyde adsorbed on reduced CeO(2)(111) [Chen et al. J. Phys. Chem. C 2011, 115, 3385]. The present findings demonstrate that surface oxygen vacancies alter the reactivity of the CeO(2)(111) surface and play a crucial role in stabilizing and activating acetaldehyde for coupling reactions.

  2. 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

  3. A perfectly stoichiometric and flat CeO2(111) surface on a bulk-like ceria film

    NASA Astrophysics Data System (ADS)

    Barth, C.; Laffon, C.; Olbrich, R.; Ranguis, A.; Parent, Ph.; Reichling, M.

    2016-02-01

    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.

  4. A perfectly stoichiometric and flat CeO2(111) surface on a bulk-like ceria film.

    PubMed

    Barth, C; Laffon, C; Olbrich, R; Ranguis, A; Parent, Ph; Reichling, M

    2016-02-16

    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.

  5. 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

    2014-08-29

    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.

  6. Preparation and catalytic behavior of CeO2 nanoparticles on Al2O3 crystal

    NASA Astrophysics Data System (ADS)

    Hattori, Takashi; Kobayashi, Katsutoshi; Ozawa, Masakuni

    2017-01-01

    In this work, we examined the preparation, morphology, and catalytic behavior of CeO2 nanoparticles (NPs) on Al2O3(0001) crystal substrates. A CeO2 NP layer was prepared by the dipping method using a CeO2 nanocrystal colloid solution. Even after heat treatment at 1000 °C, the CeO2 NP layer maintained the granular morphology of CeO2 with a grain diameter of less than 40 nm. CeO2 NPs on an Al2O3 crystal showed higher oxidation activity for gaseous hydrogen at moderate temperatures and enhanced oxygen release properties of CeO2, compared with CeO2 powder. This was due to the highly dispersed CeO2 NPs and the interaction between CeO2 NPs and Al2O3; this clarified the importance of the Al2O3 support for the CeO2 catalyst.

  7. The effect of fission-energy Xe ion irradiation on the structural integrity and dissolution of the CeO2 matrix

    NASA Astrophysics Data System (ADS)

    Popel, A. J.; Le Solliec, S.; Lampronti, G. I.; Day, J.; Petrov, P. K.; Farnan, I.

    2017-02-01

    This work considers the effect of fission fragment damage on the structural integrity and dissolution of the CeO2 matrix in water, as a simulant for the UO2 matrix of spent nuclear fuel. For this purpose, thin films of CeO2 on Si substrates were produced and irradiated by 92 MeV 129Xe23+ ions to a fluence of 4.8 × 1015 ions/cm2 to simulate fission damage that occurs within nuclear fuels along with bulk CeO2 samples. The irradiated and unirradiated samples were characterised and a static batch dissolution experiment was conducted to study the effect of the induced irradiation damage on dissolution of the CeO2 matrix. Complex restructuring took place in the irradiated films and the irradiated samples showed an increase in the amount of dissolved cerium, as compared to the corresponding unirradiated samples. Secondary phases were also observed on the surface of the irradiated CeO2 films after the dissolution experiment.

  8. Lattice-matched Cu2ZnSnS4/CeO2 solar cell with open circuit voltage boost

    NASA Astrophysics Data System (ADS)

    Crovetto, Andrea; Yan, Chang; Iandolo, Beniamino; Zhou, Fangzhou; Stride, John; Schou, Jørgen; Hao, Xiaojing; Hansen, Ole

    2016-12-01

    We report a reproducible enhancement of the open circuit voltage in Cu2ZnSnS4 solar cells by introduction of a very thin CeO2 interlayer between the Cu2ZnSnS4 absorber and the conventional CdS buffer. CeO2, a non-toxic earth-abundant compound, has a nearly optimal band alignment with Cu2ZnSnS4 and the two materials are lattice-matched within 0.4%. This makes it possible to achieve an epitaxial interface when growing CeO2 by chemical bath deposition at temperatures as low as 50 °C. The open circuit voltage improvement is then attributed to a decrease in the interface recombination rate through formation of a high-quality heterointerface.

  9. Structural characterization of nanosized CeO(2)-SiO(2), CeO(2)-TiO(2), and CeO(2)-ZrO(2) catalysts by XRD, Raman, and HREM techniques.

    PubMed

    Reddy, Benjaram M; Khan, Ataullah; Lakshmanan, Pandian; Aouine, Mimoun; Loridant, Stéphane; Volta, Jean-Claude

    2005-03-03

    Structural characteristics of nanosized ceria-silica, ceria-titania, and ceria-zirconia mixed oxide catalysts have been investigated using X-ray diffraction (XRD), Raman spectroscopy, BET surface area, thermogravimetry, and high-resolution transmission electron microscopy (HREM). The effect of support oxides on the crystal modification of ceria cubic lattice was mainly focused. The investigated oxides were obtained by soft chemical routes with ultrahighly dilute solutions and were subjected to thermal treatments from 773 to 1073 K. The XRD results suggest that the CeO(2)-SiO(2) sample primarily consists of nanocrystalline CeO(2) on the amorphous SiO(2) surface. Both crystalline CeO(2) and TiO(2) anatase phases were noted in the case of CeO(2)-TiO(2) sample. Formation of cubic Ce(0.75)Zr(0.25)O(2) and Ce(0.6)Zr(0.4)O(2) (at 1073 K) were observed in the case of the CeO(2)-ZrO(2) sample. Raman measurements disclose the fluorite structure of ceria and the presence of oxygen vacancies/Ce(3+). The HREM results reveal well-dispersed CeO(2) nanocrystals over the amorphous SiO(2) matrix in the cases of CeO(2)-SiO(2), isolated CeO(2), and TiO(2) (anatase) nanocrystals, some overlapping regions in the case of CeO(2)-TiO(2), and nanosized CeO(2) and Ce-Zr oxides in the case of CeO(2)-ZrO(2) sample. The exact structural features of these crystals as determined by digital diffraction analysis of HREM experimental images reveal that the CeO(2) is mainly in cubic fluorite geometry. The oxygen storage capacity (OSC) as determined by thermogravimetry reveals that the OSC of the mixed oxide systems is more than that of pure CeO(2) and is system dependent.

  10. Effects of CeO2 Nanoparticles on Terrestrial Isopod Porcellio scaber: Comparison of CeO2 Biological Potential with Other Nanoparticles.

    PubMed

    Malev, Olga; Trebše, Polonca; Piecha, Małgorzata; Novak, Sara; Budič, Bojan; Dramićanin, Miroslav D; Drobne, Damjana

    2017-02-01

    Nano-sized cerium dioxide (CeO2) particles are emerging as an environmental issue due to their extensive use in automobile industries as fuel additives. Limited information is available on the potential toxicity of CeO2 nanoparticles (NPs) on terrestrial invertebrates through dietary exposure. In the present study, the toxic effects of CeO2 NPs on the model soil organism Porcellio scaber were evaluated. Nanotoxicity was assessed by monitoring the lipid peroxidation (LP) level and feeding rate after 14-days exposure to food amended with nano CeO2. The exposure concentration of 1000 μg of CeO2 NPs g(-1) dry weight food for 14 days significantly increased both the feeding rate and LP. Thus, this exposure dose is considered the lowest observed effect dose. At higher exposure doses of 2000 and 5000 μg of CeO2 NPs g(-1) dry weight food, NPs significantly decreased the feeding rate and increased the LP level. Comparative studies showed that CeO2 NPs are more biologically potent than TiO2 NPs, ZnO NPs, CuO NPs, CoFe2O4 NPs, and Ag NPs based on feeding rate using the same model organism and experimental setup. Based on comparative metal oxide NPs toxicities, the present results contribute to the knowledge related to the ecotoxicological effects of CeO2 NPs in terrestrial invertebrates exposed through feeding.

  11. Oxygen transport in unreduced, reduced and Rh(III)-doped CeO2 nanocrystals.

    PubMed

    Sayle, Thi X T; Parker, Stephen C; Sayle, Dean C

    2007-01-01

    Ceria, CeO2, based materials are a major (active) component of exhaust catalysts and promising candidates for solid oxide fuel cells. In this capacity, oxygen transport through the material is pivotal. Here, we explore whether oxygen transport is influenced (desirably increased) compared with transport within the bulk parent material by traversing to the nanoscale. In particular, atomistic models for ceria nanocrystals, including perfect: CeO2; reduced: CeO1.95 and doped: Rh0.1Ce0.9O1.95, have been generated. The nanocrystals were about 8 nm in diameter and each comprised about 16,000 atoms. Oxygen transport can also be influenced, sometimes profoundly, by microstructural features such as dislocations and grain-boundaries. However, these are difficult to generate within an atomistic model using, for example, symmetry operations. Accordingly, we crystallised the nanocrystals from an amorphous precursor, which facilitated the evolution of a variety of microstructures including: twin-boundaries and more general grain-boundaries and grain-junctions, dislocations and epitaxy, isolated and associated point defects. The shapes of the nanocrystals are in accord with HRTEM data and comprise octahedral morphologies with {111} surfaces, truncated by (dipolar) {100} surfaces together with a complex array of steps, edges and corners. Oxygen transport data was then calculated using these models and compared with data calculated previously for CeO1.97/ YSZ thin films and the (bulk) parent material, CeO197. Oxygen transport was calculated to increase in the order: CeO2 nanocrystal < (reduced) CeO1.95 nanocrystal approximately Rh0.1Ce0.9O1.95 nanocrystal < CeO1.97/YSZ thin film < (reduced) CeO1.97 (bulk) parent material; the mechanism was determined to be primarily vacancy driven. Our findings indicate that reducing one- (thin film) or especially three- (nanocrystal) dimensions to the nanoscale may prove deleterious to oxygen transport. Conversely, we observed dynamic evolution and

  12. Growth and structural analysis of diluted magnetic oxide Co-doped CeO 2-δ films deposited on Si and SrTiO 3 (1 0 0)

    NASA Astrophysics Data System (ADS)

    Zheng, Y.; Vodungbo, B.; Vidal, F.; Selmane, M.; Demaille, D.

    2008-07-01

    The diluted magnetic oxide, Co-doped CeO 2-δ, displays ferromagnetism at room temperature [A. Tiwari, V.M. Bhosle, S. Ramachandran, N. Sudhakar, J. Narayan, S. Budak, A. Gupta, Appl. Phys. Lett. 88 (2006) 142511; B. Vodungbo, Y. Zheng, F. Vidal, D. Demaille, V.H. Etgens, D.H. Mosca, Appl. Phys. Lett. 90 (2007) 062510]. For this study, Co-doped CeO 2-δ thin films were grown on silicon and SrTiO 3 substrates by pulsed laser deposition. Their structure was analyzed using X-ray diffraction and transmission electron microscopy. On native silicon wafer, the films are textured. The preferential orientation is CeO 2 (1 0 0) for a growth under oxygen ambient (0.05 mbar) and CeO 2 (1 1 1) for a growth under vacuum (10 -6 mbar). When a buffer layer of CeO 2 is previously deposited under oxygen ambient, the films adopt the CeO 2 (1 0 0) preferential orientation, even if subsequent growth is carried out under vacuum. On SrTiO 3 (1 0 0), the films are epitaxied under oxygen ambient or under vacuum with an oxygen-grown CeO 2 buffer layer. In epitaxial films grown under vacuum, increasing contents of Co atoms (below 7%) induce an expansion of the CeO 2 unit cell and a decrease of crystalline order. The relationship between the structural order and the magnetic behaviour, in particular the magnetic anisotropy, is discussed. The present study suggests that the ferromagnetic behaviour is not related to grain boundaries and that the epitaxy strains are not responsible for the magnetic anisotropy. This strongly supports a ferromagnetism related to point defects (oxygen vacancies) in Co-doped CeO 2-δ films.

  13. 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.

  14. Visible light induced degradation of methylene blue using CeO2/V2O5 and CeO2/CuO catalysts.

    PubMed

    Saravanan, R; Joicy, S; Gupta, V K; Narayanan, V; Stephen, A

    2013-12-01

    In the present study, the nanocatalysts CeO2, V2O5, CuO, CeO2/V2O5 and CeO2/CuO were synthesized by thermal decomposition method. This method is simple, fast and cost effective compared with other preparation methods. The synthesized catalysts were characterized by different techniques. The XRD and XPS results confirmed the structure and the oxidization states of the nanocomposite materials. DRS results suggested that the prepared CeO2/V2O5 and CeO2/CuO nanocomposites can generate more electrons and holes under visible light irradiation. The photocatalytic activities of prepared catalysts were evaluated using the degradation of aqueous methylene blue solution as a model compound under visible light irradiation. In addition, the nanocomposite (CeO2/V2O5 and CeO2/CuO) materials were employed to degrade the textile effluent under visible light condition.

  15. 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.

  16. Size effect of Raman scattering on CeO2 nanocrystal by hydrothermal method

    NASA Astrophysics Data System (ADS)

    Hattori, Takashi; Kobayashi, Katsutoshi; Ozawa, Masakuni

    2017-01-01

    In this study, we prepared surface-modified CeO2 nanocrystals (NCs) by a hydrothermal method, and calcined CeO2 NCs at various temperatures between 400 and 1000 °C for 3 h in air to obtain crystal-size-controlled CeO2 NCs. We investigated the correlation between the Raman spectra and the crystal sizes of the CeO2 powder. The peak position of the F2g mode of CeO2 was shifted to lower energies as the crystal size decreased and the peak broadened. The present hydrothermally driven CeO2 NCs showed no change in lattice constant depending on crystal size after heat treatment. The Raman peak position of the F2g mode as a function of inverse CeO2 crystal size corresponded to the models for phonon confinement without the combination of strain and defect effects. Moreover, it was also suggested that the Raman peak width of CeO2 NCs without strain also showed dependence on particle size.

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

    PubMed

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

    2016-10-17

    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 Ce(3+)/Ce(4+) 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 Ce(3+)/Ce(4+) 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.

  18. 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.

  19. 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

  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. 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.

  3. 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.

  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. 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.

  7. 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.

  8. Controlled hydrothermal synthesis of CeO2 nanospheres and their excellent magnetic properties

    NASA Astrophysics Data System (ADS)

    Niu, Xiaofei

    2017-04-01

    Monodisperse spherical CeO2 nanostructures with irregular and rough surfaces have successfully been synthesized via a facile hydrothermal technology. XRD, SEM, XPS, Raman scattering, and M-H curves were employed to characterize the samples. The results showed that the spherical CeO2 nanostructures have a cubic fluorite structure and that there are Ce3+ ions and oxygen vacancies in the surface of the samples. The M-H curve of CeO2 nanospheres exhibits excellent room-temperature ferromagnetism (RT-FM), which is likely ascribed to the effects of the Ce3+ ions and oxygen vacancies.

  9. The Preparation, Characterization and Photocatalytic Activity of Mixed P25/CeO2 Nanocomposites

    NASA Astrophysics Data System (ADS)

    Liu, I.-Tsan; Hon, Min-Hsiung; Teoh, Lay Gaik

    2017-03-01

    This study uses the wet chemical method to synthesize P25 (TiO2)/CeO2 composites by mixing P25 and Ce(NO3)3·6H2O at different volumetric concentrations. X-ray diffraction, transmission electron microscopy and ultraviolet-visible diffuse reflectance spectroscopy are used to analyze the structure, morphology, optical properties and photocatalytic activity of the TiO2/CeO2 composites with different compositions. The pollutant, methylene blue solution, was used for analysis. The results show that the photocatalytic activity of the composite catalysts is greater than that of pure TiO2 or pure CeO2. The catalyst, TiO2 55%/CeO2 (v/v), exhibits the greatest level of photocatalytic activity.

  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. The Preparation, Characterization and Photocatalytic Activity of Mixed P25/CeO2 Nanocomposites

    NASA Astrophysics Data System (ADS)

    Liu, I.-Tsan; Hon, Min-Hsiung; Teoh, Lay Gaik

    2017-01-01

    This study uses the wet chemical method to synthesize P25 (TiO2)/CeO2 composites by mixing P25 and Ce(NO3)3·6H2O at different volumetric concentrations. X-ray diffraction, transmission electron microscopy and ultraviolet-visible diffuse reflectance spectroscopy are used to analyze the structure, morphology, optical properties and photocatalytic activity of the TiO2/CeO2 composites with different compositions. The pollutant, methylene blue solution, was used for analysis. The results show that the photocatalytic activity of the composite catalysts is greater than that of pure TiO2 or pure CeO2. The catalyst, TiO2 55%/CeO2 (v/v), exhibits the greatest level of photocatalytic activity.

  12. Transport and deposition of CeO2 nanoparticles in water-saturated porous media.

    PubMed

    Li, Zhen; Sahle-Demessie, Endalkachew; Hassan, Ashraf Aly; Sorial, George A

    2011-10-01

    Ceria nanoparticles are used for fuel cell, metal polishing and automobile exhaust catalyst; however, little is known about the impact of their release to the environment. The stability, transport and deposition of engineered CeO2 nanoparticles through water-saturated column packed with sand were studied by monitoring effluent CeO2 concentration. The influence of solution chemistry such as ionic strength (1-10 mM) and pH (3-9) on the mobility and deposition of CeO2 nanoparticles was investigated by using a three-phase (deposition-rinse-reentrainment) procedure in packed bed columns. The results show that water chemistry governs the transport and deposition of CeO2 nanoparticles. Transport is significantly hindered at acidic conditions (pH 3) and high ionic strengths (10 mM and above), and the deposited CeO2 particles may not be re-entrained by increasing the pH or lowering the ionic strength of water. At neutral and alkaline conditions (pH6 and 9), and lower ionic strengths (below 10 mM), partial breakthrough of CeO2 nanoparticles was observed and particles can be partially detached and re-entrained from porous media by changing the solution chemistry. A mathematical model was developed based on advection-dispersion-adsorption equations and it successfully predicts the transport, deposition and re-entrainment of CeO2 nanoparticles through a packed bed. There is strong agreement between the deposition rate coefficients calculated from experimental data and predicted by the model. The successful prediction for attachment and detachment of nanoparticles during the deposition and re-entrainment phases is unique addition in this study. This work can be applied to access the risk of CeO2 nanoparticles transport in contaminated ground water.

  13. Surface reaction network of CO oxidation on CeO2/Au(110) inverse model catalysts.

    PubMed

    Ding, Liangbing; Xiong, Feng; Jin, Yuekang; Wang, Zhengming; Sun, Guanghui; Huang, Weixin

    2016-11-30

    CeO2/Au(110) inverse model catalysts were prepared and their activity toward the adsorption and co-adsorption of O2, CO, CO2 and water was studied by means of X-ray photoelectron spectroscopy, low energy electron diffraction, thermal desorption spectra and temperature-programmed reaction spectra. The Au surface of CeO2/Au(110) inverse model catalysts molecularly adsorbs CO, CO2 and water, and the polycrystalline CeO2 surface of CeO2/Au(110) inverse model catalysts molecularly adsorbs O2, and molecularly and reactively adsorbs CO, CO2 and water. By controllably preparing co-adsorbed surface species on CeO2/Au(110) inverse model catalysts, we successfully identified various surface reaction pathways of CO oxidation to produce CO2 with different barriers both on the CeO2 surface and at the Au-CeO2 interface, including CO oxidation by various oxygen species, and water/hydroxyl group-involved CO oxidation. These results establish a surface reaction network of CO oxidation catalyzed by Au/CeO2 catalysts, greatly advancing the fundamental understandings of catalytic CO oxidation reactions.

  14. 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.

  15. Enhanced photocatalytic performances of CeO2/TiO2 nanobelt heterostructures.

    PubMed

    Tian, Jian; Sang, Yuanhua; Zhao, Zhenhuan; Zhou, Weijia; Wang, Dongzhou; Kang, Xueliang; Liu, Hong; Wang, Jiyang; Chen, Shaowei; Cai, Huaqiang; Huang, Hui

    2013-11-25

    CeO2 /TiO2 nanobelt heterostructures are synthesized via a cost-effective hydrothermal method. The as-prepared nanocomposites consist of CeO2 nanoparticles assembled on the rough surface of TiO2 nanobelts. In comparison with P25 TiO2 colloids, surface-coarsened TiO2 nanobelts, and CeO2 nanoparticles, the CeO2 /TiO2 nanobelt heterostructures exhibit a markedly enhanced photocatalytic activity in the degradation of organic pollutants such as methyl orange (MO) under either UV or visible light irradiation. The enhanced photocatalytic performance is attributed to a novel capture-photodegradation-release mechanism. During the photocatalytic process, MO molecules are captured by CeO2 nanoparticles, degraded by photogenerated free radicals, and then released to the solution. With its high degradation efficiency, broad active light wavelength, and good stability, the CeO2 /TiO2 nanobelt heterostructures represent a new effective photocatalyst that is low-cost, recyclable, and will have wide application in photodegradation of various organic pollutants. The new capture-photodegradation-release mechanism for improved photocatalysis properties is of importance in the rational design and synthesis of new photocatalysts.

  16. Structure and Optical Properties of CeO2 Nanoparticles Synthesized by Precipitation

    NASA Astrophysics Data System (ADS)

    Liu, I.-Tsan; Hon, Min-Hsiung; Teoh, Lay Gaik

    2013-08-01

    Cerium dioxide (CeO2) has special electrical and optical properties, and chemical and thermal stability. It has been used in semiconductor devices and as a luminescent material. In this work, CeO2 nanoparticles were synthesized by the precipitation method and the product annealed at various temperatures. Thermogravimetric analysis (TGA)/differential scanning calorimetry (DSC) results show that the optimum annealing temperature for fabrication of CeO2 nanoparticles is greater than 500°C. When the calcination temperature is increased from 550°C to 1050°C, Fourier-transform infrared (FTIR) results show that the water and impurities are almost completely removed, after calcination at 750°C. The x-ray diffraction (XRD) results suggest that the synthesized CeO2 exhibits a cubic fluorite structure. The crystallite size of the CeO2 increases from 8 nm to 75 nm when the calcination temperature is increased from 550°C to 1050°C. The absorption spectrum in the ultraviolet (UV) region from 372 nm to 395 nm demonstrates their applicability as UV-filter materials, and the shift of the estimated E g,eff from 3.21 eV to 3.65 eV demonstrates their applicability in photoelectric devices. CeO2 would be potentially important for applications such as insulator structures, stable capacitor devices, and light-emitting diodes (LEDs).

  17. 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.

  18. 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.

  19. 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.

  20. Fabrication of CeO 2 buffer layer with high deposition rate on biaxially textured Ni-3%W substrate by electron beam evaporation

    NASA Astrophysics Data System (ADS)

    Lee, J. B.; Park, S. K.; Kim, B. J.; Lee, H. J.; Kim, S. S.; Moon, S. H.; Lee, H. G.; Hong, G. W.

    2011-11-01

    CeO2 has been used as a buffer layer of a coated conductor because of good chemical and structural compatibility with YBCO. But cracks were often observed at the surface for films thicker than 100 nm deposited at a high temperature because of a large difference in a thermal expansion coefficient between metal and CeO2. The deposition rate was limited to be slow for getting good epitaxy. In order to increase the film deposition rate, while maintaining the epitaxy till a final thickness, two-step deposition process was tested. The thin seed layer with a thickness less than 10 nm was deposited with a deposition rate of 3 Å/s, and the homo-epitaxial layer at a thickness more than 240 nm was deposited at a deposition rate of 30 Å/s. The resulting CeO2 films deposited at 600 °C showed a good texture with a Δφ of 5.3°, Δω of 4.2° and Ra of 2.2 nm. The two-step process may be option for a low cost buffer layer for Ni-3%W metal substrates for the coated conductor.

  1. 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

  2. Single-step process to prepare CeO2 nanotubes with improved catalytic activity.

    PubMed

    González-Rovira, Leandro; Sánchez-Amaya, José M; López-Haro, Miguel; del Rio, Eloy; Hungría, Ana B; Midgley, Paul; Calvino, José J; Bernal, Serafín; Botana, F Javier

    2009-04-01

    CeO(2) nanotubes have been grown electrochemically using a porous alumina membrane as a template. The resulting material has been characterized by means of scanning electron microscopy (SEM), X-ray energy dispersive spectroscopy, high-angle annular dark-field scanning transmission electron microscopy tomography, high-resolution electron microscopy (HREM), and electron energy loss spectroscopy. According to SEM, the outer diameter of the nanotubes corresponds to the pore size (200 nm) of the alumina membrane, and their length ranges between 30 and 40 microm. HREM images have revealed that the width of the nanotube walls is about 6 nm. The catalytic activity of these novel materials for the CO oxidation reaction is compared to that of a polycrystalline powder CeO(2) sample prepared by a conventional route. The activity of the CeO(2) nanotubes is shown to be in the order of 400 times higher per gram of oxide at 200 degrees C (77.2 x 10(-2) cm(3) CO(2) (STP)/(gxs) for the nanotube-shaped CeO(2) and 0.16 x 10(-2) cm(3) CO(2) (STP)/(gxs) for the powder CeO(2)).

  3. Formation of CeO2 nanotubes from Ce(OH)CO3 nanorods through Kirkendall diffusion.

    PubMed

    Chen, Guozhu; Sun, Sixiu; Sun, Xun; Fan, Weiliu; You, Ting

    2009-02-16

    In this paper, CeO(2) nanotubes based on the Kirkendall effect (for simplicity, this type of nanotubes is denoted as K-type CeO(2) nanotubes) are fabricated through a solid-liquid interface reaction between Ce(OH)CO(3) nanorods and NaOH solutions. Our studies indicate the formation mechanism of K-type CeO(2) nanotubes is quite different from those of CeO(2) nanotubes subjected to template (T-type CeO(2) nanotubes) and lamellar rolling (L-type CeO(2) nanotubes) reported previously by our group. The K-type CeO(2) nanotubes are prepared by congregating Kirkendall voids and subsequent calcinations. The time evolution processes are imaged by TEM, and the results show that as the reaction processes, interior spaces are formed and enlarged in Ce(OH)CO(3) nanorods to form K-type CeO(2) nanotubes. In contrast, the interior space in T-type CeO(2) nanotubes decreases with reaction time. XRD is applied to study the phase transformation in the formation process of K-type CeO(2) nanotubes. Our study also indicates NaOH and reaction temperature are two key factors responsible for formation of K-type CeO(2) nanotubes. Combined with the T- and L-type nanotubes, three types of CeO(2) nanotubes with different formation mechanisms are successfully synthesized in one reaction system, which might afford some guidance for the synthesis of other inorganic nanotubes.

  4. Particle-specific toxicity and bioavailability of cerium oxide (CeO2) nanoparticles to Arabidopsis thaliana.

    PubMed

    Yang, Xinping; Pan, Haopeng; Wang, Peng; Zhao, Fang-Jie

    2017-01-15

    The use of manufactured cerium oxide nanoparticles (CeO2-NPs) in consumer products has increased markedly over the past decade, and their release into natural ecosystems is unavoidable. This study investigated the phytotoxicity and uptake of CeO2-NPs in Arabidopsis thaliana grown in an agar medium. Although low concentrations of CeO2-NPs had stimulatory effects on plant growth, at higher concentrations, CeO2-NPs reduced growth and had adverse effects on the antioxidant systems and photosystem. Importantly, the toxicity resulted from the nanoparticles per se, rather than from the dissolved Ce ions. CeO2-NPs were taken up and subsequently translocated to shoot tissues, and transmission electron microscopy (TEM) showed the presence of a large number of needle-like particle aggregations in the intercellular regions and the cytoplasm of leaf cells. The up-translocation factor to shoots was independent of the concentrations of Ce in the roots and the supplied forms of Ce (i.e. CeO2-NPs, CeO2-bulk, and ionic Ce), suggesting that endocytosis is likely to be a general mechanism responsible for the translocation of these Ce compounds. These findings provide important information regarding the toxicity and uptake of CeO2-NPs in plants, which needs to be considered in environmental risk assessment for the safe use and disposal of CeO2-NPs.

  5. 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.

  6. Fabrication of CeO2 nanoparticle-modified silk for UV protection and antibacterial applications.

    PubMed

    Lu, Zhisong; Mao, Cuiping; Meng, Mei; Liu, Sangui; Tian, Yunli; Yu, Ling; Sun, Bai; Li, Chang Ming

    2014-12-01

    To endow silk with UV-shielding ability and antibacterial activity, CeO2 nanoparticles were immobilized on silk surface via a dip-coating approach without changing silk structure. Surface density of the nanoparticles could be easily adjusted by controlling the number of dip-coating cycle. Enhanced thermal stability of the modified silk is exhibited in thermogravimetric analysis (TGA) and derivative thermogravimetric analysis (DTG). The excellent UV-protection ability and antibacterial property of the CeO2 nanoparticle-coated silk are demonstrated in UV-vis diffuse reflectance spectroscopy and colony-forming capability test, respectively. Based on the data, it can be concluded that CeO2 nanoparticles could be used as a very promising coating material to modify silk for UV-protection and antibacterial applications.

  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. Intense up-conversion luminescence in Er3+/Yb3+ co-doped CeO2 powders.

    PubMed

    Singh, Vijay; Rathaiah, M; Venkatramu, V; Haase, Markus; Kim, S H

    2014-03-25

    The Er(3+) and Er(3+)/Yb(3+) co-doped CeO2 powders have been prepared by a urea combustion route. The structural, morphological, compositional and vibrational analysis of the Er(3+):CeO2 and Er(3+)/Yb(3+):CeO2 powders have been studied by X-ray diffraction, scanning electron microscopy, energy dispersive X-ray and Fourier transform infrared spectroscopy. The optical and luminescence properties of Er(3+):CeO2 and Er(3+)/Yb(3+):CeO2 powders have been studied by using laser excited spectroscopy. The effects of Yb(3+) doping on up-conversion luminescence of Er(3+) co-doped CeO2 powders were studied. The ratio of red to green intensity is decreased in Er(3+):CeO2 whereas the ratio is increased in Er(3+)/Yb(3+):CeO2 powders with increase of power. The effect of co-doping with the Yb(3+) ions on the visible luminescence of Er(3+) and the energy transfer mechanism responsible for the variation in the green and red intensity are discussed. The results indicate that these materials may be suitable for display and light emitting devices.

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

    PubMed

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

    2015-05-05

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

  13. 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 ...

  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. 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.

  16. Effect of Zn doping on structural, optical and thermal properties of CeO2 nanoparticles

    NASA Astrophysics Data System (ADS)

    Ramasamy, V.; Vijayalakshmi, G.

    2015-09-01

    The undoped and Zn doped CeO2 nanoparticles were synthesized by chemical precipitation method at room temperature. The undoped and Zn doped CeO2 nanoparticles have been characterized by X-ray powder diffraction (XRD), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), ultraviolet visible and photoluminescence (PL) spectroscopy, Fourier transform infrared spectroscopy (FTIR) and thermogravimetry and differential thermal analysis (TG-DTA). The cubic fluorite structures of the CeO2 nanoparticles were determined by XRD. The influence of particle size on structural parameters such as lattice parameter (a), inter planar distance (d), dislocation density (δ), microstrain (ε), lattice strain (η) and texture co-efficient (TC) were also determined. The lattice strains were determined by Williamson-Hall plot method. The effect of Zn doping with shifting of the bands were observed by UV-Vis spectroscopy and also their optical band gap were determined. The emission spectra and energy band diagram of the undoped and Zn doped samples were derived from PL spectroscopy. The structural bond vibrations of undoped and Zn doped CeO2 nanoparticles were analyzed by FTIR spectroscopy. The thermal property (weight loss and decomposition) of the sample is observed by TG-DTA curve.

  17. 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

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

    DOE PAGES

    Alammar, Tarek; Noei, Heshmat; Wang, Yuemin; ...

    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

  19. 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.

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

    PubMed

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

    This article reports the green fabrication of cerium oxide nanoparticles (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.

  1. 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.

  2. Synthesis, characterization, and ecotoxicity of CeO2 nanoparticles with differing properties

    NASA Astrophysics Data System (ADS)

    Alam, Bushra; Philippe, Allan; Rosenfeldt, Ricki R.; Seitz, Frank; Dey, Sonal; Bundschuh, Mirco; Schaumann, Gabriele E.; Brenner, Sara A.

    2016-10-01

    CeO2 nanoparticles with various characteristics find an increasing number of applications in the electronic, medical, and other industries and are therefore likely released in the environment. This calls for investigations linking the physicochemical properties of these particles with their potential environmental impacts. In this study, CeO2 nanoparticle powders were prepared using three different precursors [Ce(NO3)3, CeCl3, and Ce(CH3COO)3] and annealing temperatures (300, 500, and 700 °C). This procedure resulted in nine different types of nanoparticles with differing size (5-90 nm), morphology, surface Ce3+/Ce4+ ratio, and slightly different crystal structures as characterized using transmission electron microscopy, dynamic light scattering, X-ray photoelectron spectroscopy, and X-ray diffraction measurements with Rietveld refinement. These CeO2 nanoparticles underwent toxicity testing at concentrations up to 64 mg L-1 using Daphnia magna. Toxic effects were observed for three particle types with EC50 values between 5 and 64 mg L-1. No clear correlation was observed between the physicochemical properties (size, shape, oxygen occupancy, Ce3+/Ce4+ ratio) of the nanoparticles and their toxicity. However, toxicity was correlated with the amount of Ce remaining suspended in the test medium after 24 h. This indicated that toxic effects may depend on the colloidal stability of CeO2 nanoparticles during the first day of exposure. Therefore, being readily suspended and remaining stable for several days in the aquatic media increases the likelihood that CeO2 nanoparticles will cause unwanted adverse effects.

  3. Microwave synthesis of pure and doped cerium (IV) oxide (CeO2) nanoparticles for methylene blue degradation.

    PubMed

    El Rouby, W M A; Farghali, A A; Hamdedein, A

    2016-11-01

    Cerium (IV) oxide (CeO2), samarium (Sm) and gadolinium (Gd) doped CeO2 nanoparticles were prepared using microwave technique. The effect of microwave irradiation time, microwave power and pH of the starting solution on the structure and crystallite size were investigated. The prepared nanoparticles were characterized using X-ray diffraction, FT-Raman spectroscopy, and transmission electron microscope. The photocatalytic activity of the as-prepared CeO2, Sm and Gd doped CeO2 toward degradation of methylene blue (MB) dye was investigated under UV light irradiation. The effect of pH, the amount of catalyst and the dye concentration on the degradation extent were studied. The photocatalytic activity of CeO2 was kinetically enhanced by trivalent cation (Gd and Sm) doping. The results revealed that Gd doped CeO2 nanoparticles exhibit the best catalytic degradation activity on MB under UV irradiation. For clarifying the environmental safety of the by products produced from the degradation process, the pathways of MB degradation were followed using liquid chromatography/mass spectroscopy (LC/MS). The total organic carbon content measurements confirmed the results obtained by LC/MS. Compared to the same nanoparticles prepared by another method, it was found that Gd doped CeO2 prepared by hydrothermal process was able to mineralize MB dye completely under UV light irradiation.

  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. Effects and implications of trophic transfer and accumulation of CeO2 nanoparticles in a marine mussel.

    PubMed

    Conway, Jon R; Hanna, Shannon K; Lenihan, Hunter S; Keller, Arturo A

    2014-01-01

    Bivalves are hypothesized to be key organisms in the fate and transport of engineered nanomaterials (ENMs) in aquatic environments due to their ability to filter and concentrate particles from water, but how different exposure pathways influence their interactions with ENMs is not well understood. In a five-week experiment, we tested how interactions between CeO2 ENMs and a marine mussel, Mytilus galloprovincialis, are affected through two exposure methods, direct and through sorption to phytoplankton. We found that phytoplankton sorbed ENMs in <1 h. The exposure methods used did not result in significantly different mussel tissue or pseudofeces Ce concentrations. Approximately 99% of CeO2 was captured and excreted in pseudofeces and average pseudofeces mass doubled in response to CeO2 exposure. Final mean dry tissue Ce concentration (±SE) for treatments exposed to 3 mg L(-1) CeO2 directly was 33 ± 9 μg g(-1) Ce, and 0 ± 0, 19 ± 4, 21 ± 3, and 28 ± 5 μg g(-1) for treatments exposed to 0, 1, 2, and 3 mg L(-1) CeO2 sorbed to phytoplankton. Clearance rates increased with CeO2 concentration but decreased over time in groups exposed to CeO2 directly, indicating stress. These results show the feedback between ENM toxicity and transport and the likelihood of biological mediation in the fate and transport of ENMs in aquatic environments.

  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. 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.

  8. Distribution, bioaccumulation, trophic transfer, and influences of CeO2 nanoparticles in a constructed aquatic food web.

    PubMed

    Zhao, Xingchen; Yu, Miao; Xu, Dan; Liu, Aifeng; Hou, Xingwang; Hao, Fang; Long, Yanmin; Zhou, Qunfang; Jiang, Guibin

    2017-04-06

    In view of the final destination of nanomaterials, the water system would be the important sink. However, the environmental behavior of nanomaterials is rather confusing due to the complexity of the real environment. In this study, a fresh water ecosystem, including water, sediment, water lettuce, water silk, Asian clam, snail, water flea, the Japanese Medaka, and the Yamato shrimp, was constructed to study the distribution, bioaccumulation and potential impacts of CeO2 nanoparticles (CeO2 NPs) via long-term exposure. The results demonstrated most of the CeO2 NPs deposited in the sediment (88.7%) when the partition approached constantly 30 days later. The bioaccumulated Ce in 6 tested biota species was negatively correlated with its trophic level, showing no biomagnification of CeO2 NPs through this food web. CeO2 NP exposure induced visual abnormalities in hydrophytes including chlorophyll loss in water silk and water lettuce, ultrastructural changes in pyrenoids of water silk and root elongation in water lettuce. The generation of hydroxyl radical (OH) and cell wall loosening induced by CeO2 NP exposure might mediate the increased root growth in water lettuce. The findings on the environmental behavior of CeO2 NPs in water system have provided useful information on the risk assessment of nanomaterials.

  9. 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

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

    DOE PAGES

    Calaza, Florencia C.; Chen, Tsung -Liang; Mullins, David R.; ...

    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. 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.

  12. 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.

  13. 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.

  14. Efficient MnOx-Co3O4-CeO2 catalysts for formaldehyde elimination

    NASA Astrophysics Data System (ADS)

    Lu, Suhong; Li, Kelun; Huang, Fenglin; Chen, Canchang; Sun, Bo

    2017-04-01

    A series of highly efficient MnOx-Co3O4-CeO2 mixed oxides, synthesized by a sol-gel citric acid method, were applied to eliminate indoor formaldehyde (HCHO). The influence of the molar ratio of Mn/Co/Ce was investigated. The catalyst could efficiently eliminate HCHO into CO2 and H2O when the molar ratio of Mn/Co/Ce was 16/19/1. Complete HCHO conversion was achieved at a temperature as low as 100 °C. The prepared samples were characterized by N2 adsorption and desorption, XRD, H2-TPR and O2-TPD techniques to explain the improvement of catalytic activity. The results show that the introduction of MnOx into Co3O4-CeO2 could improve the high dispersion of Co3O4 and then increase the surface areas. Especially, the addition of MnOx enhanced reducibility and abundant surface active oxygen of MnOx-Co3O4-CeO2, which contributed to the excellent catalytic activity toward complete elimination of HCHO.

  15. Simple Route to Obtain Nanostructured CeO2 Microspheres and CO Gas Sensing Performance.

    PubMed

    López-Mena, Edgar R; Michel, Carlos R; Martínez-Preciado, Alma H; Elías-Zuñiga, Alex

    2017-12-01

    In this work, nanostructured CeO2 microspheres with high surface area and mesoporosity were prepared by the coprecipitation method, in absence of a template. The reaction between cerium nitrate and concentrated formic acid produced cerium formate, at room temperature. Further, calcination at 300 °C yielded single-phase CeO2 microspheres, with a diameter in the range 0.5-2.6 μm, the surface of these microspheres is completely nanostructured (diameter about 30-90 nm). CeO2 microspheres were used to fabricate a sensor device, and it was tested for intermediate CO gas concentrations (200-800 ppm). The detection of 200 ppm carbon monoxide was observed at 275 °C, with a response time of 9 s, using an applied frequency of 100 kHz. The detection of changes on the CO gas concentration was studied at different temperatures and applied frequencies. The results revealed a reproducible and stable gas sensing response.

  16. Electronic structure and excitations in oxygen deficient CeO2-δ from DFT calculations

    NASA Astrophysics Data System (ADS)

    Jarlborg, T.; Barbiellini, B.; Lane, C.; Wang, Yung Jui; Markiewicz, R. S.; Liu, Zhi; Hussain, Zahid; Bansil, A.

    2014-04-01

    The electronic structures of supercells of CeO2-δ have been calculated within the density functional theory (DFT). The equilibrium properties such as lattice constants, bulk moduli, and magnetic moments are well reproduced by the generalized gradient approximation (GGA). Electronic excitations are simulated by robust total-energy calculations for constrained states with atomic core holes or valence holes. Pristine ceria CeO2 is found to be a nonmagnetic insulator with magnetism setting in as soon as oxygens are removed from the structure. In the ground state of defective ceria, the Ce-f majority band resides near the Fermi level but appears at about 2 eV below the Fermi level in photoemission spectroscopy experiments due to final-state effects. We also tested our computational method by calculating threshold energies in Ce-M5 and O-K x-ray absorption spectroscopy and comparing theoretical predictions with the corresponding measurements. Our result that f electrons reside near the Fermi level in the ground state of oxygen-deficient ceria is crucial for understanding the catalytic properties of CeO2 and related materials.

  17. O vacancies on steps on the CeO2(111) surface.

    PubMed

    Kozlov, Sergey M; Neyman, Konstantin M

    2014-05-07

    Cerium dioxide is a compound important for heterogeneous catalysis, energy technologies, biomedical applications, etc. One of its most remarkable properties is low O vacancy (Ovac) formation energy Ef. Nanostructuring of ceria was shown to decrease Ef and to make the oxide material more active in oxidative reactions. Here we investigate computationally formation of Ovac on CeO2(111) surfaces nanostructured by steps with experimentally observed structures. To facilitate the search for Ovac + 2Ce(3+) configurations that yield the lowest Ef values we proposed and employed an efficient computational scheme where DFT + U calculations were preceded by a pre-screening procedure based on the results of plain DFT calculations. Ef values on the steps were calculated to be up to 0.7 eV lower than on a regular CeO2(111) surface. Some energetically stable Ovac + 2Ce(3+) configurations were found to include subsurface Ce(3+) ions. The present results quantify to what extent the roughness of the CeO2(111) surface affects its reducibility.

  18. Simple Route to Obtain Nanostructured CeO2 Microspheres and CO Gas Sensing Performance

    NASA Astrophysics Data System (ADS)

    López-Mena, Edgar R.; Michel, Carlos R.; Martínez-Preciado, Alma H.; Elías-Zuñiga, Alex

    2017-03-01

    In this work, nanostructured CeO2 microspheres with high surface area and mesoporosity were prepared by the coprecipitation method, in absence of a template. The reaction between cerium nitrate and concentrated formic acid produced cerium formate, at room temperature. Further, calcination at 300 °C yielded single-phase CeO2 microspheres, with a diameter in the range 0.5-2.6 μm, the surface of these microspheres is completely nanostructured (diameter about 30-90 nm). CeO2 microspheres were used to fabricate a sensor device, and it was tested for intermediate CO gas concentrations (200-800 ppm). The detection of 200 ppm carbon monoxide was observed at 275 °C, with a response time of 9 s, using an applied frequency of 100 kHz. The detection of changes on the CO gas concentration was studied at different temperatures and applied frequencies. The results revealed a reproducible and stable gas sensing response.

  19. Raman study of CeO2 texture as a buffer layer in the CeO2/La2Zr2O7/Ni architecture for coated conductors.

    PubMed

    Jiménez, C; Caroff, T; Bartasyte, A; Margueron, S; Abrutis, A; Chaix-Pluchery, O; Weiss, F

    2009-04-01

    The CeO(2)/La(2)Zr(2)O(7)/Ni piled-up structure is a very promising architecture for YBa(2)Cu(3)O(7) (YBCO) coated conductors. We have grown YBCO/CeO(2)/LZO/Ni epitaxial structures by metalorganic decomposition (MOD) and metalorganic chemical vapor deposition (MOCVD) methods. The crystallographic quality of the CeO(2) layer is not well determined by conventional X-ray diffraction (XRD) due to the superposition of LZO and CeO(2) reflections. An alternative simple Raman spectroscopy analysis of the crystalline quality of the CeO(2) films is proposed. The F(2g) Raman mode of CeO(2) can be quantified either by using two polarization configurations (crossed or parallel) or at two different rotation angles around the normal axis (0 degrees and 45 degrees ) to obtain information about the sample texture. The sample texture can be determined via a quality factor (referred to as the Raman intensity ratio, RIR) consisting of calculating the ratio of the integrated intensity of the CeO(2) F(2g) mode at 0 degrees and 45 degrees in parallel polarization. This factor correlates with superconducting performance and the technique can be used as an on-line nondestructive characterization method.

  20. Studies on the Surface Morphology and Orientation of CeO2 Films Deposited by Pulsed Laser Ablation

    NASA Astrophysics Data System (ADS)

    Develos, Katherine; Kusunoki, Masanobu; Ohshima, Shigetoshi

    1998-11-01

    We studied the surface morphology and orientation of CeO2 films grown by pulsed laser ablation (PLA) on r-cut (1\\=102) Al2O3 substrates and evaluated the effects of predeposition annealing conditions of Al2O3 and film thickness of CeO2. The annealing of Al2O3 substrates improves the smoothness of the surface and performing this in high vacuum leads to better crystallinity and orientation of deposited CeO2 films compared to those annealed in oxygen. A critical value of the film thickness was found beyond which the surface roughness increases abruptly. Atomic force microscopy (AFM) study showed that the surface of CeO2 films is characterized by a mazelike pattern. Increasing the film thickness leads to the formation of larger islands which cause the increase in the surface roughness of the films. The areal density and height of these islands increased with film thickness.

  1. Microstructure and corrosion resistance of Ni-based alloy laser coatings with nanosize CeO2 addition

    NASA Astrophysics Data System (ADS)

    Zhang, Shi Hong; Li, Ming Xi; Yoon, Jae Hong; Cho, Tong Yul; Zhu He, Yi; Lee, Chan Gyu

    2008-07-01

    Micron-size Ni-base alloy (NBA) powders were mixed with both 1.5 wt.% (hereinafter %) micron-size CeO2 (m-CeO2) and also 1.5% and 3.0% nano-size CeO2 (n- CeO2) powders. These mixtures were coated on low-carbon steel (Q235) by 2.0 kW CO2 laser cladding. The effects on the microstructures, phases and electrochemical corrosion of the coatings upon the addition of m- and n- CeO2 powders to NBA (m- and n- CeO2 /NBA) have been investigated. The results showed that a smooth coating was prepared under suitable processing parameters (P= 2.0 kW, V= 180 mm min- 1) by adding 1.5% n- CeO2. In addition to the primary phases of γ-Ni, Cr23 C6 and Ni3 B in the Ni-base alloy coating, CeNi3 was formed in Ni-base alloy coatings with both n- CeO2 and m-CeO2 particles, and CeNi5 appeared in the coating upon decreasing the size of CeO2 particles. Well-developed dendrites were observed in the Ni-base alloy coating; directional dendrites grew at the interface in the coating upon the addition of m-CeO2, whereas fine and multioriented dendrites grew upon decreasing the size of CeO2 particles to the nanoscale. Actinomorphic dendrites and compact equiaxed dendrites grew from the interface to near the surface upon increasing the content of n- CeO2 from 1.5 to 3.0%. In strongly acidic HNO3 solution, the severe corrosion of dendrites occurred and there were many corrosion pits in the Ni-base alloy coating; intercrystalline corrosion also has a dominant role upon the addition of m-CeO2, whereas uniform corrosion occurs in the coating as the size of CeO2 particles is decreased to nanoscale.

  2. In vitro skin decontamination of the organophosphorus pesticide Paraoxon with nanometric cerium oxide CeO2.

    PubMed

    Salerno, Alicia; Devers, Thierry; Bolzinger, Marie-Alexandrine; Pelletier, Jocelyne; Josse, Denis; Briançon, Stéphanie

    2017-04-01

    Organophosphorus compounds (OP), which mainly penetrate via the percutaneous pathway, represent a threat for both military and civilians. Body surface decontamination is vital to prevent victims poisoning. The development of a cost-effective formulation, which could be efficient and easy to handle in case of mass contamination, is therefore crucial. Metal oxides nanoparticles, due their large surface areas and the large amount of highly reactive sites, present high reactivity towards OP. First, this study aimed at evaluating the reaction of CeO2 nanoparticles, synthetized by microwave path and calcined at 500 or 600 °C, with Paraoxon (POX) in aqueous solution. Results showed that both nanoparticles degraded 60%-70% of POX. CeO2 calcined at 500 °C, owing to its larger specific area, was the most effective. Moreover, the degradation was significantly increased under Ultra-Violet irradiation (initial degradation rate doubled). Then, skin decontamination was studied in vitro using the Franz cell method with pig-ear skin samples. CeO2 powder and an aqueous suspension of CeO2 (CeO2-W) were applied 1 h after POX exposure. The efficiency of decontamination, including removal and/or degradation of POX, was compared to Fuller's earth (FE) and RSDL lotion which are, currently, the most efficient systems for skin decontamination. CeO2-W and RSDL were the most efficient to remove POX from the skin surface and decrease skin absorption by 6.4 compared to the control not decontaminated. FE reduced significantly (twice) the absorbed fraction of POX, contrarily to CeO2 powder. Considering only the degradation rate of POX, the products ranged in the order CeO2 > RSDL > CeO2-W > FE (no degradation). This study showed that CeO2 nanoparticles are a promising material for skin decontamination of OP if formulated as a dispersion able to remove POX like CeO2-W and to degrade it as CeO2 powder.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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

  9. 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

  10. 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.

  11. 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.

  12. Effects of deposited Pt particles on the reducibility of CeO2(111).

    PubMed

    Bruix, Albert; Migani, Annapaola; Vayssilov, Georgi N; Neyman, Konstantin M; Libuda, Jörg; Illas, Francesc

    2011-06-21

    The interaction of Pt particles with the regular CeO(2)(111) surface has been studied using Pt(8) clusters as representative examples. The atomic and electronic structure of the resulting model systems have been obtained through periodic spin-polarized density functional calculations using the PW91 exchange-correlation potential corrected with the inclusion of a Hubbard U parameter. The focus is on the effect of the metal-support interaction on the surface reducibility of ceria. Several initial geometries and orientations of Pt(8) with respect to the ceria substrate have been explored. It has been found that deposition of Pt(8) over the ceria surface results in spontaneous oxidation of the supported particle with a concomitant reduction of up to two Ce(4+) cations to Ce(3+). Oxygen vacancy formation on the CeO(2)(111) surface and oxygen spillover to the adsorbed particle have also been considered. The presence of the supported Pt(8) particles has a rather small effect (∼0.2 eV) on the O vacancy formation energy. However, it is predicted that the spillover of atomic oxygen from the substrate to the metal particle greatly facilitates the formation of oxygen vacancies: the calculated energy required to transfer an oxygen atom from the CeO(2)(111) surface to the supported Pt(8) particle is only 1.00 eV, i.e. considerably smaller than 2.25 eV necessary to form an oxygen vacancy on the bare regular ceria surface. This strongly suggests that the propensity of ceria systems to store and release oxygen is directly affected by the presence of supported Pt particles.

  13. First Principles study of clean and CO covered CeO2 surfaces

    NASA Astrophysics Data System (ADS)

    Grohmann, Rainer; Bihlmayer, Gustav; Vogtenhuber, Doris; Redinger, Joseph; Podloucky, Raimund

    2000-03-01

    By application of a full-potential linearized augmented plane wave method (FLEUR package: G. Bihlmayer, S. Blügel, J. Redinger, R. Podloucky, M. Weinert, D. Vogtenhuber, unpublished.) energetics, relaxed geometry and electronic structure of bulk CeO2 and of its (110) and (111) clean surfaces were calculated. Results and analysis are presented for perfect and O-defect surfaces. Because of the importance of ceria in catalysis adsorption of CO at several high-symmetry positions is studied and discussed.

  14. Reverse Monte Carlo studies of CeO2 using neutron and synchrotron radiation techniques

    NASA Astrophysics Data System (ADS)

    Clark, Adam H.; Marchbank, Huw R.; Hyde, Timothy I.; Playford, Helen Y.; Tucker, Matthew G.; Sankar, Gopinathan

    2017-03-01

    A reverse Monte Carlo analysis method was employed to extract the structure of CeO2 from Neutron total scattering (comprising both neutron diffraction (ND) and pair-distribution functions (PDF) and Ce L3- and K-edge EXAFS data. Here it is shown that there is a noticeable difference between using short ranged x-ray absorption spectroscopy data and using medium-long range PDF and ND data in regards to the disorder of the cerium atoms. This illustrates the importance of considering multiple length scales and radiation sources.

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

    PubMed Central

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

    2016-01-01

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

  16. Reversible switching of room temperature ferromagnetism in CeO2-Co nanoparticles

    NASA Astrophysics Data System (ADS)

    Sacanell, J.; Paulin, M. A.; Ferrari, V.; Garbarino, G.; Leyva, A. G.

    2012-04-01

    We investigated the reversible ferromagnetic (FM) behavior of pure and Co doped CeO2 nanopowders. The as-sintered samples displayed an increasing paramagnetic contribution upon Co doping. Room temperature FM is obtained simply by performing thermal treatments in vacuum at temperatures as low as 500 °C and it can be switched off by performing thermal treatments in oxidizing conditions. The FM contribution is enhanced as we increase the time of the thermal treatment in vacuum. Those systematic experiments establish a direct relation between ferromagnetism and oxygen vacancies and open a path for developing materials with tailored properties.

  17. 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.

  18. 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.

  19. Simulation and experimental study of rheological properties of CeO2-water nanofluid

    NASA Astrophysics Data System (ADS)

    Loya, Adil; Stair, Jacqueline L.; Ren, Guogang

    2015-10-01

    Metal oxide nanoparticles offer great merits over controlling rheological, thermal, chemical and physical properties of solutions. The effectiveness of a nanoparticle to modify the properties of a fluid depends on its diffusive properties with respect to the fluid. In this study, rheological properties of aqueous fluids (i.e. water) were enhanced with the addition of CeO2 nanoparticles. This study was characterized by the outcomes of simulation and experimental results of nanofluids. The movement of nanoparticles in the fluidic media was simulated by a large-scale molecular thermal dynamic program (i.e. LAMMPS). The COMPASS force field was employed with smoothed particle hydrodynamic potential (SPH) and discrete particle dynamics potential (DPD). However, this study develops the understanding of how the rheological properties are affected due to the addition of nanoparticles in a fluid and the way DPD and SPH can be used for accurately estimating the rheological properties with Brownian effect. The rheological results of the simulation were confirmed by the convergence of the stress autocorrelation function, whereas experimental properties were measured using a rheometer. These rheological values of simulation were obtained and agreed within 5 % of the experimental values; they were identified and treated with a number of iterations and experimental tests. The results of the experiment and simulation show that 10 % CeO2 nanoparticles dispersion in water has a viscosity of 2.0-3.3 mPas.

  20. Nature of size-dependent lattice distortions in doped CeO2

    NASA Astrophysics Data System (ADS)

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

    2013-11-01

    Electron paramagnetic resonance spectroscopy of Gd3+ probe ions is used to investigate the nature of size dependent lattice distortions in bulk and nanocrystalline CeO2 with crystallite sizes of 600 and 10 nm, respectively, and doped with 0.5 and 1 cation% Y. The Gd3+ ions in bulk CeO2 are primarily located in almost perfect cubic crystal field, and the presence of the nearest neighbor vacancies results in trigonal distortion of this crystal field. In contrast, for nanocrystalline ceria, although the long-range symmetry remains unchanged, decreasing size results in local distortion of the crystal-field that is significantly different than that induced by the presence of nearest-neighbor oxygen vacancies. Different types of distortions are observed for the cation sites in the core and the surface regions of the nanocrystallites. Such lattice distortions at short-range are fundamental to the nanocrystalline state, being related to the increased ratio of the surface:bulk energy at nanometer length scales and provides mechanistic understanding of previously reported lattice parameter changes and phase transitions in nanocrystalline oxides.

  1. Clustering of Oxygen Vacancies at CeO2(111 ) : Critical Role of Hydroxyls

    NASA Astrophysics Data System (ADS)

    Wu, Xin-Ping; Gong, Xue-Qing

    2016-02-01

    By performing density functional theory calculations corrected by an on site Coulomb interaction, we find that the defects at the CeO2(111 ) surface observed by the scanning tunneling microscopy (STM) measurements of Esch et al. [Science 309, 752 (2005)] are not mere oxygen vacancies or fluorine impurities as suggested by Kullgren et al. [Phys. Rev. Lett. 112, 156102 (2014)], but actually the hydroxyl-vacancy combined species. Specifically, we show that hydroxyls play a critical role in the formation and propagation of oxygen vacancy clusters (VCs). In the presence of neighboring hydroxyls, the thermodynamically unstable VCs can be significantly stabilized, and the behaviors of oxygen vacancies become largely consistent with the STM observations. In addition to the clarification of the long term controversy on the surface defect structures of CeO2(111 ) , the "hydroxyl-vacancy model" proposed in this work emphasizes the coexistence of hydroxyls and oxygen vacancies, especially VCs, which is important for understanding the catalytic and other physicochemical properties of reducible metal oxides.

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

    DOE PAGES

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

    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

  3. Structure of Nano-sized CeO2 Materials: Combined Scattering and Spectroscopic Investigations.

    PubMed

    Marchbank, Huw R; Clark, Adam H; Hyde, Timothy I; Playford, Helen Y; Tucker, Matthew G; Thompsett, David; Fisher, Janet M; Chapman, Karena W; Beyer, Kevin A; Monte, Manuel; Longo, Alessandro; Sankar, Gopinathan

    2016-11-04

    The structure of several nano-sized ceria, CeO2 , systems was investigated using neutron and X-ray diffraction and X-ray absorption spectroscopy. Whilst both diffraction and total pair distribution functions (PDFs) revealed that in all of the samples the occupancy of both Ce(4+) and O(2-) are very close to the ideal stoichiometry, the analysis using Reverse Monte Carlo technique revealed significant disorder around oxygen atoms in the nano-sized ceria samples in comparison to the highly crystalline NIST standard. In addition, the analysis revealed that the main differences observed in the pair correlations from various X-ray and neutron diffraction techniques were attributable to the particle size of the CeO2 prepared by the reported three methods. Furthermore, detailed analysis of the Ce L3 - and K-edge EXAFS data support this finding; in particular the decrease in higher shell coordination numbers with respect to the NIST standard, is attributed to differences in particle size.

  4. 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.

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

    DOE PAGES

    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

  6. 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.

  7. 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

  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. 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.

  10. 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

    2014-01-08

    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.

  11. Effects of CeO2 nanoparticles on sludge aggregation and the role of extracellular polymeric substances - Explanation based on extended DLVO.

    PubMed

    You, Guoxiang; Hou, Jun; Wang, Peifang; Xu, Yi; Wang, Chao; Miao, Lingzhan; Lv, Bowen; Yang, Yangyang; Luo, Hao

    2016-11-01

    The extended DLVO (XDLVO) theory was applied to elucidate the potential effects of CeO2 nanoparticles (CeO2 NPs) on sludge aggregation and the role of extracellular polymeric substances (EPS). In this study, seven different concentrations of CeO2 NPs were added to activated sludge cultured in sequencing batch reactors (SBRs) and compared with a control test that received no CeO2 NPs. After exposure to 50mg/L CeO2 NPs, a negligible change (p>0.1) occurred in the sludge volume index (SVI), whereas the flocculability and aggregation of the sludge decreased by 18.8% and 11.2%, respectively, resulting in a high effluent turbidity. The XDLVO theory demonstrated that the adverse effects of the CeO2 NPs on sludge aggregation were due to an enhanced barrier energy. Compared to the van der Waals energies (WA) and the electric double layer (WR), the acid-base interaction (WAB) markedly changed for the various concentrations of CeO2 NPs. The EPS played a decisive role in the sludge surface characteristics, as the removal of EPS equals to the negative effects induced by 5-10mg/L CeO2 NPs on the sludge flocculability and aggregation. The presence of CeO2 NPs induced negative contributions to the tight boundary EPS (TB-EPS) and core bacteria while positive contributions to the total interaction energy of the loose boundary EPS (LB-EPS).

  12. 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.

  13. BiVO(4)/CeO(2) nanocomposites with high visible-light-induced photocatalytic activity.

    PubMed

    Wetchakun, Natda; Chaiwichain, Saranyoo; Inceesungvorn, Burapat; Pingmuang, Kanlaya; Phanichphant, Sukon; Minett, Andrew I; Chen, Jun

    2012-07-25

    Preparation of bismuth vanadate and cerium dioxide (BiVO4/CeO2) nanocomposites as visible-light photocatalysts was successfully obtained by coupling a homogeneous precipitation method with hydrothermal techniques. The BiVO4/CeO2 nanocomposites with different mole ratios were synthesized and characterized by X-ray diffraction (XRD), Raman spectroscopy, and transmission electron microscopy (TEM). Absorption range and band gap energy, which are responsible for the observed photocatalyst behavior, were investigated by UV-vis diffuse reflectance (UV-vis DR) spectroscopy. Photocatalytic activities of the prepared samples were examined by studying the degradation of model dyes Methylene Blue, Methyl Orange, and a mixture of Methylene Blue and Methyl Orange solutions under visible-light irradiation (>400 nm). Results clearly show that the BiVO4/CeO2 nanocomposite in a 0.6:0.4 mol ratio exhibited the highest photocatalytic activity in dye wastewater treatment.

  14. High-Performance Ru1 /CeO2 Single-Atom Catalyst for CO Oxidation: A Computational Exploration.

    PubMed

    Li, Fengyu; Li, Lei; Liu, Xinying; Zeng, Xiao Cheng; Chen, Zhongfang

    2016-10-18

    By means of density functional theory computations, we examine the stability and CO oxidation activity of single Ru on CeO2 (111), TiO2 (110) and Al2 O3 (001) surfaces. The heterogeneous system Ru1 /CeO2 has very high stability, as indicated by the strong binding energies and high diffusion barriers of a single Ru atom on the ceria support, while the Ru atom is rather mobile on TiO2 (110) and Al2 O3 (001) surfaces and tends to form clusters, excluding these systems from having a high efficiency per Ru atom. The Ru1 /CeO2 exhibits good catalytic activity for CO oxidation via the Langmuir-Hinshelwood mechanism, thus is a promising single-atom catalyst.

  15. 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.

  16. CeO2 nanocrystallines ensemble-on-nitrogen-doped graphene nanocomposites: one-pot, rapid synthesis and excellent electrocatalytic activity for enzymatic biosensing.

    PubMed

    Du, Xiaojiao; Jiang, Ding; Chen, Saibo; Dai, Liming; Zhou, Lei; Hao, Nan; You, Tianyou; Mao, Hanping; Wang, Kun

    2017-03-15

    Ceria nanomaterials for heterogeneous catalysis have attracted much attention due to their excellent properties and have been extensively applied in recent years. But the poor electron conductivity and the aggregation behavior severely affect their electrocatalytic performances. In this paper, we prepared a novel catalyst based on CeO2 nanocrystallines (CeO2 NCs) ensemble-on-nitrogen-doped graphene (CeO2-NG) nanocomposites through a one-step heat-treatment without the need of the precursor. The results confirmed that the high dispersion of CeO2 NCs with the uniform size distribution of about 5nm on the surface of nitrogen-doped graphene (NG) sheets could be easily obtained via the one-step procedure and the resultant CeO2-NG nanocomposites were an excellent electrode material possessing outstanding electrochemical features for electron transfer. Luminol, an important electroactive substance, was further chosen to inspect the electrocatalytic properties of the as-prepared CeO2-NG nanocomposites. The studies showed that the presence of the NG in CeO2-NG nanocomposites could facilitate the electrochemical redox process of luminol. Compared with pristine CeO2 NCs, the synthesized CeO2-NG nanocomposites can enhance the electrochemiluminescence (ECL) intensity by 3.3-fold and decrease the onset ECL potential for about 72mV in the neutral condition. Employing above superiority, selecting cholesterol oxidase (ChOx) as the model oxidase, a facile ECL method for cholesterol detection with the CeO2-NG nanocomposites as the matrix to immobilize enzyme ChOx was developed. The results demonstrated CeO2-NG nanocomposites exhibited excellent performances in terms of sensitivity and catalytic activities, indicating that NG-based nanomaterials have great promise in electrocatalytic and enzymatic biosensing fields.

  17. 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.

  18. 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

  19. 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.

  20. Entropic contributions enhance polarity compensation for CeO2(100) surfaces

    NASA Astrophysics Data System (ADS)

    Capdevila-Cortada, Marçal; López, Núria

    2016-11-01

    Surface structure controls the physical and chemical response of materials. Surface polar terminations are appealing because of their unusual properties but they are intrinsically unstable. Several mechanisms, namely metallization, adsorption, and ordered reconstructions, can remove thermodynamic penalties rendering polar surfaces partially stable. Here, for CeO2(100), we report a complementary stabilization mechanism based on surface disorder that has been unravelled through theoretical simulations that: account for surface energies and configurational entropies; show the importance of the ion distribution degeneracy; and identify low diffusion barriers between conformations that ensure equilibration. Disordered configurations in oxides might also be further stabilized by preferential adsorption of water. The entropic stabilization term will appear for surfaces with a high number of empty sites, typically achieved when removing part of the ions in a polar termination to make the layer charge zero. Assessing the impact of surface disorder when establishing new structure-activity relationships remains a challenge.

  1. A simple method to obtain Fe-doped CeO2 nanocrystals at room temperature

    NASA Astrophysics Data System (ADS)

    Almeida, J. M. A.; Santos, P. E. C.; Cardoso, L. P.; Meneses, C. T.

    2013-02-01

    Ce1-xFexO2 nanocrystals (0

  2. Entropic contributions enhance polarity compensation for CeO2(100) surfaces.

    PubMed

    Capdevila-Cortada, Marçal; López, Núria

    2017-03-01

    Surface structure controls the physical and chemical response of materials. Surface polar terminations are appealing because of their unusual properties but they are intrinsically unstable. Several mechanisms, namely metallization, adsorption, and ordered reconstructions, can remove thermodynamic penalties rendering polar surfaces partially stable. Here, for CeO2(100), we report a complementary stabilization mechanism based on surface disorder that has been unravelled through theoretical simulations that: account for surface energies and configurational entropies; show the importance of the ion distribution degeneracy; and identify low diffusion barriers between conformations that ensure equilibration. Disordered configurations in oxides might also be further stabilized by preferential adsorption of water. The entropic stabilization term will appear for surfaces with a high number of empty sites, typically achieved when removing part of the ions in a polar termination to make the layer charge zero. Assessing the impact of surface disorder when establishing new structure-activity relationships remains a challenge.

  3. Use of site symmetry in supercell models of defective crystals: polarons in CeO2.

    PubMed

    Evarestov, R A; Gryaznov, D; Arrigoni, M; Kotomin, E A; Chesnokov, A; Maier, J

    2017-03-22

    In supercell calculations of defective crystals, it is common to place a point defect or vacancy in the atomic position with the highest possible point symmetry. Then, the initial atomic structure is often arbitrary distorted before its optimization, which searches for the total energy minimum. In this paper, we suggest an alternative approach to the application of supercell models and show that it is necessary to preliminarily analyze the site symmetry of the split Wyckoff positions of the perfect crystal supercell atoms (which will be substituted or removed in defective crystals) and then perform supercell calculations with point defects for different possible site symmetries, to find the energetically most favorable defect configuration, which does not necessarily correspond to the highest site symmetry. Using CeO2 as an example, it is demonstrated that this use of the site symmetry of the removed oxygen atoms in the supercells with vacancies allows us to obtain all the possible atomic and magnetic polaron configurations, and predict which vacancy positions correspond to the lowest formation energies associated with small polarons. We give a simple symmetry based explanation for the existence of controversies in the literature on the nature of the oxygen vacancies in CeO2. In particular, the experimentally observed small polaron formation could arise for oxygen vacancies with the lowest Cs site symmetry, which exist in 3 × 3 × 3 and larger supercells. The results of first principles calculations using a linear combination of atomic orbitals and hybrid exchange-correlation functionals are compared with those from previous studies, obtained using a widely used DFT+U approach.

  4. 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.

  5. Catalytic wet air oxidation of phenol over CeO2-TiO2 catalyst in the batch reactor and the packed-bed reactor.

    PubMed

    Yang, Shaoxia; Zhu, Wanpeng; Wang, Jianbing; Chen, Zhengxiong

    2008-05-30

    CeO2-TiO2 catalysts are prepared by coprecipitation method, and the activity and stability in the catalytic wet air oxidation (CWAO) of phenol are investigated in a batch reactor and packed-bed reactor. CeO2-TiO2 mixed oxides show the higher activity than pure CeO2 and TiO2, and CeO2-TiO2 1/1 catalyst displays the highest activity in the CWAO of phenol. In a batch reactor, COD and TOC removals are about 100% and 77% after 120 min in the CWAO of phenol over CeO2-TiO2 1/1 catalyst at reaction temperature of 150 degrees C, the total pressure of 3 MPa, phenol concentration of 1000 mg/L, and catalyst dosage of 4 g/L. In a packed-bed reactor using CeO2-TiO2 1/1 particle catalyst, over 91% COD and 80% TOC removals are obtained at the reaction temperature of 140 degrees C, the air total pressure of 3.5 MPa, the phenol concentration of 1000 mg/L for 100 h continue reaction. Leaching of metal ions of CeO2-TiO2 1/1 particle catalyst is very low during the continuous reaction. CeO2-TiO2 1/1 catalyst exhibits the excellent activity and stability in the CWAO of phenol.

  6. Co3O4-CeO2/C as a Highly Active Electrocatalyst for Oxygen Reduction Reaction in Al-Air Batteries.

    PubMed

    Liu, Kun; Huang, Xiaobing; Wang, Haiyan; Li, Fuzhi; Tang, Yougen; Li, Jingsha; Shao, Minhua

    2016-12-21

    Developing high-performance and low-cost electrocatalysts for oxygen reduction reaction (ORR) is still a great challenge for Al-air batteries. Herein, CeO2, a unique ORR promoter, was incorporated into ketjenblack (KB) supported Co3O4 catalyst. We developed a facile two-step hydrothermal approach to fabricate Co3O4-CeO2/KB as a high-performance ORR catalyst for Al-air batteries. The ORR activity of Co3O4/KB was significantly increased by mixing with CeO2 nanoparticles. In addition, the Co3O4-CeO2/KB showed a better electrocatalytic performance and stability than 20 wt % Pt/C in alkaline electrolytes, making it a good candidate for highly active ORR catalysts. Co3O4-CeO2/KB favored a four-electron pathway in ORR due to the synergistic interactions between CeO2 and Co3O4. In full cell tests, the Co3O4-CeO2/KB exhibited a higher discharge voltage plateau than CeO2/KB and Co3O4/KB when used in cathode in Al-air batteries.

  7. 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...

  8. 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.

  9. 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.

  10. Effects of CeO2 on the XPS valence band spectra of coal under the combustion initialization stage at 400°C

    NASA Astrophysics Data System (ADS)

    Qi, Cheng-lin; Zhang, Jian-liang; Ma, Chao; Feng, Gen-sheng; Song, Zhong-ping

    2013-04-01

    In order to get the catalytic mechanism of CeO2 on graphite and coal at 400°C, the morphologies of coal, graphite, and CeO2 before and after combustion were analyzed through X-ray photoelectron spectroscopy (XPS). It is found that the particle size of coal is mostly between 11.727 and 64.79 μm, while the particle size of CeO2 is between 1.937 and 11.79 μm. The agglomeration of coal and CeO2 can be seen by scanning electron microscopy (SEM) after reaction. XPS results show that with the addition of CeO2, the intensity of binding energy gets stronger, but there is no energy peak transition. Comparing the character of coal with and without the addition of CeO2, it can be seen that the C-C bond fractures first at 400°C, while the C-H energy-band takes electrons at the same time to be far away from the Fermi level, and the O 2s, O 2p, and C sp hybrid orbitals are all excited. Adding CeO2 can enhance the activity of the whole coal. In addition, through XPS analysis, combined with the oxygen transfer theory and the electron transfer theory, the catalytic mechanism of CeO2 for pulverized coal combustion could be obtained.

  11. CeO2 nanocrystals and solid-phase heteroepitaxy of CeAlO3 interlayer on Al2O3(0 0 0 1) substrate

    NASA Astrophysics Data System (ADS)

    Hattori, Takashi; Ozawa, Masakuni

    2017-04-01

    Grain growth and interfacial solid state of CeO2 nanocrystals (NCs) layer on Al2O3(0 0 0 1) substrate were examined. CeO2 NCs layer on Al2O3(0 0 0 1) was prepared by dipping method using CeO2 nanocrystals colloid solution. After heat treatment at 1000 °C in air, CeO2 NCs layer was formed on Al2O3(0 0 0 1). The CeO2 NCs sintered to form a surface layer with an interlayer of CeAlO3 after heat treatment at 950 °C in H2/Ar, leading to dense and smooth CeO2 NCs layer on Al2O3(0 0 0 1) substrate. CeAlO3 was grown via diffusion of CeO2-x (non-stoichiometric CeO2) and Al2O3, suggesting solid-phase reaction heteroepitaxy mechanism on Al2O3(0 0 0 1) single crystal substrate.

  12. 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.

  13. Comparative study of structural, optical and impedance measurements on V2O5 and V-Ce mixed oxide thin films

    NASA Astrophysics Data System (ADS)

    Malini, D. Rachel; Sanjeeviraja, C.

    2015-06-01

    Vanadium pentoxide (V2O5) and Vanadium-Cerium mixed oxide thin films at different molar ratios of V2O5 and CeO2 have been deposited at 200 W rf power by rf planar magnetron sputtering in pure argon atmosphere. The structural and optical properties were studied by taking X-ray diffraction and transmittance and absorption spectra respectively. The amorphous thin films show an increase in transmittance and optical bandgap with increase in CeO2 content in as-prepared thin films. The impedance measurements for as-deposited thin films show an increase in electrical conductivity with increase in CeO2 material.

  14. 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.

  15. Crystal growth and photoluminescence properties of Sm3+ doped CeO2 nanophosphors by solvothermal method.

    PubMed

    Yang, Hyun Kyoung; Moon, Byung Kee; Choi, Byung Chun; Jeong, Jung Hyun; Kim, Kwang Ho

    2013-09-01

    The phosphor of CeO2 activated with the trivalent rare-earth Sm3+ ions were synthesized by using a solvothermal method. The CeO2:Sm3+ powders were finally obtained through calcination process sintered in the air at 800-1200 degrees C. The synthesized phosphors were characterized systematically by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), photoluminescence (PL) and photoluminescence excitation spectra (PLE). The XRD and FE-SEM results reveal that the phosphor exhibit agglomerated spherical shape and with the increase of sintering temperature peaks become sharper and narrower and the crystal sizes also increase, respectively. The room temperature photoluminescence spectra of Sm3+ doped CeO2 powders were recorded on a PTI (Photon Technology International) flurimeter using a Xe-arc lamp with a power of 60 W. The emitted radiation was dominated by the orange light with the characteristic emission of Sm3+ from the transitions of 4G5/2 --> 6H5/2,7/2. The sharp emission properties show that the CeO2 has the potential to serve as a host material for rare-earth doped laser crystal and phosphor material.

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

    DOE PAGES

    Wang, Shichao; Xie, Hong; Lin, Yuyuan; ...

    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

  17. A comparative investigation of SO2 oxidative transfer over CuO with a CeO2 surface

    NASA Astrophysics Data System (ADS)

    Liu, Yifeng; Shen, Benxian; Pi, Zhipeng; Chen, Hua; Zhao, Jigang

    2017-04-01

    To further improve the catalytic desulfurization function of the Mg-Al spinel sulfur transfer agent in a fluid catalytic cracking (FCC) unit, the reaction paths of SO2 oxidation by O2 over the metal oxide surface of CuO (111) and CeO2 (111) were investigated. In reference to the fact that SO2 reacting with O2 over CuO was a Mars-van Krevelen cycle, a similar reaction law for SO2 oxidation over CeO2 was also verified by characterization methods (e.g., IR, XPS). Meanwhile, the molecular simulation results indicated that the rate-control step of SO2 oxidation over CeO2 (111) and CuO (111) was a SO3 desorption step. The lower energy barrier in the rate-control step corresponded to better catalytic performance; hence, it could explain the reason that CeO2 had a better sulfur oxidization transfer performance than CuO.

  18. 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.

  19. Enhanced photocatalytic activity of CeO2 using β-cyclodextrin on visible light assisted decoloration of methylene blue.

    PubMed

    Pitchaimuthu, Sakthivel; Velusamy, Ponnusamy

    2014-01-01

    An attempt has been made to enhance the photocatalytic activity of CeO(2) for visible light assisted decoloration of methylene blue (MB) dye in aqueous solutions by β-cyclodextrin (β-CD). The inclusion complexation patterns between host and guest (i.e., β-CD and MB) have been confirmed with UV-visible spectral data. The interaction between CeO(2) and β-CD has also been characterized by field emission scanning electron microscopy analysis. The photocatalytic activity of the catalyst under visible light was investigated by measuring the photodegradation of MB in aqueous solution. The effects of key operational parameters such as initial dye concentration, initial pH, CeO(2) concentration as well as illumination time on the decolorization extents were investigated. Among the processing parameters, the pH of the reaction solution played an important role in tuning the photocatalytic activity of CeO(2). The maximum photodecoloration rate was achieved at basic pH (pH 11). Under the optimum operational conditions, approximately 99.6% dye removal was achieved within 120 min. The observed results indicate that the decolorization of the MB followed a pseudo-first order kinetics.

  20. Cyclotron production of radioactive CeO(2) nanoparticles and their application for in vitro uptake studies.

    PubMed

    Simonelli, Federica; Marmorato, P; Abbas, K; Ponti, J; Kozempel, J; Holzwarth, U; Franchini, F; Rossi, F

    2011-03-01

    Nowadays, a wide variety of nanoparticles (NPs) are applied in different fields such as medical science and industry. Due to their large commercial volume, the OECD Working Party on Manufactured Nanomaterials (NMs) has proposed to study a set of 14 nanomaterials, one of which being cerium oxide (CeO(2)). In particular, CeO(2) based NPs are widely used in automotive industry, healthcare, and cosmetics. In this paper, we propose a method for the production of radioactive CeO(2) NPs.We demonstrate that they maintain the same physicochemical characteristics as the “cold” ones in terms of size distribution and Zeta potential; we develop a new protocol to assess their cellular interaction in immortalized mouse fibroblast cell line Balb/3T3, a model for the study of basal cytotoxicity and carcinogenic potential induced by chemicals and in the present case by NPs. Experimental result of this work, which shows a quasi-linear concentration-uptake response of cells, can be useful as a reference dose-uptake curve for explaining effects following biological uptake after exposure to CeO(2) NPs.

  1. 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.

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

    DOE PAGES

    Lei, Wanying; Zhang, Tingting; Gu, Lin; ...

    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

  3. CeO2 NPs, toxic or protective to phytoplankton? Charge of nanoparticles and cell wall as factors which cause changes in cell complexity.

    PubMed

    Sendra, M; Yeste, P M; Moreno-Garrido, I; Gatica, J M; Blasco, J

    2017-07-15

    CeO2 nanoparticles (CeO2 NPs) are well-known for their catalytic properties and antioxidant potential. Recent uses in therapy are based on the Ce(+3) ions released by CeO2 NPs. Reactions involving redox cycles between Ce(+3) and Ce(+4) oxidation stage seem to promote scavenging of reactive oxygen species (ROS), thus protecting cells from oxygen damage. However, the internalization of CeO2 NPs and release of Ce(+3) could be responsible for a toxic effect on cells. The literature reports controversial results on the toxicity of CeO2 NPs to phytoplankton. Therefore, we have tested the potential toxic effect of two CeO2 NPs (with positive and negative zeta potential) and bulk CeO2 (at 0.1, 1, 10, 100 and 200mg·L(-1)) on three species of microalgae from different environments: marine diatom (Phaeodactylum tricornutum), marine chlorophyte (Nannochloris atomus) and freshwater chlorophyte (Chlamydomonas reinhardtii) over 72h in batch cultures. Responses measured in the microalgae population are: growth, chlorophyll a, cell size, cell complexity, percentage of ROS, and percentage of cell membrane damage. Positive zeta potential CeO2 NPs provoked greater cell complexity (up to 78, 172 and 23 times more cell complexity than in controls found for C. reinhardtii, P. tricornutum and N. atomus respectively) than negative zeta potential CeO2 NPs. The SSC signal detected by flow cytometry measured increases of particles entering cells, and this is related to cell viability and levels of intracellular ROS (correlation between SSC and percentage of ROS of 0.72 and 0.97 found for C. reinhardtii and P. tricornutum). When increased cellular complexity over controls is between 2 and 6 times greater, CeO2 (in bulk or nanoparticulate form) seems to protect against ROS. When increased cellular complexity is from 7 to 23 times greater, CeO2 does not provoke toxic responses; however, when increased cellular complexity over controls is very high, from 61 to 172 times, increased ROS production and toxic responses are found. Results show that two factors, the charge of CeO2 NPs and cell wall structure, constitute the primary barrier to the possible accumulation of CeO2 NPs within phytoplankton cytosol.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. Functional Paper-Based Platform for Rapid Capture and Detection of CeO2 Nanoparticles.

    PubMed

    Othman, Ali; Andreescu, Daniel; Karunaratne, Dinusha P; Babu, S V; Andreescu, Silvana

    2017-04-12

    Development of systems for capture, sequestration, and tracking of nanoparticles (NPs) is becoming a significant focus in many aspects of nanotechnology and environmental research. These systems enable a broad range of applications for evaluating concentration, distribution, and effects of NPs for environmental, clinical, epidemiological, and occupational exposure studies. Herein, we describe the first example of a ligand-graft multifunctional platform for capture and detection of cerium oxide (CeO2 or ceria) NPs. The approach involves the use of redox-active ligands containing o-dihydroxy functionality, enabling multivalent binding, surface retention, and formation of charge transfer complexes between the grafted ligand and the NPs. Using this strategy, paper-based and microarray-printed platforms with NP-capture ability involving either catechol or ascorbic acid as ligands were successfully fabricated. Surface modification was determined by infrared spectroscopy, electron microscopy, X-ray spectroscopy, and thermogravimetric analysis. Functionality was demonstrated for the rapid assessment of NPs in chemical mechanical planarization (CMP) slurries and CMP wastewaters. This novel approach can enable further development of devices and separation technologies including platforms for retention and separation of NPs and measurement tools for detection of NPs in various environments.

  10. Methanol decomposition on low index and stepped CeO2 surfaces from GGA+U

    NASA Astrophysics Data System (ADS)

    Reimers, Walter G.; Branda, María M.

    2017-02-01

    GGA + U calculations have been carried out to study the complete methanol decomposition on the more stable Ceria surfaces, i.e. (111), (221), (331) and (110). These results have shown that the methanol adsorption is exothermic on oxidized as well as on the partially reduced surfaces though the adsorption energy is greater for the latest. The first dehydrogenation step of methanol is highly probable for all the studied sites with activation barriers smaller than 0.2 eV. The first dehydrogenation reaction could also occur by breaking the Csbnd H methyl bond, but we found that this reaction is very unlikely. Reaction and activation energies for the second dehydrogenation - from methoxy to formaldehyde, are very similar for perfect (111) and stepped surfaces but these activation barriers are not negligible, almost ten times as many the first step barriers. Next, the formaldehyde decomposition to formyl and CO species on perfect CeO2(111) have an important energetic cost, therefore these reactions could occur only on stepped surfaces.

  11. 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.

  12. Characterization of Sm-doped CeO2 nanoparticles and their magnetic properties

    NASA Astrophysics Data System (ADS)

    Swatsitang, Ekaphan; Phokha, Sumalin; Hunpratub, Sitchai; Maensiri, Santi

    2016-03-01

    Cubic phase Sm-doped CeO2 nanoparticles (Ce1-xSmxO2, x=0, 0.05, 0.10, 0.15 and 0.20) were synthesized by the polymer pyrolysis method. X-ray diffraction (XRD), Raman spectroscopy, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and vibrating sample magnetometer (VSM) were employed to characterize the phase, morphology, valence states and magnetic properties of the samples. The samples were calcined at the low temperature of 600 °C which resulted in crystallite sizes of 10-20 nm. Raman and XPS spectra showed the presence of Ce4+, Ce3+ and Sm3+ ions and oxygen vacancies in the samples. Magnetization curves obtained from all samples exhibited ferromagnetic behavior at room temperature (RT-FM) with a maximum value of 0.012 emu/g for x=0.15. The data exhibited a good fit to bound magnetic polaron (BMP) model curves which account for the RT-FM behaviour by having sufficient concentrations of electrons bound to oxygen vacancies to facilitate a long-range exchange interaction between Ce3+ ions. However, the relatively low values obtained for the BMP concentrations suggest that other mechanisms may also be at play.

  13. 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.

  14. Exceptional capability of nanosized CeO(2) materials to "dissolve" lanthanide oxides established by time-gated excitation and emission spectroscopy.

    PubMed

    Tiseanu, Carmen; Parvulescu, Vasile; Avram, Daniel; Cojocaru, Bogdan; Sanchez-Dominguez, Margarita

    2014-05-28

    The atomic scale homogeneity of Ce and Zr oxygen bonds represents the main reason for enhanced total oxygen storage capability of CeO2-ZrO2 (Ce/Zr = 1) as compared to that of CeO2. Here, we demonstrate that the addition of 10% Eu(3+) by wet impregnation on preformed nanosized CeO2-ZrO2 (Ce/Zr = 1) followed by calcination induces a remarkable homogeneity of 10% Eu(3+)-CeO2-ZrO2 solid solution. By use of time-resolved emission and excitation spectroscopies, the improvement of the nanoscale chemical and structural homogeneity of 10% Eu(3+)-CeO2-ZrO2 calcined at 1000 as compared to sample calcined at 750 °C is demonstrated. Based on the comparison of luminescence properties of 10% Eu(3+) impregnated on preformed nanosized CeO2-ZrO2 and CeO2, we also show that the presence of zirconium does not only preserve the ability of cerium oxide to "dissolve" lanthanide oxide, but also determines an important stabilization of defects (oxygen vacancies) generated upon Eu(3+) doping.

  15. Baize-like CeO2 and NiO/CeO2 nanorod catalysts prepared by dealloying for CO oxidation

    NASA Astrophysics Data System (ADS)

    Zhang, Xiaolong; Li, Kun; Shi, Wenyu; Wei, Caihua; Song, Xiaoping; Yang, Sen; Sun, Zhanbo

    2017-01-01

    Baize-like monolithic CeO2 and NiO/CeO2 nanorod catalysts were prepared by combined dealloying and calcination and the catalytic activities were evaluated using CO catalytic oxidation. The CeO2 catalysts were composed of nanorods and exhibited a three-dimensional supporting structure with pores. After introduction of NiO, dispersed NiO nanosheets and nanoparticles were supported on the surface of CeO2 nanorods and they were not well-crystallined due to CeO2 inhibiting the NiO crystallization. The Raman and x-ray photoelectron spectroscopy analyses revealed that the introduction of NiO species into CeO2 generated more coordinate unsaturated Ni atoms, oxygen vacancies, defects and active sites for CO catalytic reactions. The reaction activation energy of NiO/CeO2 nanorod catalyst prepared from the Al83Ce10Ni7 precursor alloy was just 31.2 kJ mol-1 and the CO conversion can reach up to 97% at 240 °C, which was superior to that of pure CeO2 and nanoporous NiO. The enhanced catalytic activity of baize-like NiO/CeO2 nanorods can be attributed to the strong synergistic effects between finely dispersed NiO species and surface oxygen vacancies in CeO2 nanorods.

  16. Local structure and nanoscale homogeneity of CeO2-ZrO2: differences and similarities to parent oxides revealed by luminescence with temporal and spectral resolution.

    PubMed

    Tiseanu, Carmen; Parvulescu, Vasile; Avram, Daniel; Cojocaru, Bogdan; Boutonnet, Magali; Sanchez-Dominguez, Margarita

    2014-01-14

    Although homogeneity at the atomic level of CeO2-ZrO2 with a Ce/Zr atomic ratio close to unity is considered to be one of the main causes for the increased total oxygen storage capacity (OSC), the characterization approaches of homogeneity remain a major challenge. We propose a simple, yet effective method, to assess both structural and compositional homogeneity of CeO2-ZrO2 by using Eu(3+) luminescence measured with time and dual spectral resolution (emission and excitation). For Eu(3+)-CeO2-ZrO2 calcined at 750 °C, the X-ray diffraction, Raman and High-Resolution Transmission Electron Microscopy data converge to a single pseudo-cubic phase. However, the evolution of Eu(3+)-delayed luminescence from cubic ceria-like to tetragonal zirconia-like emission reveals the formation of CeO2- and ZrO2-rich nanodomains and provides evidence for early phase separation. For Eu(3+)-CeO2-ZrO2 calcined at 1000 °C, the emission of Eu(3+) reveals both structural and compositional inhomogeneity. Our study identifies the differences between the local structure properties of CeO2 and ZrO2 parent oxides and CeO2-ZrO2 mixed oxide, also confirming the special chemical environment of the oxygen atoms in the mixed oxide as reported earlier by Extended X-ray Absorption Fine Structure investigations.

  17. Baize-like CeO2 and NiO/CeO2 nanorod catalysts prepared by dealloying for CO oxidation.

    PubMed

    Zhang, Xiaolong; Li, Kun; Shi, Wenyu; Wei, Caihua; Song, Xiaoping; Yang, Sen; Sun, Zhanbo

    2017-01-27

    Baize-like monolithic CeO2 and NiO/CeO2 nanorod catalysts were prepared by combined dealloying and calcination and the catalytic activities were evaluated using CO catalytic oxidation. The CeO2 catalysts were composed of nanorods and exhibited a three-dimensional supporting structure with pores. After introduction of NiO, dispersed NiO nanosheets and nanoparticles were supported on the surface of CeO2 nanorods and they were not well-crystallined due to CeO2 inhibiting the NiO crystallization. The Raman and x-ray photoelectron spectroscopy analyses revealed that the introduction of NiO species into CeO2 generated more coordinate unsaturated Ni atoms, oxygen vacancies, defects and active sites for CO catalytic reactions. The reaction activation energy of NiO/CeO2 nanorod catalyst prepared from the Al83Ce10Ni7 precursor alloy was just 31.2 kJ mol(-1) and the CO conversion can reach up to 97% at 240 °C, which was superior to that of pure CeO2 and nanoporous NiO. The enhanced catalytic activity of baize-like NiO/CeO2 nanorods can be attributed to the strong synergistic effects between finely dispersed NiO species and surface oxygen vacancies in CeO2 nanorods.

  18. 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.

  19. 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.

  20. 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.

  1. In-situ powder X-ray diffraction investigation of reaction pathways for the BaCO(3)-CeO(2)-In(2)O(3) and CeO(2)-In(2)O(3) systems.

    PubMed

    Bhella, Surinderjit Singh; Shafi, Shahid P; Trobec, Francesca; Bieringer, Mario; Thangadurai, Venkataraman

    2010-02-15

    We report the first in-situ powder X-ray diffraction (PXRD) study of the BaCO(3)-CeO(2)-In(2)O(3) and CeO(2)-In(2)O(3) systems in air over a wide range of temperature between 25 and 1200 degrees C. Herein, we are investigating the formation pathway and chemical stability of perovskite-type BaCe(1-x)In(x)O(3-delta) (x = 0.1, 0.2, and 0.3) and corresponding fluorite-type Ce(1-x)In(x)O(2-delta) phases. The potential direct solid state reaction between CeO(2) and In(2)O(3) for the formation of indium-doped fluorite-type phase is not observed even up to 1200 degrees C in air. The formation of the BaCe(1-x)In(x)O(3-delta) perovskite structures was investigated and rationalized using in-situ PXRD. Furthermore the decomposition of the indium-doped perovskites in CO(2) is followed using high temperature diffraction and provides insights into the reaction pathway as well as the thermal stability of the Ce(1-x)In(x)O(3-delta) system. In CO(2) flow, BaCe(1-x)In(x)O(3-delta) decomposes above T = 600 degrees C into BaCO(3) and Ce(1-x)In(x)O(2-delta). Furthermore, for the first time, the in-situ PXRD confirmed that Ce(1-x)In(x)O(2-delta) decomposes above 800 degrees C and supported the previously claimed metastability. The maximum In-doping level for CeO(2) has been determined using PXRD. The lattice constant of the fluorite-type structure Ce(1-x)In(x)O(2-delta) follows the Shannon ionic radii trend, and crystalline domain sizes were found to be dependent on indium concentration.

  2. Environmentally friendly synthesis of CeO2 nanoparticles for the catalytic oxidation of benzyl alcohol to benzaldehyde and selective detection of nitrite.

    PubMed

    Tamizhdurai, P; Sakthinathan, Subramanian; Chen, Shen-Ming; Shanthi, K; Sivasanker, S; Sangeetha, P

    2017-04-13

    Cerium oxide nanoparticles (CeO2 NPs) are favorable in nanotechnology based on some remarkable properties. In this study, the crystalline CeO2 NPs are successfully prepared by an efficient microwave combustion (MCM) and conventional route sol-gel (CRSGM) methods. The structural morphology of the as-prepared CeO2 NPs was investigated by various spectroscopic and analytical techniques. Moreover, the XRD pattern confirmed the formation of CeO2 NPs as a face centered cubic structure. The magnetometer studies indicated the low saturation magnetization (23.96 emu/g) of CeO2 NPs for weak paramagnetic and high saturation magnetization (32.13 emu/g) of CeO2 NPs for super paramagnetic. After that, the oxidation effect of benzyl alcohol was investigated which reveals good conversion and selectivity. Besides, the CeO2 NPs modified glassy carbon electrode (GCE) used for the detection of nitrite with linear concentration range (0.02-1200 μM), low limit of detection (0.21 μM) and higher sensitivity (1.7238 μAμM(-1) cm(-2)). However, the CeO2 NPs modified electrode has the fast response, high sensitivity and good selectivity. In addition, the fabricated electrode is applied for the determination of nitrite in various water samples. Eventually, the CeO2 NPs can be regarded as an effective way to enhance the catalytic activity towards the benzyl alcohol and nitrite.

  3. 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.

  4. 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

  5. Decomposition of GD on CeO2/Alumina Adsorbents in a Gas Chromatograph On-Column Injector Tube Reactor

    DTIC Science & Technology

    2006-10-01

    CeO2/alumina; the major products were pinacolyl methylphosphonic acid , methyl phosphonic acid , and dipinacolyl methylphosphonate. 15. SUBJECT TERMS GD...microcrystalline and nanocrystalline metal oxides yields the hydrolysate of the parent phosphorous compound as the major producta The rate of reaction of G and...on A120 3 (e. q. most recent version of the M295 kit) and nanosize MgO is extremely fast under certain conditions.b’ 1 Mitchell and co-workers at

  6. 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

    2015-05-07

    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.

  7. 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.

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

    DOE PAGES

    Yang, Sangmo; Lee, Shinbuhm; Jian, Jie; ...

    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

  9. 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

    2015-08-05

    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.

  10. 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.

  11. 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

  12. 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.

  13. A novel synthesis method to produce silver-doped CeO2 nanotubes based on Ag nanowire templates.

    PubMed

    Mondragón-Galicia, G; Pérez-Hernández, R; Gutiérrez-Wing, C E; Mendoza-Anaya, D

    2011-10-06

    Silver nanowires were used as templates to synthesize silver-doped CeO(2) (Ag-CeO(2)) nanotubes by the precipitation method. The precipitated solid was dried at 100 °C for 24 h and calcined at 500 °C for 5 h. A TEM, HRTEM, LV-SEM and XRD study was carried out to determine the micro and nanostructural characteristics of the samples. LV-SEM analysis allowed us to observe microtubular empty structures constituted by Ce, O and Ag as indicated by EDS. These tubular structures, with an external diameter from 120 to 280 nm and an internal diameter from 40 to 80 nm, were mainly composed of 11 nm ceria nanoparticles. This kind of structures was obtained when CeO(2) nanoparticles covered the Ag nanowires during the synthesis. Due to the presence of ammonium hydroxide used during the synthesis, a fraction of the silver nanowire reacts and Ag atoms begin to migrate outside the ceria microtube. When the sintering process is applied, the Kirkendall effect can occur. So, out-diffusion of the remnant Ag through the interface is faster than the in-diffusion of the shell material (CeO(2)), which eventually results in a coaxial nanotube on completion of the non-equilibrium interdiffusion, leaving the central core completely empty, driving the formation of hollow tubular Ag-CeO(2) structures as a result.

  14. 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.

  15. Ruthenium nanoparticles supported on CeO2 for catalytic permanganate oxidation of butylparaben.

    PubMed

    Zhang, Jing; Sun, Bo; Guan, Xiaohong; Wang, Hui; Bao, Hongliang; Huang, Yuying; Qiao, Junlian; Zhou, Gongming

    2013-11-19

    This study developed a heterogeneous catalytic permanganate oxidation system with ceria supported ruthenium, Ru/CeO2 (0.8‰ as Ru), as catalyst for the first time. The catalytic performance of Ru/CeO2 toward butylparaben (BP) oxidation by permanganate was strongly dependent on its dosage, pH, permanganate concentration and temperature. The presence of 1.0 g L(-1) Ru/CeO2 increased the oxidation rate of BP by permanganate at pH 4.0-8.0 by 3-96 times. The increase in Ru/CeO2 dosage led to a progressive enhancement in the oxidation rate of BP by permanganate at neutral pH. The XANES analysis revealed that (1) Ru was deposited on the surface of CeO2 as Ru(III); (2) Ru(III) was oxidized by permanganate to its higher oxidation state Ru(VI) and Ru(VII), which acted as the co-oxidants in BP oxidation; (3) Ru(VI) and Ru(VII) were reduced by BP to its initial state of Ru(III). Therefore, Ru/CeO2 acted as an electron shuttle in catalytic permanganate oxidation process. LC-MS/MS analysis implied that BP was initially attacked by permanganate or Ru(VI) and Ru(VII) at the aromatic ring, leading to the formation of various hydroxyl-substituted and ring-opening products. Ru/CeO2 could maintain its catalytic activity during the six successive runs. In conclusion, catalyzing permanganate oxidation with Ru/CeO2 is a promising technology for degrading phenolic pollutants in water treatment.

  16. 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.

  17. 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.

  18. A novel high-performance supercapacitor based on high-quality CeO2/nitrogen-doped reduced graphene oxide nanocomposite

    NASA Astrophysics Data System (ADS)

    Heydari, Hamid; Gholivand, Mohammad Bagher

    2017-03-01

    In this work, we have developed a novel nanocomposite via deposition of ceria (CeO2) on nitrogen-doped reduced graphene (CeO2/NRGO). NRGO was synthesized through a facile, safe, and scalable method to achieve simultaneous thermal reduction along with nitrogen doping of graphene oxide (GO) in air at much lower reaction temperature. CeO2/NRGO was prepared via a sonochemical method in which ceria nanoparticles were uniformly distributed on NRGO sheets. The structure and morphology of CeO2/NRGO nanocomposites were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared (FT-IR), and Raman spectroscopy. Electrochemical properties of the proposed nanocomposite electrodes were investigated by cyclic voltammetry (CV), galvanostatic charge/discharge, continuous cyclic voltammetry (CCV), and electrochemical impedance spectroscopy (EIS) measurements. CeO2-NRGO nanocomposite electrodes showed excellent supercapacitive behavior, including much higher specific capacitance (230 F g-1 at 2 mV s-1) and higher rate capability compared to pure N-graphene. The cycling stability of the electrodes was measured by continues cyclic voltammetry (CCV) technique. The CCV showed that the specific capacitance of the CeO2/NRGO and NRGO nanocomposite maintained at 94.1 and 93.2% after 4000 cycles. The results suggest its promising potential as efficient electrode material for supercapacitors.

  19. First-principles DFT+U investigation of charged states of defects and fission gas atoms in CeO2

    NASA Astrophysics Data System (ADS)

    Shi, Lei; Vathonne, Emerson; Oison, Vincent; Freyss, Michel; Hayn, Roland

    2016-09-01

    Cerium dioxide (CeO2) is considered as a model material for the experimental study of radiation damage in the standard nuclear fuel uranium dioxide (UO2). In this paper, we present a first-principles study in the framework of the DFT+U approach to investigate the charged point defects and the incorporation of the fission gases Xe and Kr in CeO2 and compare it with published data in UO2. All intrinsic charge states are considered for point defects in contrast to previous published studies. Our calculations prove that CeO2 shows similar behavior to UO2 in the formation of point defects with the same charge states under stoichiometric and nonstoichiometric conditions. The charge states of vacancies have an important effect on the incorporation of fission gas atoms in CeO2. The bound Schottky defect with the two oxygen vacancies along the (100) direction is found to be energetically preferable to trap Xe and Kr atoms both in CeO2 and UO2. Xe and Kr atoms in the cation vacancy sites under nonformal charge states (different from 4 - ) in CeO2, unlike in UO2, lose electrons to their neighboring atoms, which is traced back to the absence of the +5 valence state for Ce in contrast to its existence for U.

  20. 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

    2015-11-07

    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.

  1. 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.

  2. Comparative toxicity assessment of CeO2 and ZnO nanoparticles towards Sinorhizobium meliloti, a symbiotic alfalfa associated bacterium: use of advanced microscopic and spectroscopic techniques.

    PubMed

    Bandyopadhyay, Susmita; Peralta-Videa, Jose R; Plascencia-Villa, Germán; José-Yacamán, Miguel; Gardea-Torresdey, Jorge L

    2012-11-30

    Cerium oxide (CeO(2)) and zinc oxide (ZnO) nanoparticles (NPs) are extensively used in a variety of instruments and consumer goods. These NPs are of great concern because of potential toxicity towards human health and the environment. The present work aimed to assess the toxic effects of 10nm CeO(2) and ZnO NPs towards the nitrogen fixing bacterium Sinorhizobium meliloti. Toxicological parameters evaluated included UV/Vis measurement of minimum inhibitory concentration, disk diffusion tests, and dynamic growth. Ultra high-resolution scanning transmission electron microscopy (STEM) and infrared spectroscopy (FTIR) were utilized to determine the spatial distribution of NPs and macromolecule changes in bacterial cells, respectively. Results indicate that ZnO NPs were more toxic than CeO(2) NPs in terms of inhibition of dynamic growth and viable cells counts. STEM images revealed that CeO(2) and ZnO NPs were found on bacterial cell surfaces and ZnO NPs were internalized into the periplasmic space of the cells. FTIR spectra showed changes in protein and polysaccharide structures of extra cellular polymeric substances present in bacterial cell walls treated with both NPs. The growth data showed that CeO(2) NPs have a bacteriostatic effect, whereas ZnO NPs is bactericidal to S. meliloti. Overall, ZnO NPs were found to be more toxic than CeO(2) NPs.

  3. Investigation of surface defect states in CeO2-y nanocrystals by Scanning-tunneling microscopy/spectroscopy and ellipsometry

    NASA Astrophysics Data System (ADS)

    Radović, Marko; Stojadinović, Bojan; Tomić, Nataša; Golubović, Aleksandar; Matović, Branko; Veljković, Ivana; Dohčević-Mitrović, Zorana

    2014-12-01

    Synthesis process strongly influences the nanocrystalline CeO2-y defective structure. The presence of surface defects, in the form of oxygen vacancies in different charge states (F centers), can change the electronic properties of ceria nanocrystals. Nanocrystalline CeO2-y samples were synthesized using three different methods (precipitation, self-propagating room temperature, and hydrothermal synthesis). Raman spectroscopy was used to identify the presence of oxygen vacancies which presumably were formed at the nanoparticle surface. The defect concentration depended on the crystallite size of differently prepared CeO2-y samples. Scanning tunneling microscopy/spectroscopy and ellipsometry were employed to investigate the electronic band structure of defective CeO2-y nanocrystals. Scanning tunneling spectroscopy measurements demonstrated that inside the band gap of CeO2-y nanocrystals, besides the filled 4 f states, appeared additional states which were related to occupied and empty F center defect states. From the ellipsometric measurements, using the critical points model, the energy positions of different F centers states and the values of the reduced band gap energies were determined. The analysis of obtained data pointed out that depending on the synthesis method, different types of F centers (F+ and F0) can be formed in the CeO2-y nanocrystals. The formation of different F center defect states inside the ceria gap have a strong impact on the electrical, optical, and magnetic properties of ceria nanocrystals.

  4. 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.)

  5. 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.

  6. 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.

  7. New route to CeO2/LaCoO3 with high oxygen mobility for total benzene oxidation

    NASA Astrophysics Data System (ADS)

    Wang, Xiuyun; Zuo, Jiachang; Luo, Yongjin; Jiang, Lilong

    2017-02-01

    Electrospun LaCoO3 and Ce(NO3)3·6H2O were used as precursors to synthesize CeO2/LaCoO3 (SSI-LaCoCe) with high oxygen mobility by solid state impregnation. Besides, electrospinning and ball milling technologies were also adopted to prepare the other two La-Co-Ce oxides, which are denoted as ES-LaCoCe and BM-LaCoCe, respectively. The catalysts were evaluated for total benzene oxidation in comparison with bare electrospun LaCoO3 and CeO2, and characterized by means of O2-TPSR, XRD, BET, TEM, H2-TPR, O2-TPD, and XPS. Relative to LaCoO3, an enhanced catalytic performance can be obtained for La-Co-Ce oxides. Importantly, the concentration of surface adsorbed oxygen species from the highest to the lowest is SSI-LaCoCe > BM-LaCoCe > ES-LaCoCe, which is in good agreement with the order of catalytic activity in terms of T50. The high oxygen mobility in SSI-LaCoCe can be connected with sufficient interaction between active LaCoO3 and CeO2. On the other hand, O2-TPSR analysis match well with the catalytic behaviors of La-Co-Ce oxides. Moreover, the catalyst with the best performance, SSI-LaCoCe, also represents good thermal stability during the long-term continuous test.

  8. 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.

  9. Mechanical Properties and Corrosion Behavior of CeO2 and SiC Incorporated Al5083 Alloy Surface Composites

    NASA Astrophysics Data System (ADS)

    Amra, M.; Ranjbar, Khalil; Dehmolaei, R.

    2015-08-01

    In this investigation, nano-sized cerium oxide (CeO2) and silicon carbide (SiC) particles were stirred and mixed into the surface of an Al5083 alloy rolled plate using friction stir processing (FSP) to form a surface nano-composite layer. For this purpose, various volume ratios of the reinforcements either separately or in the combined form were packed into a pre-machined groove on the surface of the plate. Microstructural features, mechanical properties, and corrosion behavior of the resultant surface composites were determined. Microstructural analysis, optical microscopy and scanning electron microscopy, showed that reinforcement particles were fairly dispersed inside the stir zone and grain refinement was gained. Compared with the base alloy, all of the FSP composites showed higher hardness and tensile strength values with the maximum being obtained for the composite containing 100% SiC particles, i.e., Al5083/SiC. The corrosion behavior of the samples was studied by conducting potentiodynamic polarization tests and assessed in terms of corrosion potential, pitting potential, and passivation range. The result shows a significant increase in corrosion resistance of the base alloy; i.e., the longest passivation range when CeO2 alone was incorporated into the surface by acting as cathodic inhibitors. Composites reinforced with SiC particles exhibited lower pitting resistance due to the formation of microgalvanic couples between cathodic SiC particles and anodic aluminum matrix. The study was aimed to fabricate metal matrix surface composites with improved hardness, tensile strength, and corrosion resistance by the incorporation of CeO2 and SiC reinforcement particles into the surface of Al5083 base alloy. Optimum mechanical properties and corrosion resistance were obtained for the FSP composite Al5083/(75%CeO2 + 25%SiC). In this particular FSP composite, hardness and tensile strength were increased by 30, and 14%, respectively, and passivation range was increased to 0.19 V/SCE compared to the base alloy with no passivation range.

  10. 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.

  11. Engineering of nanoscale defect patterns in CeO2 nanorods via ex situ and in situ annealing.

    PubMed

    Sakthivel, Tamil Selvan; Reid, David L; Bhatta, Umananda M; Möbus, Günter; Sayle, Dean C; Seal, Sudipta

    2015-03-12

    Single-crystalline ceria nanorods were fabricated using a hydrothermal process and annealed at 325 °C-800 °C. As-synthesized CeO2 nanorods contain a high concentration of defects, such as oxygen vacancies and high lattice strains. Annealing resulted in an improved lattice crystalline quality along with the evolution of novel cavity-shaped defects in the nanorods with polyhedral morphologies and bound by e.g. {111} and {100} (internal) surfaces, confirmed for both air (ex situ) and vacuum (in situ) heating. We postulate that the cavities evolve via agglomeration of vacancies within the as-synthesized nanorods.

  12. 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

  13. 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

  14. 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

    2015-08-05

    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.

  15. Aspect ratio plays a role in the hazard potential of CeO2 nanoparticles in mouse lung and zebrafish gastrointestinal tract.

    PubMed

    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

    2014-05-27

    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 at 21 days but did not induce 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 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.

  16. In-situ transmission electron microscopy study of oxygen vacancy ordering and dislocation annihilation in undoped and Sm-doped CeO2 ceramics during redox processes

    NASA Astrophysics Data System (ADS)

    Ding, Yong; Chen, Yu; Pradel, Ken C.; Liu, Meilin; Lin Wang, Zhong

    2016-12-01

    Ceria (CeO2) based ceramics have been widely used for many applications due to their unique ionic, electronic, and catalytic properties. Here, we report our findings in investigating into the redox processes of undoped and Sm-doped CeO2 ceramics stimulated by high-energy electron beam irradiation within a transmission electron microscope (TEM). The reduced structure with oxygen vacancy ordering has been identified as the CeO1.68 (C-Ce2O3+δ) phase via high-resolution TEM. The reduction of Ce4+ to Ce3+ has been monitored by electron energy-loss spectroscopy. The decreased electronic conductivity of the Sm-doped CeO2 (Sm0.2Ce0.8O1.9, SDC) is revealed by electron holography, as positive electrostatic charges accumulated at the surfaces of SDC grains under electron beam irradiation, but not at CeO2 grains. The formation of the reduced CeO1.68 domains corresponds to lattice expansion compared to the CeO2 matrix. Therefore, the growth of CeO1.68 nuclei builds up strain inside the matrix, causing annihilation of dislocations inside the grains. By using in-situ high-resolution TEM and a fast OneView camera recording system, we investigated dislocation motion inside both CeO2 and SDC grains under electron beam irradiation. The dislocations prefer to dissociate into Shockley partials bounded by stacking faults. Then, the partials can easily glide in the {111} planes to reach the grain surfaces. Even the Lomer-Cottrell lock can be swept away by the phase change induced strain field. Our results revealed the high mobility of dislocations inside CeO2 and SDC grains during their respective redox processes.

  17. 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.

  18. 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

    2016-03-08

    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.

  19. 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.

  20. Laser clad Ni-base alloy added nano- and micron-size CeO 2 composites

    NASA Astrophysics Data System (ADS)

    Zhang, Shi Hong; Li, Ming Xi; Cho, Tong Yul; Yoon, Jae Hong; Lee, Chan Gyu; He, Yi Zhu

    2008-07-01

    Micron-size Ni-base alloy (NBA) powders are mixed with both 1.5 wt% (%) micron-CeO 2 (m-CeO 2) and also 1.0-3.0% nano-CeO 2 (n-CeO 2) powders. These mixtures are coated on low carbon steel (Q235) by 2.0 kW CO 2 laser cladding. The effects on microstructures, microhardness and wear resistance of the coating by the addition of m- and n-CeO 2 powders to NBA (m- and n-CeO 2/NBA) have been investigated. Addition to the primary phases of γ-Ni, Cr 23C 6 and Ni 3B of NBA coating, CeNi 3 shows up both in m- and n-CeO 2/NBA coatings and CeNi 5 appears only in n-CeO 2/NBA coating. Directional dendrite and coarse equiaxed dendrite are grown in m-CeO 2/NBA coating from interface to central zone, whereas multi-oriented dendrite and fine equiaxed dendrite growth by addition of n-CeO 2. The microhardness and wear resistance of coatings are greatly improved by CeO 2 powder addition, and compared to the addition of 1.0% and 3.0%, 1.5% n-CeO 2/NBA is the best. Hardness and wear resistance of the coating improves with decreasing CeO 2 size from micron to nano.

  1. [Catalytic wet air oxidation of phenol with Ru/ZrO2-CeO2 catalyst].

    PubMed

    Wang, Jian-bing; Zhu, Wan-peng; Wang, Wei; Yang, Shao-xia

    2007-07-01

    Wet air oxidation of phenol with Ru/ZrO2-CeO2 was systematically investigated and results showed that Ru/ZrO2-CeO2 could significantly increase the removal of COD and phenol. At the reaction temperature of 170 degrees C and pressure of 3MPa, about 99% COD and 100% phenol was removed respectively after 120 min. The optimal conditions were: reaction temperature, 170 degrees C; reaction pressure, 3 MPa; catalyst dosage, 5 g/L; agitator speed, 500 r/min. By analyzing intermediates, a simplified scheme of phenol oxidation was brought out. It includes two main steps. The first step is the production of organic acids, which is fast. The second step is the oxidation of organic acid, in which the oxidation of acetic acid is slow. Complete oxidation of acetic acid needs high temperature at which the radicals assault the C-H bond of a carbon and acetic acid is oxidized into carbon dioxide and water through formic acid.

  2. 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.

  3. 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.

  4. 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.

  5. Nanoscale mechanochemical wear of phosphate laser glass against a CeO2 particle in humid air

    NASA Astrophysics Data System (ADS)

    Yu, Jiaxin; He, Hongtu; Zhang, Yafeng; Hu, Hailong

    2017-01-01

    Using an atomic force microscope, the friction and wear of phosphate laser glass against a CeO2 particle were quantitatively studied both in humid air and in vacuum, to reveal the water molecules induced mechanochemical wear mechanism of phosphate laser glass. The friction coefficient of the glass/CeO2 pair in air was found to be 5-7 times higher than that in vacuum due to the formation of a capillary water bridge at the friction interface, with a contribution of the capillary-related friction to the total friction coefficient as high as 65-79%. The capillary water bridge further induced a serious material removal of glass and CeO2 particle surfaces, while supplying both a local liquid water environment to corrode the glass surface and a high shearing force to assist the stretching of the Cesbnd Osbnd P bond, accelerating the reaction between water and the glass/CeO2 pair. In vacuum, however, no discernable wear phenomena were observed, but the phase images captured by AFM tapping mode suggested the occurrence of potential strain hardening in the friction area of the glass surface.

  6. 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.

  7. Enhanced CO oxidation on CeO2/Co3O4 nanojunctions derived from annealing of metal organic frameworks.

    PubMed

    Wang, Changlai; Wang, Dongdong; Yang, Yang; Li, Ren; Chen, Changle; Chen, Qianwang

    2016-12-01

    The interface of nanojunctions plays an important role in the performance of heterogeneous catalysts. However, it is highly challenging to construct nanojunctions which are usually prepared by complex multistep processes. Metal-organic frameworks (MOFs), with designable metal centers and tunable organic ligands, are promising precursors for the one-step synthesis of nanojunctions. Herein, we prepared porous CeO2/Co3O4 nanojunctions by direct annealing of MOFs in air. These unique nanojunctions exhibit remarkable catalytic activity for CO oxidation, which can achieve complete oxidization of CO to CO2 at 110 °C. In contrast, the temperature required for 100% CO oxidation is 190 °C for pure Co3O4. Moreover, the nanojunctions can maintain complete CO conversion after 16 h at 110 °C. Density functional theory calculations revealed that the enhancement in the catalytic activity of CeO2/Co3O4 nanojunctions can be attributed to the charge transfer through the interfaces of the nanojunctions.

  8. 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.

  9. Adsorption mechanism and kinetics of azo dye chemicals on oxide nanotubes: a case study using porous CeO2 nanotubes

    NASA Astrophysics Data System (ADS)

    Wu, Junshu; Wang, Jinshu; Du, Yucheng; Li, Hongyi; Jia, Xinjian

    2016-07-01

    Metal oxide nanotubes are believed to be promising materials with adsorption functionality for water purification due to their synergistic effect of the overall microscale morphology for easy separation and nanoscale surface characters providing enough surface active absorption sites. This work shows the synthesis of uniform hierarchical porous CeO2 nanotubes via nanowire-directed templating method and describes the adsorption behavior of CeO2 nanotubes for a typical azo dye Congo red which has resistance to oxidation and decoloration in natural conditions. Fourier transform infrared spectroscopy spectra provided the evidence that Congo red was successfully coated on the surface of CeO2 nanotubes by both bidentate-type bridge link of Ce4+ cations from sulfonate SO3 - groups and the electrostatic attraction between the protonated surface generated by oxygen vacancies and dissociated sulfonate groups. The adsorption kinetic data fitted well to the pseudo-second-order kinetic equation, whereas the Langmuir isotherm equation exhibited better correlation with the experimental data. The calculated maximum adsorption capacity from the isothermal model was 362.32 mg/g. In addition, the prepared CeO2 nanotubes exhibited good recyclability and reusability as highly efficient adsorbents for Congo red removal after regeneration. These favorable performances enable the obtained CeO2 nanotubes to be promising materials for dye removal from aqueous solution.

  10. Nanoflake-assembled Al2O3-supported CeO2-ZrO2 as an efficient catalyst for oxidative dehydrogenation of ethylbenzene with CO2

    NASA Astrophysics Data System (ADS)

    Wang, Tehua; Guan, Xiaolin; Lu, Huiyi; Liu, Zhongwen; Ji, Min

    2017-03-01

    An Al2O3 material assembled by nanoflakes was used to prepare supported CeO2-ZrO2 catalyst via a deposition-precipitation method for oxidative dehydrogenation of ethylbenzene with CO2. Both unsupported and commercial Al2O3-supported CeO2-ZrO2 were prepared for comparison. It was found that the CeO2-ZrO2/nanoflake-assembled Al2O3 catalyst exhibited the best catalytic activity. The characterization results revealed that the slit-shape pores existing in nanoflake-assembled Al2O3 were responsible for the small particle size and high Ce/Zr surface ratio of supported CeO2-ZrO2 species. The dispersion of Ce1-xZrx(OH)4 precursors onto Al2O3 support surface during the deposition-precipitation process was proposed. The high dispersion and large numbers of surface oxygen vacancies of the CeO2-ZrO2 species on nanoflake-assembled Al2O3 contributed to the excellent catalytic performance in oxidative dehydrogenation of ethylbenzene with CO2. This kind of special Al2O3 is expected to be a promising support for preparing highly dispersed metal/metal oxide catalysts.

  11. 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.

  12. 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

    2014-12-10

    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.

  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. 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.

  15. Influence of CeO2 NPs on biological phosphorus removal and bacterial community shifts in a sequencing batch biofilm reactor with the differential effects of molecular oxygen.

    PubMed

    Xu, Yi; Wang, Chao; Hou, Jun; Wang, Peifang; You, Guoxiang; Miao, Lingzhan; Lv, Bowen; Yang, Yangyang

    2016-11-01

    The effects of CeO2 nanoparticles (CeO2 NPs) on a sequencing batch biofilm reactor (SBBR) with established biological phosphorus (P) removal were investigated from the processes of anaerobic P release and aerobic P uptake. At low concentration (0.1mg/L), no significant impact was observed on total phosphorus (TP) removal after operating for 8h. However, at a concentration of 20mg/L, TP removal efficiency decreased from 83.68% to 55.88% and 16.76% when the CeO2 NPs were added at the beginning of the anaerobic and aerobic periods, respectively. Further studies illustrated that the inhibition of the specific P release rate was caused by the reversible states of Ce(3+) and Ce(4+), which inhibited the activity of exopolyphosphatase (PPX) and transformation of poly-β-hydoxyalkanoates (PHA) and glycogen, as well as the uptake of volatile fatty acids (VFAs). The decrease in the specific P uptake rate was mainly attributed to the significantly suppressed energy generation and decreased abundance of Burkholderia caused by excess reactive oxygen species. The removal of chemical oxygen demand (COD) was not influenced by CeO2 NPs under aerobic conditions, due to the increased abundance of Acetobacter and Acidocella after exposure. The inhibitory effects of CeO2 NPs with molecular oxygen were reduced after anaerobic exposure due to the enhanced particle size and the presence of Ce(3+).

  16. Comparison of the effects of platinum and CeO2 on the properties of single grain, Sm-Ba-Cu-O bulk superconductors

    NASA Astrophysics Data System (ADS)

    Zhao, Wen; Shi, Yunhua; Radušovská, Monika; Dennis, Anthony R.; Durrell, John H.; Diko, Pavel; Cardwell, David A.

    2016-12-01

    SmBa2Cu3O7-δ (Sm-123) is a light-rare-earth barium-cuprate (LRE-BCO) high-temperature superconductor (HTS) with significant potential for high field industrial applications. We report the fabrication of large, single grain bulk [Sm-Ba-Cu-O (SmBCO)] superconductors containing 1 wt% CeO2 and 0.1 wt% Pt using a top-seeded melt growth process. The performance of the SmBCO bulk superconductors containing the different dopants was evaluated based on an analysis of their superconducting properties, including critical transition temperature, T c and critical current density, J c , and on sample microstructure. We find that both CeO2 and Pt dopants refine the size of Sm2BaCuO5 (Sm-211) particles trapped in the Sm-123 superconducting phase matrix, which act as effective flux pinning centres, although the addition of CeO2 results in broadly improved superconducting performance of the fully processed bulk single grain. However, 1 wt% CeO2 is significantly cheaper than 0.1 wt% Pt, which has clear economic benefits for use in medium to large scale production processes for these technologically important materials. Finally, the use of CeO2 results generally in the formation of finer Sm-211 particles and to the generation of fewer macro-cracks and Sm-211 free regions in the sample microstructure.

  17. 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.

  18. 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).

  19. Synthesis and characterization of reduced graphene oxide decorated with CeO2-doped MnO2 nanorods for supercapacitor applications.

    PubMed

    Ojha, Gunendra Prasad; Pant, Bishweshwar; Park, Soo-Jin; Park, Mira; Kim, Hak-Yong

    2017-05-15

    A novel and efficient CeO2-doped MnO2 nanorods decorated reduced graphene oxide (CeO2-MnO2/RGO) nanocomposite was successfully synthesized via hydrothermal method. The growth of the CeO2 doped MnO2 nanorods over GO sheets and reduction of GO were simultaneously carried out under hydrothermal treatment. The morphology and structure of as-synthesized nanocomposite were characterized by field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and Raman spectroscopy, which revealed the formation of CeO2-MnO2 decorated RGO nanocomposites. The electrochemical performance of as-prepared CeO2-MnO2/RGO nanocomposites as an active electrode material for supercapacitor was evaluated by cyclic voltammetry, charge-discharge, and electrochemical impedance spectroscopy (EIS) methods in 2M alkaline medium. The obtained results revealed that as-synthesized CeO2-MnO2/RGO nanocomposite exhibited higher specific capacitance (648F/g) as compared to other formulations (MnO2/RGO nanocomposites: 315.13 F/g and MnO2 nanorods: 228.5 F/g) at the scan rate of 5mV/s. After 1000 cycles, it retained ∼90.4%, exhibiting a good stability. The high surface area, enhanced electrical conductivity, and good stability possess by the nanocomposite make this material a promising candidate to be applied as a supercapacitor electrode.

  20. The Origin of Elastic Anomalies in Thin Films of Oxygen Deficient Ceria CeO(2-x)

    SciTech Connect

    A Kossoy; A Frenkel; Y Feldman; E Wachtel; A Milner; I Lubomirsky

    2011-12-31

    Self-supported films of CeO{sub 1.95} display time-scale dependent elastic moduli, a phenomenon which has been termed the chemical strain effect. In order to probe the possible structural origins of this behavior, extended X-ray absorption fine structure spectroscopy and X-ray diffraction were used. Evidence was found that, although this oxygen deficient ceria appears to maintain the fluorite structure on average, the mean Ce-O bond length is shorter than the mean Ce-oxygen vacancy distance. This finding is consistent with crystallographic data from more strongly reduced ceria in which the oxygen vacancies are ordered. By studying strain induced structural changes, we show that it is possible to relate this lattice distortion to the chemical strain effect. Similar conclusions were previously reached for films of Ce{sub 0.8}Gd{sub 0.2}O{sub 1.9}. Since the ionic radii of both Gd{sup 3+} and Ce{sup 3+} are larger than that of Ce{sup 4+}, we suggest that when cation dopants are larger than the host, ceria compounds containing a high concentration of oxygen vacancies may exhibit elastic anomalies.

  1. Interfacial interaction in monolayer transition metal dichalcogenide/metal oxide heterostructures and its effects on electronic and optical properties: The case of MX2/CeO2

    NASA Astrophysics Data System (ADS)

    Yang, Ke; Huang, Wei-Qing; Hu, Wangyu; Huang, Gui-Fang; Wen, Shuangchun

    2017-01-01

    Using the density functional theory (DFT), we systematically study the interfacial interaction in monolayer MX2 (M = Mo, W; X = S, Se)/CeO2 heterostructures and its effects on electronic and optical properties. The interfacial interaction in the MX2/CeO2 heterostructures depends largely on chalcogens, and its strength determines the band gap variation and important electronic states at the band edges of the heterostructures. The MX2/CeO2 heterostructures with the same chalcogen have similar absorption spectra, from ultraviolet to near-infrared regions. These results suggest that chalcogens importantly determine the properties of MX2/metal oxide heterostructures.

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

    DOE PAGES

    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

  4. On the adsorption and formation of Pt dimers on the CeO2(111) surface.

    PubMed

    Bruix, Albert; Nazari, Fariba; Neyman, Konstantin M; Illas, Francesc

    2011-12-28

    The direct adsorption of Pt(2) dimers on CeO(2)(111) and their formation from isolated adsorbed Pt atoms have been studied using periodic slab model calculations based on density functional theory and including the so-called on-site Hubbard parameter (GGA + U). In the most stable configuration Pt(2) is found to be almost parallel to the surface; the electronic ground state is closed shell and there is no evidence of charge transfer towards or from the surface. The formation of Pt(2) from two single adsorbed Pt atoms involves a rather small energy barrier of ~0.10 eV only. On the contrary, dissociation of adsorbed Pt(2) requires to overcome a considerable barrier of ~1.43 eV. This indicates that once Pt(2) is formed it will remain on the surface, thus likely triggering the growth of larger supported Pt particles.

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

    DOE PAGES

    Lipp, M. J.; Jeffries, J. R.; Cynn, H.; ...

    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. 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 ...

  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. 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.

  10. 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...

  11. [Experimental study of catalytic reduction of SO2 on CeO2-La2O3/gamma-Al2O3 rare earth mixed compounds].

    PubMed

    Hu, Hui; Li, Jin; Zhang, Shun-xi; Li, Sheng-li

    2004-03-01

    Addition of rare earth oxide CeO2 with variable valences to La2O3 formed a mixture of rare earth oxides. This mixture can be used as the catalyst for the reduction of SO2 by CO. In a fixed-bed flow reactor, experimental were investigated for studying the activation process of this catalyst and effect factors such as temperature and concentration ratio of reactant on the activation reaction under the following conditions: composition of the gas mixture SO2:CO = 1:3, balancing with N2 and feed flow rate 1000 mL/min. The phase structure changes of this catalyst were expressed with XRD and XPS. The results demonstrated that the activation temperature of CeO2-La2O3/gamma-Al2O3 is 50-100 degrees C lower than that of a single component La2O3/gamma-Al2O3 or CeO2/gamma-Al2O3, and the mixture of rare earth oxides has higher activity on catalytic reduction of SO2 by CO. It's most likely that the result reveals on the synergism between CeO2 and La2O3.

  12. 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

    2016-09-07

    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.

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

    PubMed

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

    2010-10-01

    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 CeO(2) 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 CeO(2) 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 CeO(2) 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 CeO(2) NPs.

  14. 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.

  15. 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.

  16. Origin of enhanced visible-light photocatalytic activity of transition-metal (Fe, Cr and Co)-doped CeO2: effect of 3 d orbital splitting

    NASA Astrophysics Data System (ADS)

    Yang, Ke; Li, Dong-Feng; Huang, Wei-Qing; Xu, Liang; Huang, Gui-Fang; Wen, Shuangchun

    2017-01-01

    Enhanced visible-light photocatalytic activity of transition-metal-doped ceria (CeO2) nanomaterials has experimentally been demonstrated, whereas there are very few reports mentioning the mechanism of this behavior. Here, we use first-principles calculations to explore the origin of enhanced photocatalytic performance of CeO2 doped with transition metal impurities (Fe, Cr and Co). When a transition metal atom substitutes a Ce atom into CeO2, t 2g and e g levels of 3 d orbits appear in the middle of band gap owing to the effect of cubic ligand field, and the former is higher than latter. Interestingly, t 2g subset of FeCe (CoCe and CrCe)-Vo-CeO2 splits into two parts: one merges into the conduction band, the other as well as e g will remain in the gap, because O vacancy defect adjacent to transition metal atom will break the symmetry of cubic ligand field. These e g and t 2g levels in the band gap are beneficial for absorbing visible-light and enhancing quantum efficiency because of forbidden transition, which is one key factor for enhanced visible-light photocatalytic activity. The band gap narrowing also leads to a redshift of optical absorbance and high photoactivity. These findings can rationalize the available experimental results and provide some new insights for designing CeO2-based photocatalysts with high photocatalytic performance.

  17. 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.

  18. [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.

  19. No genotoxicity in rat blood cells upon 3- or 6-month inhalation exposure to CeO2 or BaSO4 nanomaterials.

    PubMed

    Cordelli, Eugenia; Keller, Jana; Eleuteri, Patrizia; Villani, Paola; Ma-Hock, Lan; Schulz, Markus; Landsiedel, Robert; Pacchierotti, Francesca

    2017-01-01

    In the course of a 2-year combined chronic toxicity-carcinogenicity study performed according to Organisation for Economic Co-operation and Development (OECD) Test Guideline 453, systemic (blood cell) genotoxicity of two OECD representative nanomaterials, CeO2 NM-212 and BaSO4 upon 3- or 6-month inhalation exposure to rats was assessed. DNA effects were analysed in leukocytes using the alkaline Comet assay, gene mutations and chromosome aberrations were measured in erythrocytes using the flow cytometric Pig-a gene mutation assay and the micronucleus test (applying both microscopic and flow cytometric evaluation), respectively. Since nano-sized CeO2 elicited lung effects at concentrations of 5mg/m(3) (burdens of 0.5mg/lung) in the preceding range-finding study, whereas nano-sized BaSO4 did not induce any effect, female rats were exposed to aerosol concentrations of 0.1 up to 3mg/m(3) CeO2 or 50mg/m(3) BaSO4 nanomaterials (6h/day; 5 days/week; whole-body exposure). The blood of animals treated with clean air served as negative control, whereas blood samples from rats treated orally with three doses of 20mg/kg body weight ethylnitrosourea at 24h intervals were used as positive controls. As expected, ethylnitrosourea elicited significant genotoxicity in the alkaline Comet and Pig-a gene mutation assays and in the micronucleus test. By contrast, 3- and 6-month CeO2 or BaSO4 nanomaterial inhalation exposure did not elicit significant findings in any of the genotoxicity tests. The results demonstrate that subchronic inhalation exposure to different low doses of CeO2 or to a high dose of BaSO4 nanomaterials does not induce genotoxicity on the rat hematopoietic system at the DNA, gene or chromosome levels.

  20. Macroporous graphene capped Fe3O4 for amplified electrochemiluminescence immunosensing of carcinoembryonic antigen detection based on CeO2@TiO2.

    PubMed

    Yang, Lei; Zhu, Wenjuan; Ren, Xiang; Khan, Malik Saddam; Zhang, Yong; Du, Bin; Wei, Qin

    2017-05-15

    A novel electrochemiluminescence (ECL) signal-amplified immunosensing strategy was proposed by using gold nanoparticles (Au NPs) functionalized reduced graphene oxide (rGO) capped Fe3O4 (Au-FrGO). In this work, CeO2@TiO2 was prepared by a sol-gel method to wrap CeO2 with TiO2. In the presence of CeO2, CeO2@TiO2 exhibited better ECL activity than TiO2 with peroxydisulfate as coreactant. In addition, FrGO with macroporous structure was synthesized by self-assembly of rGO sheets capped cationic Fe3O4 nanoparticles, exhibiting larger specific surface area than rGO. Due to the low toxicity and magnetism of Fe3O4, FrGO owned more favorable biocompatibility and the application of magnetic-separation simplified the preparation procedure. After hybridizing with Au NPs, FrGO exhibited more excellent electrical conductivity and could immobilize more CeO2@TiO2 and antibodies. Therefore, a novel label-free ECL immunosensor based on Au-FrGO-CeO2@TiO2 was constructed which generated higher ECL response. To investigate the performance of the immunosensor, carcinoembryonic antigen (CEA) was chosen as a model target analyte. Under optimal conditions, the immunosensor had sensitive response to CEA in a wide linear range of 0.01pgmL(-1) to 10ngmL(-1) with a detection limit of 3.28 fg mL(-1). The proposed ECL immunosensor exhibited excellent stability, repeatability and selectivity, which opened another promising avenue for CEA determination in real serum samples.

  1. Chloride salt of conducting polyaniline synthesized in the presence of CeO2: Structural analysis of the core-shell nanocomposite

    NASA Astrophysics Data System (ADS)

    da Silva, J. S. M.; de Souza, S. M.; Trovati, G.; Sanches, E. A.

    2017-01-01

    Chloride salt of conducting Polyaniline (ES-PANI) was synthesized in the presence of cerium dioxide (CeO2) for structural and morphological evaluation of the resulting core-shell nanocomposite. X-ray Diffraction (XRD), estimative of crystallinity percentage, Le Bail Method, Scanning Electron Microscopy (SEM) and DC electrical conductivity were used for materials characterization. The resulting nanocomposite was constituted of three phases as identified by X-Ray Diffraction: ES-PANI, CeO2 and CeCl3(H2O)7, chloride hepta-hydrate cerium. Crystallinity of ES-PANI and nanocomposite were estimated around 40 and 85%, respectively. XRD patterns were also used to perform the Le Bail Method. This refinement allowed structural characterization of each phase, obtainment of cell parameters and crystallite size and shape. For ES-PANI and CeCl3(H2O)7, crystallites showed a prolate-like shape with an average size of 21 Å and 104 Å, respectively. CeO2 crystallites presented much larger size, as expected, with isotropic average size of 490 Å. SEM images showed that the nanocomposite has a core-shell morphology with both ES-PANI nanofibers and CeCl3(H2O)7 particles coating the CeO2 particles. The polymerization of ES-PANI over the CeO2 particles in order to form the nanocomposite affected the natural chain alignment of the polymer, resulting in better molecular rearrangement and larger crystallites. Finally, measurements of DC electrical conductivity of ES-PANI and nanocomposite have showed values of 1.11 × 10-4 and 2.22 × 10-4 S/cm, respectively. Nanocomposite has showed electrical conductivity 50 times greater than the pure ES-PANI. Thus, in this work we have reported a systematic structural and morphological investigation of PANI/CeO2/CeCl3(H2O)7 core-shell nanocomposite.

  2. Design strategies for P-containing fuels adaptable CeO2-MoO3 catalysts for DeNO(x): significance of phosphorus resistance and N2 selectivity.

    PubMed

    Chang, Huazhen; Jong, Min Tze; Wang, Chizhong; Qu, Ruiyang; Du, Yu; Li, Junhua; Hao, Jiming

    2013-10-15

    Phosphorus compounds from flue gas have a significant deactivation effect on selective catalytic reduction (SCR) DeNOx catalysts. In this work, the effects of phosphorus over three catalysts (CeO2, CeO2-MoO3, and V2O5-MoO3/TiO2) for NH3-SCR were studied, and characterizations were performed aiming at a better understanding of the behavior and poisoning mechanism of phosphorus over SCR catalysts. The CeO2-MoO3 catalyst showed much better catalytic behavior with respect to resistance to phosphorus and N2 selectivity compared with V2O5-MoO3/TiO2 catalyst. With addition of 1.3 wt % P, the SCR activity of V2O5-MoO3/TiO2 decreased dramatically at low temperature due to the impairment of redox property for NO oxidation; meanwhile, the activity over CeO2 and CeO2-MoO3 catalysts was improved. The superior NO oxidation activity contributes to the activity over P-poisoned CeO2 catalyst. The increased surface area and abundant acidity sites contribute to excellent activity over CeO2-MoO3 catalyst. As the content of P increased to 3.9 wt %, the redox cycle over CeO2 catalyst (2CeO2 ↔ Ce2O3 + O*) was destroyed as phosphate accumulated, leading to the decline of SCR activity; whereas, more than 80% NOx conversion and superior N2 selectivity were obtained over CeO2-MoO3 at T > 300 °C. The effect of phosphorus was correlated with the redox properties of SCR catalyst for NH3 and NO oxidation. A spillover effect that phosphate transfers from Ce to Mo in calcination was proposed.

  3. 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.

  4. 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.

  5. 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

  6. Assessing Hubbard-corrected AM05+U and PBEsol+U density functionals for strongly correlated oxides CeO2 and Ce2O3.

    PubMed

    Weck, Philippe F; Kim, Eunja

    2016-09-29

    The structure-property relationships of bulk CeO2 and Ce2O3 have been investigated using AM05 and PBEsol exchange-correlation functionals within the frameworks of Hubbard-corrected density functional theory (DFT+U) and density functional perturbation theory (DFPT+U). Compared with conventional PBE+U, RPBE+U, PW91+U and LDA+U functionals, AM05+U and PBEsol+U describe experimental crystalline parameters and properties of CeO2 and Ce2O3 with superior accuracy, especially when +U is chosen close to its value derived by the linear-response approach. The present findings call for a reexamination of some of the problematic oxide materials featuring strong f- and d-electron correlation using AM05+U and PBEsol+U.

  7. 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

  8. Assessing Hubbard-corrected AM05+U and PBEsol+U density functionals for strongly correlated oxides CeO2 and Ce2O3

    DOE PAGES

    Weck, Philippe F.; Kim, Eunja

    2016-09-12

    The structure–property relationships of bulk CeO2 and Ce2O3 have been investigated using AM05 and PBEsol exchange–correlation functionals within the frameworks of Hubbard-corrected density functional theory (DFT+U) and density functional perturbation theory (DFPT+U). Compared with conventional PBE+U, RPBE+U, PW91+U and LDA+U functionals, AM05+U and PBEsol+U describe experimental crystalline parameters and properties of CeO2 and Ce2O3 with superior accuracy, especially when +U is chosen close to its value derived by the linear-response approach. Lastly, the present findings call for a reexamination of some of the problematic oxide materials featuring strong f- and d-electron correlation using AM05+U and PBEsol+U.

  9. 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.

  10. Spontaneous organization of uniform CeO2 nanoflowers by 3D oriented attachment in hot surfactant solutions monitored with an in situ electrical conductance technique.

    PubMed

    Zhou, Huan-Ping; Zhang, Ya-Wen; Mai, Hao-Xin; Sun, Xiao; Liu, Qiang; Song, Wei-Guo; Yan, Chun-Hua

    2008-01-01

    Uniform CeO(2) nanoflowers were synthesized by rapid thermolysis of (NH(4))(2)Ce(NO(3))(6) in oleic acid (OA)/oleylamine (OM), by a unique 3D oriented-attachment mechanism. CeO(2) nanoflowers with controlled shape (cubic, four-petaled, and starlike) and tunable size (10-40 nm) were obtained by adjusting the reaction conditions including solvent composition, precursor concentration, reaction temperature, and reaction time. The nanoflower growth mechanism was investigated by in situ electrical conductance measurements, transmission electron microscopy, and UV/Vis spectroscopy. The CeO(2) nanoflowers are likely formed in two major steps, that is, initial formation of ceria cluster particles capped with various ligands (e.g., OA, OM, and NO(3) (-)) via hydrolysis of (NH(4))(2)Ce(NO(3))(6) at temperatures in the range 140-220 degrees C, and subsequent spontaneous organization of the primary particles into nanoflowers by 3D oriented attachment, due to a rapid decrease in surface ligand coverage caused by sudden decomposition of the precursor at temperatures above 220 degrees C in a strong redox reaction. After calcination at 400 degrees C for 4 h the 33.8 nm CeO(2) nanoflowers have a specific surface area as large as 156 m(2) g(-1) with high porosity, and they are highly active for conversion of CO to CO(2) in the low temperature range of 200-400 degrees C. The present approach has also been extended to the preparation of other transition metal oxide (CoO, NiO, and CuO(x)) nanoflowers.

  11. 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.

  12. Influence of shear forces on the aggregation and sedimentation behavior of cerium dioxide (CeO2) nanoparticles under different hydrochemical conditions

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

    This study contributed to a better understanding of the behavior of nanoparticles (NPs) in dynamic water. First, the aggregation behavior of CeO2 NPs at different pH values in various salt solutions was examined to determine the appropriate hydrochemical conditions for hydrodynamics study. Second, the aggregation behavior of CeO2 NPs under different shear forces was investigated at pH 4 and ionic strength 0 in various salt solutions to find out whether shear forces could influence the stability of the nanoparticles and if yes, how. Also, five-stage sedimentation tests were conducted to understand the influence of shear stress on the vertical distribution of CeO2 NPs in natural waters. The aggregation test showed that the shear force could increase the collision efficiency between NPs during aggregation and cause a relatively large mass of NPs to remain in suspension. Consequently, the nanoparticles had a greater possibility of continued aggregation. The sedimentation test under static conditions indicated that a large mass of NPs (>1000 nm) sink to the bottom layer, leaving only small aggregates dispersed in the upper or middle layer of the solution. However, later sedimentation studies under stirring conditions demonstrated that shear forces can disrupt this stratification phenomenon. These results suggest that shear forces can influence the spatial distribution of NPs in natural waters, which might lead to different toxicities of CeO2 NPs to aquatic organisms distributed in the different water layers. This study contributes to a better understanding of nanomaterial toxicology and provides a way for further research.

  13. 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.

  14. 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.

  15. 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...

  16. 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.

  17. 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

  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.

  19. 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.

  20. 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.

  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. The role of the CeO 2 /BiVO 4 interface in optimized Fe–Ce oxide coatings for solar fuels photoanodes

    DOE PAGES

    Shinde, A.; Li, G.; Zhou, L.; ...

    2016-09-09

    Solar fuel generators entail a high degree of materials integration, and efficient photoelectrocatalysis of the constituent reactions hinges upon the establishment of highly functional interfaces. Our recent application of high throughput experimentation to interface discovery for solar fuels photoanodes has revealed several surprising and promising mixed-metal oxide coatings for BiVO4. Furthermore, when using sputter deposition of composition and thickness gradients on a uniform BiVO4 film, we systematically explore photoanodic performance as a function of the composition and loading of Fe–Ce oxide coatings. This combinatorial materials integration study not only enhances the performance of this new class of materials but alsomore » identifies CeO2 as a critical ingredient that merits detailed study. A heteroepitaxial CeO2(001)/BiVO4(010) interface is identified in which Bi and V remain fully coordinated to O such that no surface states are formed. Ab initio calculations of the integrated materials and inspection of the electronic structure reveals mechanisms by which CeO2 facilitates charge transport while mitigating deleterious recombination. Our results support the observations that addition of Ce to BiVO4 coatings greatly enhances photoelectrocatalytic activity, providing an important strategy for developing a scalable solar fuels technology.« less

  3. Influence of water on the electrochemical properties of CeO2TiO2 sol-gel coatings and electrochromic devices

    NASA Astrophysics Data System (ADS)

    Sun, Dong Lan; Puetz, Joerg; Heusing, Sabine; Aegerter, Michel A.

    2002-10-01

    The paper focuses on a systematic study of the influence of water on the electrochemical and optical properties of CeO2-TiO2 amd WO3 sol-gel coatings as well as devices made with these layers. The coatings were studied electrochemically in 1 M LiC1O4 in propylene carbonate electrolyte with water content up to 3 wt%. The intercalculated and deintercalated charge was measured during Cyclic Voltammetry (CV) and Chronoamperometric (CA) cycles up to 500 cycles (TiO2-CeO2) and 7000 cycles (WO3). For CeO2-TiO2 it was found to increase from 3mC/cm2 (dry electrolyte) up to 11 mC/cm2 (3 wt% water). This increase is important for the coloration of EC-devices because the charge capacity of this counter electrode is known to be a limiting factor for the transmission change of the EC-devices. For WO3 coatings, the transmission change (Tcolored-Tbleached)is higher in wet electrolytes (1 wt% water) than dry electrolyte and above all remains constant (74%). These improvements are essentially due to an increase of the kinetics of the intercalation and deintercalation of Li+ ions. The electro-optical behavior of solid state EC-devices with and without incorporation of water in the solid electrolyte measured up to 500000 CA cycles is also presented and discussed.

  4. 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.

  5. On the difficulties of present theoretical models to predict the oxidation state of atomic Au adsorbed on regular sites of CeO2(111).

    PubMed

    Branda, María Marta; Castellani, Norberto J; Grau-Crespo, Ricardo; de Leeuw, Nora H; Hernandez, Norge C; Sanz, Javier F; Neyman, Konstantin M; Illas, Francesc

    2009-09-07

    The electronic structure and oxidation state of atomic Au adsorbed on a perfect CeO(2)(111) surface have been investigated in detail by means of periodic density functional theory-based calculations, using the LDA+U and GGA+U potentials for a broad range of U values, complemented with calculations employing the HSE06 hybrid functional. In addition, the effects of the lattice parameter a(0) and of the starting point for the geometry optimization have also been analyzed. From the present results we suggest that the oxidation state of single Au atoms on CeO(2)(111) predicted by LDA+U, GGA+U, and HSE06 density functional calculations is not conclusive and that the final picture strongly depends on the method chosen and on the construction of the surface model. In some cases we have been able to locate two well-defined states which are close in energy but with very different electronic structure and local geometries, one with Au fully oxidized and one with neutral Au. The energy difference between the two states is typically within the limits of the accuracy of the present exchange-correlation potentials, and therefore, a clear lowest-energy state cannot be identified. These results suggest the possibility of a dynamic distribution of Au(0) and Au(+) atomic species at the regular sites of the CeO(2)(111) surface.

  6. 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.

  7. Intermediate Ce3+ defect level induced photoluminescence and third-order nonlinear optical effects in TiO2-CeO2 nanocomposites

    NASA Astrophysics Data System (ADS)

    Divya, S.; Nampoori, V. P. N.; Radhakrishnan, P.; Mujeeb, A.

    2014-02-01

    We report on the linear and nonlinear optical studies of TiO2-CeO2 nanocomposites. It was found that the band gap of the nanocomposite can be tuned by varying Ce/Ti content. Nonlinear absorption characteristics of these samples were studied by employing open aperture Z-scan technique using an Nd:YAG laser (532 nm, 7 ns, 10 Hz). It has been observed that as the CeO2 amount increases, band gap of the nanocomposites decreases and the reason proposed for the change in band gap is the smudging of localised states of Ce3+ into the forbidden energy gap, thus acting as the intermediate state. Fluorescence studies confirmed the above argument. Nonlinear investigation revealed that with increase in the CeO2 amount, the two-photon absorption coefficient increased due to the modification of TiO2 dipole symmetry. Suitable candidature of the nanocomposites for the fabrication of nonlinear optical devices was proved by determining the optical limiting threshold.

  8. 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.

  9. 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).

  10. Kinetics of oxygen exchange over CeO2-ZrO2 fluorite-based catalysts.

    PubMed

    Sadovskaya, Ekaterina M; Ivanova, Yulia A; Pinaeva, Larisa G; Grasso, Giacomo; Kuznetsova, Tatiana G; van Veen, Andre; Sadykov, Vladislav A; Mirodatos, Claude

    2007-05-24

    The kinetics of 18O/16O isotopic exchange over CeO2-ZrO2-La2O3 and Pt/CeO2-ZrO2 catalysts have been investigated under the conditions of dynamic adsorption-desorption equilibrium at atmospheric pressure and a temperature range of 650-850 degrees C. The rates of oxygen adsorption-desorption on Pt sites, support surface, oxygen transfer (spillover) from Pt to the support as well as the amount of oxygen accumulated in the oxide bulk, and oxygen diffusion coefficient were estimated. The nanocrystalline structure of lanthana-doped ceria-zirconia prepared via the Pechini route with a developed network of domain boundaries and specific defects guarantees a high oxygen mobility in the oxide bulk (D = (1.5 / 2.0).10-18 m2 s-1 at 650 degrees C) and allows accumulation of over-stoichiometric/excess oxygen. For Pt/CeO2-ZrO2, oxygen transfer from Pt to support (characteristic time < 10-2 s) was shown to be responsible for the fast exchange between the gas-phase oxygen and oxygen adsorbed on the mixed oxide surface. The rate of direct exchange between the gas phase and surface oxygen is increased as well due to the increased concentration (up to 2 monolayers) of surface/near subsurface oxygen species accumulated on the oxygen vacancies (originated from the incorporation of highly dispersed Pt atoms). The characteristic time of diffusion of the oxygen localized in the subsurface layers is about 1 s. The overall quantity of over-stoichiometric oxygen and/or hydroxyl groups accumulated in the bulk can reach the equivalent of 10 monolayers, and characteristic time of oxygen diffusion within the bulk is about 20 s. All these kinetic data are required for the further step of modeling partial oxidation of hydrocarbons under steady- and unsteady-state conditions.

  11. Synthesis, characterization, and magnetic properties of monodisperse CeO2 nanospheres prepared by PVP-assisted hydrothermal method

    PubMed Central

    2012-01-01

    Ferromagnetism was observed at room temperature in monodisperse CeO2 nanospheres synthesized by hydrothermal treatment of Ce(NO3)3·6H2O using polyvinylpyrrolidone as a surfactant. The structure and morphology of the products were characterized by X-ray diffraction (XRD), Raman spectroscopy, transmission electron microscopy, high-resolution transmission electron microscopy, and field-emission scanning electron microscopy (FE-SEM). The optical properties of the nanospheres were determined using UV and visible spectroscopy and photoluminescence (PL). The valence states of Ce ions were also determined using X-ray absorption near edge spectroscopy. The XRD results indicated that the synthesized samples had a cubic structure with a crystallite size in the range of approximately 9 to 19 nm. FE-SEM micrographs showed that the samples had a spherical morphology with a particle size in the range of approximately 100 to 250 nm. The samples also showed a strong UV absorption and room temperature PL. The emission might be due to charge transfer transitions from the 4f band to the valence band of the oxide. The magnetic properties of the samples were studied using a vibrating sample magnetometer. The samples exhibited room temperature ferromagnetism with a small magnetization of approximately 0.0026 to 0.016 emu/g at 10 kOe. Our results indicate that oxygen vacancies could be involved in the ferromagnetic exchange, and the possible mechanism of formation was discussed based on the experimental results. PMID:22849756

  12. Room temperature redox reaction by oxide ion migration at carbon/Gd-doped CeO2 heterointerface probed by an in situ hard x-ray photoemission and soft x-ray absorption spectroscopies

    PubMed Central

    Tsuchiya, Takashi; Miyoshi, Shogo; Yamashita, Yoshiyuki; Yoshikawa, Hideki; Terabe, Kazuya; Kobayashi, Keisuke; Yamaguchi, Shu

    2013-01-01

    In situ hard x-ray photoemission spectroscopy (HX-PES) and soft x-ray absorption spectroscopy (SX-XAS) have been employed to investigate a local redox reaction at the carbon/Gd-doped CeO2 (GDC) thin film heterointerface under applied dc bias. In HX-PES, Ce3d and O1s core levels show a parallel chemical shift as large as 3.2 eV, corresponding to the redox window where ionic conductivity is predominant. The window width is equal to the energy gap between donor and acceptor levels of the GDC electrolyte. The Ce M-edge SX-XAS spectra also show a considerable increase of Ce3+ satellite peak intensity, corresponding to electrochemical reduction by oxide ion migration. In addition to the reversible redox reaction, two distinct phenomena by the electrochemical transport of oxide ions are observed as an irreversible reduction of the entire oxide film by O2 evolution from the GDC film to the gas phase, as well as a vigorous precipitation of oxygen gas at the bottom electrode to lift off the GDC film. These in situ spectroscopic observations describe well the electrochemical polarization behavior of a metal/GDC/metal capacitor-like two-electrode cell at room temperature. PMID:27877594

  13. A facile approach to fabrication of novel CeO2-TiO2 core-shell nanocomposite leads to excellent UV-shielding ability and lower catalytic activity

    NASA Astrophysics Data System (ADS)

    Bahadur, Newaz Mohammed; Kurayama, Fumio; Furusawa, Takeshi; Sato, Masahide; Siddiquey, Iqbal Ahmed; Hossain, Md. Mufazzal; Suzuki, Noboru

    2013-01-01

    This study reports the development of a fast and facile route for the synthesis of novel CeO2-TiO2 core-shell nanocomposite particles using microwave (MW) irradiation of the mixture of commercial CeO2, titanium-tetra- n-butoxide (TBOT) and aqueous ammonia. Solutions of TBOT in ethanol and ammonia were mixed with dispersed CeO2 nanoparticles in ethanol, and the mixture was rapidly MW irradiated at 70 °C for 2 min. The resulting nanocomposite particles were characterized in terms of phase, shell thickness, composition, surface charge, morphology, and chemical state of the elements by XRD, TEM, XPS, SEM, Zeta potential analyzer, XRF, and FT-IR. Conventional methods of the synthesis of CeO2-TiO2 nanocomposite require a long time, and TiO2 is rarely found as a coated material. In contrast, the MW method was able to synthesize CeO2-TiO2 core-shell nanocompsite particles within a very short time. CeO2-TiO2 nanocomposite particles were fairly unaggregated with an average titania layer thickness of 2-5 nm. The obtained nanocomposites retained the crystalline cubic phase of CeO2, and the phase of coated TiO2 was amorphous. The catalytic activities of uncoated and TiO2-coated CeO2 nanoparticles for the oxidation of organic compounds were evaluated by the degradation study of methylene blue in air atmosphere at 403 K. The enhanced UV-shielding ability and visible transparency of the nanocomposite obtained by UV visible spectroscopic measurements suggested that the core-shell material has novel characteristics for using as a sunscreen material.

  14. The importance of CeO 2 growth temperature and its post-annealing for the improvement of the microwave surface resistance of DyBa 2Cu 3O z films

    NASA Astrophysics Data System (ADS)

    Murugesan, M.; Obara, H.; Nakagawa, Y.; Yamasaki, H.; Kosaka, S.

    2007-06-01

    We report here the influence of growth temperature of CeO 2 buffer layer T) as well as the post-annealing of the buffer layer on the crystallinity and the microwave surface resistance Rs of DyBa 2Cu 3O z (DBCO) films grown by pulsed laser deposition (PLD). It is found that (i) an increase in the T) facilitates the epitaxial growth of the CeO 2 films, which is a prerequisite to obtain the high quality superconducting films and (ii) the post-annealing of buffer layer at 1050 °C in flowing O 2 for 1 h leads to a profound improvement in the morphology and in the crystallinity of CeO 2 films. Apparently, there exists a critical growth temperature ( T)=800-820C, as found in this and previous study [J.C. Nie, H. Yamasaki, Y. Nakagawa, K.D. Bagarinao, M. Murugesan, H. Obara, Y. Mawatari, J. Crystal Growth 284 (2005) 417]) for CeO 2, below which the crystalline quality of CeO 2 films might not be improved merely by the post-annealing. It is explained that for T)<800C, the as-grown CeO 2 grains are longitudinal in shape, and it forms corrugated structure upon annealing. This poor morphology yields a deteriorated crystallinity (i.e., a large value of Δ ω and Δ φ, and the formation of secondary phase) for the CeO 2 as well as the overlying DBCO films, and hence a poor microwave performance of DBCO films for T)<800C. We also observed that the Rs in DBCO films monotonously decreased with increase in the growth temperature of CeO 2. Further, the post-annealing of the CeO 2 buffer layer prior to DBCO deposition greatly helps to reduce the Rs at the liquid N 2 temperature region, which is immensely required for the use of superconducting films in the passive microwave device components. Thus, the 800-820 °C of T) and the post-annealing of CeO 2 at 1050 °C in flowing O 2 for 1 h may be readily exploited to grow RBCO (R=Y or rare-earth elements) films for microwave applications on the technologically viable r-Al 2O 3 substrates.

  15. Soot combustion over Ce1-xFexO2-δ and CeO2/Fe2O3 catalysts: Roles of solid solution and interfacial interactions in the mixed oxides

    NASA Astrophysics Data System (ADS)

    Li, Hongcheng; Li, Kongzhai; Wang, Hua; Zhu, Xing; Wei, Yonggang; Yan, Dongxia; Cheng, Xianming; Zhai, Kang

    2016-12-01

    Two series of CeO2-Fe2O3 catalysts (CeO2-based and Fe2O3-supported oxides) with varying composition were synthesized by a hydrothermal method and characterized using various techniques. The comparison on the activity and thermal stability of different catalysts for low-temperature soot oxidation was also performed. The presence of both Ce-Fe-O solid solution and CeO2-Fe2O3 interaction were observed over the two types of catalysts. The oxygen vacancy in the solid solution is the crucial active site to facilitating the soot combustion over the CeO2-based samples. Small CeO2 nanoparticles are well dispersed on the Fe2O3-supported catalysts, which results in the formation of Fe-O-Ce species due to the strong CeO2-Fe2O3 interaction. The Fe-O-Ce species could achieve the coupling of the Ce4+-Ce3+ and Fe3+-Fe2+ couples in the CeO2-Fe2O3 interface, which is also identified as an active species for catalytic soot oxidation. The concentration of oxygen vacancy is closely related to the content of iron in ceria lattice, while the formation of Fe-O-Ce species strongly relies on the particle size of CeO2. It is also found that the oxygen vacancy is more active than the Fe-O-Ce species for soot oxidation, but it is very easy to decompose at high temperature, resulting in obvious deactivation of catalysts. By contrast, the Fe-O-Ce species is very stable under high-temperature treatments. For the fresh samples, the CeO2-based and Fe2O3-supported catalysts showed comparable catalytic activity. After long term aging at 800 °C, the loss on activity over the CeO2-based catalyst (Ce-Fe-O solid solution) is much higher than that over the Fe2O3-supported sample. The Fe2O3-supported catalysts are more suitable for practical application than the Ce-Fe-O solid solution.

  16. Promotional effect of fluorine on the selective catalytic reduction of NO with NH3 over CeO2-TiO2 catalyst at low temperature

    NASA Astrophysics Data System (ADS)

    Zhang, Rui; Zhong, Qin; Zhao, Wei; Yu, Lemeng; Qu, Hongxia

    2014-01-01

    In order to investigate the effect of F on CeO2-TiO2 catalyst for the selective catalytic reduction (SCR) of NO with NH3, a series of F-doped CeO2-TiO2 catalysts were prepared by co-precipitation method. Compared with Ce0.3TiF0 catalyst, Ce0.3TiF1.5 catalyst exhibited the best catalytic activity, yielding 92.19% NO conversion at 180 °C. The catalysts were characterized by Brunauer-Emmett-Teller (BET) surface area, X-ray powder diffraction (XRD), photoluminescence (PL) spectra, Raman spectra, X-ray photoelectron spectroscopy (XPS) and Diffused reflectance infrared Fourier transform spectroscopy (DRIFTS) techniques. It was found that the enhanced catalytic activity was ascribed to several beneficial effects produced by the introduction of F: inhibition of the crystallization, decrease of the particle size, increase of the oxygen vacancies (F+ centers) and lattice defects. Raman measurements disclosed the formation of superoxide (O2-) ions in chemisorbed oxygen which was crucial for the formation of reaction intermediates (NO2-, NO3-). The study of DRIFTS proved that the addition of F could bring more ad-NOx and reaction intermediates. The NH3-TPD studies confirmed that the right amount of F could improve the number of acid sites over CeO2-TiO2 catalyst, especially the Lewis acid sites. These factors simultaneously enhanced the catalytic activity for NH3-SCR of NO. The effect of H2O and SO2 on the NO conversion was also investigated in our work.

  17. 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.

  18. 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.

    PubMed

    Seminovski, Yohanna; Tereshchuk, Polina; Kiejna, Adam; Da Silva, Juarez L F

    2016-09-28

    Finite site platinum particles, Ptn, supported on reduced or unreduced cerium oxide surfaces, i.e., CeO2-x(111) (0

  19. 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.

  20. CeO2-supported Au38(SR)24 nanocluster catalysts for CO oxidation: a comparison of ligand-on and -off catalysts

    NASA Astrophysics Data System (ADS)

    Nie, Xiaotao; Zeng, Chenjie; Ma, Xiangang; Qian, Huifeng; Ge, Qingjie; Xu, Hengyong; Jin, Rongchao

    2013-06-01

    The catalytic properties of atomically precise, thiolate-protected Au38(SR)24 (R = CH2CH2Ph) nanoclusters supported on CeO2 were investigated for CO oxidation in a fixed bed quartz reactor. Oxygen (O2) thermal pretreatment of Au38(SR)24/CeO2 at a temperature between 100 and 175 °C largely enhanced the catalytic activity, while pretreatment at higher temperatures (>200 °C) for removing thiolate instead gave rise to a somewhat lower activity than that for 175 °C pretreatment, and the ligand-off clusters were also found to be less stable. The CO conversion in the case of wet feed-gas (i.e. the presence of H2O vapor) was appreciably higher than the case of dry feed-gas when the reaction temperature was kept relatively low (between 60 and 80 °C), and interestingly the ligand-on and ligand-off catalysts exhibited opposite response to water vapor. Finally, we discussed some insights into the catalytic reaction involving the well-defined gold nanocluster catalyst.

  1. Stresses exerted by ZnO, CeO2 and anatase TiO2 nanoparticles on the Nitrosomonas europaea.

    PubMed

    Fang, Xiaohua; Yu, Ran; Li, Bingquan; Somasundaran, Ponisseril; Chandran, Kartik

    2010-08-15

    Recent studies have shown that nano-bio interfaces are the most complex and the least understood. Notably, nanotoxicity of these nanoparticles is not even well recognized. In this work, we examined the toxic effects of different nanoparticles on bacteria cells (Nitrosomonas europaea). The four nanoparticles involved are: 25 nm anatase TiO(2), 200 nm anatase TiO(2), ZnO and CeO(2) particles. These particles will have different electrical charges in the cell cultivating media. It has been observed that even with only 4 h of dosing, all of the particles caused apparent morphological damage to the cells. Experimental results suggest that ZnO particles exert the stress on cells by its dissolution and releasing of Zn(2+) ions. The TEM and AUC (analytical ultracentrifuge) result suggest that cells become heavier in presence of CeO(2) and TiO(2) particles. No visible clear intrusions of bulk nanoparticles were observed. However, both the analytical ultracentrifuge and TEM results show that cells are heavier when being damaged.

  2. Raman and impedance spectroscopic studies of the specific features of the transport properties of electrolytes based on CeO2

    NASA Astrophysics Data System (ADS)

    Sal'nikov, V. V.; Pikalova, E. Yu.

    2015-10-01

    The solid solutions CeO2-(Sm,Nd)2O3 have been prepared by the solid-phase synthesis. The microstructure, density, and electrical conductivity of ceramic samples obtained by rolling with an organic binder, followed by sintering in air at a temperature of 1600°C have been investigated. The contributions to the total conductivity from the grain volume and grain boundaries in the temperature range of 250-700°C have been separated using impedance spectroscopy. The impedance spectroscopy data have revealed a significant effect of grain boundaries on the transport properties of the solid electrolyte with a Sm dopant as compared to the electrolyte with Nd. The optical properties of the polycrystalline electrolytes Ce1- x Nd x O2-δ and Ce0.8Sm0.2O2-δ have been studied using Raman spectroscopy. In the spectrum of the ceramic samples, there are two modes: a mode of CeO2 at a frequency of 465 cm-1 and an additional mode at a frequency of ~550 cm-1 due to vibrations associated with oxygen vacancies, the intensity of which depends on the dopant concentration and the energy of the dopant cation-oxygen vacancy bond. The binding energy of oxygen vacancies in the fluorite structure correlates with the behavior of bulk conductivity, and the solid solutions with samarium exhibit the highest bulk conductivity.

  3. 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.

  4. Gold stabilized aqueous sols immobilized on mesoporous CeO2-Al2O3 as catalysts for the preferential oxidation of carbon monoxide.

    PubMed

    Storaro, Loretta; Lenarda, Maurizio; Moretti, Elisa; Talon, Aldo; Porta, Francesca; Moltrasio, Bernardo; Canton, Patrizia

    2010-10-15

    Nanostructured Au/Al(2)O(3)-CeO(2) catalysts with a low content of precious metal (0.9% wt.) were prepared immobilizing two different stabilized Au sols on a high surface area Al(2)O(3)-CeO(2) mixed oxide with a uniform pore size distribution, synthesized by a one-pot methodology. The samples were characterized by elemental analysis, N(2) physisorption, XRPD, TEM and (27)Al-MAS NMR techniques. The catalytic activity of the two samples in the preferential oxidation of CO in excess of H(2) (CO-PROX) was comparatively evaluated in the 35-110 degrees C temperature range. The Au-THPS/AlCe20 sample, prepared immobilizing a sol obtained reducing an aqueous solution of gold tetrachloroaurate salt with bis[tetrakis(hydroxymethyl)phosphonium sulfate], resulted very active and selective at low temperatures and its catalytic activity was correlated with the structural characteristics of the metal particles and of the ordered mesoporous support.

  5. 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.

  6. Synthesis and physicochemical characterizations of nanostructured Pt/Al2O3-CeO2 catalysts for total oxidation of VOCs.

    PubMed

    Abbasi, Zahra; Haghighi, Mohammad; Fatehifar, Esmaeil; Saedy, Saeed

    2011-02-28

    Pt/Al(2)O(3)-CeO(2) nanocatalysts with Pt loading of 1% and ceria loading of 10, 20 and 30% were successfully prepared via wet impregnation method to be utilized in catalytic oxidation of BTX. The nanocatalysts were characterized using XRD, FESEM, TEM, N(2) adsorption, FTIR and TPR-H(2) techniques. The XRD patterns confirmed the formation of cerium oxide as the crystalline phase on alumina with the average crystallite size of 8.1-8.7 nm, derived by Scherrer equation. FESEM images confirmed that these nanocatalysts had ceria particles in nano-ranges. TEM analysis showed that platinum particles were fairly well dispersed on Al(2)O(3)-CeO(2) with an average size of 5-20 nm. BET surface area presented large surface area for nanocatalysts. TPR patterns showed that by adding 1% platinum to support, the reducibility is highly increased. These patterns also revealed the promoting effect of ceria on reducibility of Pt and Al(2)O(3). The results of toluene oxidation indicated that the synthesized nanocatalysts were highly active and able to remove nearly 100% of toluene and xylene and about 85% of benzene as representative VOCs. The presence of nanoparticles along with good characteristics of the synthesized nanocatalysts presented them as highly efficient materials for catalytic oxidation of VOCs.

  7. Doping Effects on the Electronic Structure of an Anisotropic Kondo Semiconductor CeOs2Al10: An Optical Study with Re and Ir Substitution

    NASA Astrophysics Data System (ADS)

    Kimura, Shin-ichi; Takao, Hitoshi; Kawabata, Jo; Yamada, Yoshihiro; Takabatake, Toshiro

    2016-12-01

    An anisotropic Kondo semiconductor CeOs2Al10 exhibits an unusual antiferromagnetic order at rather high transition temperature T0 of 28.5 K. Two possible origins of the magnetic order have been proposed so far, one is the Kondo coupling of the hybridization between the conduction (c) and the 4f states and the other is the charge-density wave/charge ordering along the orthorhombic b-axis. To clarify the origin of the magnetic order, we have investigated the electronic structure of hole- and electron-doped CeOs2Al10 [Ce(Os1-yRey)2Al10 and Ce(Os1-xIrx)2Al10, respectively] by using optical conductivity spectra along the b-axis. The intensity of the c-f hybridization gap at ħω ˜ 50 meV continuously decreases from y = 0.10 to x = 0.12 via x = y = 0. On the other hand, the intensity of the charge excitation observed at ħω ˜ 20 meV has the maximum at x = y = 0 as similar with the doping dependence of T0. The fact that the charge excitation is strongly related to the magnetic order strengthens the possibility of the charge density wave/charge ordering as the origin of the magnetic order.

  8. 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.

  9. 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.

  10. 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.

  11. 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

    2016-04-06

    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.

  12. 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).

  13. Effect of CeO2 doping on catalytic activity of Fe2O3/gamma-Al2O(3) catalyst for catalytic wet peroxide oxidation of azo dyes.

    PubMed

    Liu, Yan; Sun, Dezhi

    2007-05-08

    In order to find a catalyst with high activity and stability for catalytic wet peroxide oxidation (CWPO) process under normal condition, with Fe(2)O(3)/gamma-Al(2)O(3) and Fe(2)O(3)-CeO(2)/gamma-Al(2)O(3) catalysts prepared by impregnation method, the effect of CeO(2) doping on the structure and catalytic activity of Fe(2)O(3)/gamma-Al(2)O(3) for catalytic wet peroxide oxidation of azo dyes at 25 degrees C and atmospheric pressure is evaluated using BET, SEM, XRF, XRD, XPS and chemical analysis techniques, and test results show that, better dispersion and smaller size of Fe(2)O(3) crystal can be achieved by adding CeO(2), and the content of chemisorbed oxygen can also be increased on the surface of catalyst. CWPO experimental results indicate that azo dyes in simulated wastewater can be efficiently mineralized and the catalytic activity of Fe(2)O(3)-CeO(2)/gamma-Al(2)O(3) can be increased by about 10% compared with that of Fe(2)O(3)/gamma-Al(2)O(3) because of the promotion of the structural and redox properties of the ferric oxide by ceria doped. Leaching tests indicate that Fe(2)O(3)/gamma-Al(2)O(3) and Fe(2)O(3)-CeO(2)/gamma-Al(2)O(3) are stable with a negligible amount of irons found in the aqueous solution after reaction for 2h. It can therefore be concluded from results and discussion that in comparison with Fe(2)O(3)/gamma-Al(2)O(3), Fe(2)O(3)-CeO(2)/gamma-Al(2)O(3) is a suitable catalyst, which can effectively degrade contaminants at normal temperature and atmospheric pressure.

  14. Advanced treatment of municipal secondary effluent by catalytic ozonation using Fe3O4-CeO2/MWCNTs as efficient catalyst.

    PubMed

    Bai, Zhiyong; Wang, Jianlong; Yang, Qi

    2017-02-23

    The advanced treatment of municipal secondary effluent was performed by catalytic ozonation using Fe3O4-CeO2/MWCNTs as catalyst. The experimental results showed that in catalytic ozonation system, the removal efficiency of soluble COD was more than 46% after 30 min reaction, and about 36% of effluent organic matters (EfOMs) were mineralized, which was four times higher than that in single ozonation system. Moreover, proteins, humic acids, and UV254 decreased obviously after 30 min reaction, but polysaccharides did not significantly decrease. In catalytic ozonation system, the ozone utilization increased, which is favorable for the degradation of EfOM. The organic compounds and alkalinity were the main hydroxyl radical consumers in municipal secondary effluent. The catalytic ozonation process was also effective for the degradation of two target micropollutants (sulfamethazine and carbamazepine). The catalyst could be stable after five-time reuse for catalytic ozonation of effluent.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. FTIR study of CO adsorption on Rh/MgO modified with Co, Ni, Fe, or CeO2 for the catalytic partial oxidation of methane.

    PubMed

    Li, Dalin; Sakai, Shigemasa; Nakagawa, Yoshinao; Tomishige, Keiichi

    2012-07-07

    The surface state of Rh/MgO catalysts modified with Co, Ni, Fe, or CeO(2) after the reduction and partial oxidation pretreatments as well as during the catalytic partial oxidation of methane has been investigated by FTIR of adsorbed CO. The results of CO adsorption on the reduced catalysts suggest the formation of Rh-M alloy on Rh-M/MgO (M = Co, Ni, Fe) and Rh particles partially covered with reduced ceria on Rh-CeO(2)/MgO. The strength of CO adsorption on Rh/MgO is weakened by the modification with Co, Ni, Fe, or CeO(2). Partial oxidation pretreatment of Rh/MgO leads to a significant decrease in the CO adsorption due to the oxidation of Rh. In contrast, on partially oxidized Rh-M/MgO (M = Co, Ni, Fe) and Rh-CeO(2)/MgO, the preferential oxidation of the surface M atoms or reduced ceria maintains the metallic Rh and preserves the CO adsorbed on the surface Rh atoms. The CO adsorption during the reaction of catalytic partial oxidation of methane on Rh/MgO and Rh-Ni/MgO is similar to that on the reduced catalysts. On the other hand, the CO adsorption during the reaction on Rh-Co/MgO, Rh-Fe/MgO, and Rh-CeO(2)/MgO is different from that on the reduced catalysts, and this is related to the structural change of these catalysts during the reaction.

  20. The influence of Mn-doped CeO2 on the activity of CuO/CeO2 in CO oxidation and NO + CO model reaction

    NASA Astrophysics Data System (ADS)

    Deng, Changshun; Huang, Qingqing; Zhu, Xiying; Hu, Qun; Su, Wenli; Qian, Junning; Dong, Lihui; Li, Bin; Fan, Minguang; Liang, Caiyuan

    2016-12-01

    This work is mainly focused on the investigation of the influence of Mn-doped CeO2 supported by CuO on the physicochemical and catalytic properties for CO oxidation and NO + CO model reaction. The obtained samples were characterized using N2-physisorption (BET), XRD, LRS, TEM, EDS-Mapping, ICP-AES, XPS, H2-TPR, O2-TPD, in situ DRIFTS, CO oxidation, and NO + CO model reaction. The results imply that appropriate doping MnOx into the lattice of CeO2 will cause an obvious change in the properties of the catalyst and the Cu/CeMn-10: 1 catalyst shows the largest specific surface area, the most uniformity of structure, and the most extent of lattice expansion. A few addition of MnOx is more conducive to the generation of low valence manganese ion in the process of calcination, which may contribute to the synergetic introduction. This further results in more Cu+ due to the shifting of redox equilibrium (Cu2+ + Ce3+ ↔ Cu+ + Ce4+) to right, as well as more oxygen vacancies. Moreover, the capability of Cu/CeMn-10: 1 on desorb/transform/decompose of the adsorbed NO species is more effective than that of Cu/CeO2. The results of catalytic performance show that Cu+/Cu0 species play a key role, and the activity is mainly related to the specific surface area, the content of Cu+ and Ce3+, the reduction, desorption capability of chemisorbed O2- (and/or O-) species as well as adsorption behaviors of these catalysts for CO oxidation and NO + CO reaction. Finally, possible reaction mechanisms are tentatively proposed to understand the reactions.

  1. 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

    2016-09-06

    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.

  2. 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.

  3. 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.

  4. 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.

  5. The CO methanation on Rh/CeO 2 and CeO 2/Rh model catalysts: a comparative study

    NASA Astrophysics Data System (ADS)

    Jenewein, B.; Fuchs, M.; Hayek, K.

    2003-06-01

    Like other reducible oxides, ceria promotes the CO methanation reaction on noble metals, but after high-temperature reduction the promotion is usually reduced and limited to transient conditions. We studied the effect of low- and high-temperature reduction on two types of Rh/ceria model catalysts: "thin film catalysts" consisting of well-defined regular Rh nanoparticles partly embedded in the crystalline ceria support, and "inverse catalysts", i.e. UHV grown ceria submonolayers on polycrystalline Rh surfaces. The turnover rates on either catalyst were related to the free Rh surface area and to the dimensions of the metal-oxide boundary. On thin film catalysts the rates decrease strongly with reduction temperature up to 723 K while no significant structural changes are detectable by ex situ electron microscopy. On ceria-modified surfaces the reaction is initially favoured after reduction below 573 K, but promotion converts to inhibition with increasing reduction temperature. The changing number of Ce III/Ce IV ions on the surface, the oxygen transport to and from the interface, and changes in the free Rh surface area resulting from spreading and reordering of the ceria overlayer are discussed as possible reasons for the observed effects.

  6. 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.

  7. 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.

  8. Morphology, structural properties and reducibility of size-selected CeO2− x nanoparticle films

    PubMed Central

    D’Addato, Sergio; Gasperi, Gabriele; Benedetti, Francesco; Luches, Paola; Grillo, Vincenzo; Bertoni, Giovanni; Valeri, Sergio

    2015-01-01

    Summary Non-stoichiometric ceria nanoparticles (NPs) were obtained by a gas aggregation source with a magnetron and were mass-selected with a quadrupole mass filter. By varying magnetron power, Ar gas flow, and the length of the aggregation tube, NPs with an average diameter of 6, 9, and 14 nm were synthesized and deposited onto a substrate, thus obtaining NP films. The morphology of the films was studied with scanning electron microscopy, while high resolution transmission electron microscopy was used to gain a deeper insight into the atomic structure of individual NPs. By using X-ray photoelectron spectroscopy we analyzed the degree of reduction of the NPs of different diameters, before and after thermal treatments in vacuum (reduction cycle) and in O2 atmosphere (oxidation cycle) at different temperatures. From this analysis we inferred that the size is an important parameter only at intermediate temperatures. As a comparison, we evaluated the reducibility of an ultra-thin ceria film with the same surface to volume ratio as the 9 nm diameter NPs film, observing that NPs are more reducible than the ceria film. PMID:25671152

  9. 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.

  10. Origins and implications of the ordering of oxygen vacancies and localized electrons on partially reduced CeO2(111)

    DOE PAGES

    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

  11. Interplay of dopant, defects and electronic structure in driving ferromagnetism in Co-doped oxides: TiO2, CeO2 and ZnO

    NASA Astrophysics Data System (ADS)

    Ali, Bakhtyar; Shah, Lubna R.; Ni, C.; Xiao, J. Q.; Shah, S. Ismat

    2009-11-01

    A comprehensive study of the defects and impurity (Co)-driven ferromagnetism is undertaken in the oxide semiconductors: TiO2, ZnO and CeO2. The effect of magnetic (Co2+) and non-magnetic (Cu2+) impurities in conjunction with defects, such as oxygen vacancies (Vo), 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 TiO2 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.

  12. Short-term effects of TiO2, CeO2, and ZnO nanoparticles on metabolic activities and gene expression of Nitrosomonas europaea.

    PubMed

    Yu, Ran; Fang, Xiaohua; Somasundaran, Ponisseril; Chandran, Kartik

    2015-06-01

    Nanosized TiO2 (n-TiO2), CeO2 (n-CeO2), and ZnO (n-ZnO) and bulk ZnO were chosen for a 4-h exposure study on a model ammonia oxidizing bacterium, Nitrosomonas europaea. n-ZnO displayed the most serious cytotoxicity while n-TiO2 was the least toxic one. The change of cell morphologies, the retardance of specific oxygen uptake rates and ammonia oxidation rates, and the depression of amoA gene expressions under NP stresses were generally observed when the cell densities and membrane integrities were not significantly impaired yet. The TEM imaging and the synchrotron X-ray fluorescence microscopy of the NPs impacted cells revealed the increase of the corresponding intracellular Ti, Ce or Zn contents and suggested the intracellular NP accumulation. The elevation of intracellular S contents accompanied with higher K contents implied the possible activation of thiol-containing glutathione and thioredoxin production for NP stress alleviation. The NP cytotoxicity was not always a function of NP concentration. The 200 mg L(-1) n-TiO2 or n-CeO2 impacted cells displayed the similar ammonia oxidation activities but higher amoA gene expression levels than the 20 mg L(-1) NPs impacted ones. Such phenomenon further indicated the possible establishment of an anti-toxicity mechanism in N. europaea at the genetic level to redeem the weakened AMO activities along with the NP aggregation effects.

  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. Renewable H2 from glycerol steam reforming: effect of La2O3 and CeO2 addition to Pt/Al2O3 catalysts.

    PubMed

    Montini, Tiziano; Singh, Rakesh; Das, Piyali; Lorenzut, Barbara; Bertero, Nicolás; Riello, Pietro; Benedetti, Alvise; Giambastiani, Giuliano; Bianchini, Claudio; Zinoviev, Sergey; Miertus, Stanislav; Fornasiero, Paolo

    2010-05-25

    Glycerol is the main byproduct of biodiesel production and its increased production volume derives from the increasing demand for biofuels. The conversion of glycerol to hydrogen-rich mixtures presents an attractive route towards sustainable biodiesel production. Here we explored the use of Pt/Al(2)O(3)-based catalysts for the catalytic steam reforming of glycerol, evidencing the influence of La(2)O(3) and CeO(2) doping on the catalyst activity and selectivity. The addition of the latter metal oxides to a Pt/Al(2)O(3) catalyst is found to significantly improve the glycerol steam reforming, with high H(2) and CO(2) selectivities. A good catalytic stability is achieved for the Pt/La(2)O(3)/Al(2)O(3) system working at 350 degrees C, while the Pt/CeO(2)/Al(2)O(3) catalyst sharply deactivates after 20 h under similar conditions. Studies carried out on fresh and exhausted catalysts reveal that both systems maintain high surface areas and high Pt dispersions. Therefore, the observed catalyst deactivation can be attributed to coke deposition on the active sites throughout the catalytic process and only marginally to Pt nanoparticle sintering. This work suggests that an appropriate support composition is mandatory for preparing high-performance Pt-based catalysts for the sustainable conversion of glycerol into syngas.

  15. 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

    2012-03-06

    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.

  16. 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.

  17. Synthesis of novel CoOx decorated CeO2 hollow structures with an enhanced photocatalytic water oxidation performance under visible light irradiation.

    PubMed

    Fang, Siman; Li, Songsong; Ge, Lei; Han, Changcun; Qiu, Ping; Gao, Yangqin

    2017-02-01

    Cobalt oxide decorated octahedral ceria hollow structures (CoOx/CeO2) with various contents of CoOx nanoparticles were prepared via a simple chemical impregnation method. The obtained samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), UV-Vis diffuse-reflectance spectroscopy (DRS), surface photovoltage spectroscopy (SPV) and transient photovoltage spectroscopy (TPV). The photocatalytic oxygen evolution via water oxidation was investigated for the as-prepared CoOx/CeO2 nanocage composites. The photocatalytic results indicate that the CoOx/CeO2 nanocage composite with 1 mol% CoOx shows the highest photocatalytic activity. The excellent photocatalytic activity can be attributed to the improved visible-light absorption of CoOx/CeO2 composites and the efficient separation of excited electron-hole pairs between CoOx and CeO2, which can effectively enhance the lifetime of charge carriers in the CoOx-modified samples and then improve the oxygen evolution activity. Cobalt oxide is expected to be an excellent water oxidation co-catalyst for semiconductor photocatalysts.

  18. Communication: Improving the density functional theory+U description of CeO2 by including the contribution of the O 2p electrons

    NASA Astrophysics Data System (ADS)

    Plata, José J.; Márquez, Antonio M.; Sanz, Javier Fdez.

    2012-01-01

    Density functional theory (DFT) based approaches within the local-density approximation or generalized gradient approximation frameworks fail to predict the correct electron localization in strongly correlated systems due to the lack of cancellation of the Coulomb self-interaction. This problem might be circumvented either by using hybrid functionals or by introducing a Hubbard-like term to account for the on site interactions. This latter DFT+U approach is less expensive and therefore more practical for extensive calculations in solid-state computational simulations. By and large, the U term only affects the metal electrons, in our case the Ce 4f ones. In the present work, we report a systematic analysis of the effect of adding such a U term also to the oxygen 2p electrons. We find that using a set of Uf = 5 eV and Up = 5eV effective terms leads to improved description of the lattice parameters, band gaps, and formation and reduction energies of CeO2.

  19. Fluorine impurities at CeO2(111): Effects on oxygen vacancy formation, molecular adsorption, and surface re-oxidation

    NASA Astrophysics Data System (ADS)

    Wolf, Matthew J.; Kullgren, Jolla; Broqvist, Peter; Hermansson, Kersti

    2017-01-01

    We investigate the effects of anion doping with fluorine impurities on the chemistry of the CeO2 (111) facet, using the results of DFT + U calculations. We consider three prototypical processes: the formation of oxygen vacancies, the adsorption of O2 and H2O molecules, and the re-oxidation of the surface with fragments of the two molecules. We find that the first two of these processes are not strongly affected, but that the presence of F lowers the energy gained in the re-oxidation of the surface in comparison to the healing of an oxygen vacancy, by 1.47 eV in the case of O2 (provided that the F is part of a cluster) and by 0.92 eV in the case of H2O. Based on these results, we suggest that F could enhance the redox chemistry of ceria by toggling between being in the surface and on the surface, effectively facilitating the release of lattice O by acting as a "place holder" for it. Finally, we find that the desorption of F as either 1/2 F2 or HF is energetically unfavourable, suggesting that F doped ceria should be stable in the presence of O2 and H2O.

  20. Orientation-dependent x-ray Raman scattering from cubic crystals: Natural linear dichroism in MnO and CeO2

    NASA Astrophysics Data System (ADS)

    Gordon, R. A.; Haverkort, M. W.; Gupta, Subhra Sen; Sawatzky, G. A.

    2009-11-01

    Information on valence orbitals and electronic interactions in single crystal systems can be obtained through orientation-dependent x-ray measurements, but this can be problematic for a cubic system. Polarisation-dependent x-ray absorption measurements are common, but are dominated by dipole transitions which, for a cubic system, are isotropic even though a cubic system is not. Many edges, particularly for transition metals, do have electric quadrupole features that could lead to dichroism but proximity to the dipole transition can make interpretation challenging. X-ray Raman Spectroscopy (XRS) can also be used to perform orientation-dependent near-edge measurements - not only dependent on the direction of the momentum transfer but also its magnitude, q. Previous XRS measurements on polycrystalline materials revealed that multipole (higher order than dipole) transitions are readily observable in the pre-threshold region of rare earth N4,5 edges, actually replacing the dipole at high-q. We have extended these studies to examine orientation-dependent XRS for CeO2 and MnO single crystals, as prototype systems for theoretical treatment. Dichroism is observed at both the Ce N4,5 and Mn M2,3 edges in these cubic materials.

  1. 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.

  2. Sur le système Uo 2-CeO 2; étude cristallographique à haute température

    NASA Astrophysics Data System (ADS)

    Lorenzelli, R.; Touzelin, B.

    1980-12-01

    L'étude du système UO 2-CeO 2, par rayons X à haute température, et en atmosphère contrôlée a permis de tracer le diagramme ternaire U-Ce-O entre l'ambiante et 1000°C. La réduction des oxydes conduit pour Ce/U + Ce >/ 20 at%, à la coexistence de deux phases cfc à la température ambiante. La température de disparition de ce domaine biphasé croît avec le rapport Ce/U + Ce. Pour 70% at de Ce, elle a lieu à T= 260°C. L'existence d'un large domaine monophasé au-dessus de cette température permet d'envisager la structure de défauts dans ce système (essentiellement des lacunes d'oxygène). La limite expérimentale de réduction qui tend vers la composition O/Ce = 1.714 est très inférieure à celle observée par Markin et al. [2]. Pour les teneurs en Ce/U + Ce > 0.50, l'existence d'une phase type M 2O 3 est observée en équilibre avec la phase type MO 2-x.

  3. Effect of fluorine additive on CeO2(ZrO2)/TiO2 for selective catalytic reduction of NO by NH3.

    PubMed

    Jin, Qijie; Shen, Yuesong; Zhu, Shemin

    2017-02-01

    A series of CeO2(ZrO2)/TiO2 catalysts with fluorine additive were prepared by impregnation method and tested for selective catalytic reduction (SCR) of NO by NH3. These samples were characterized by XRD, N2-BET, Raman spectra, SEM, TEM, NH3-TPD, H2-TPR and XPS, respectively. Results showed that the optimal catalyst with the appropriate HF exhibited excellent performance for NH3-SCR and more than 96% NO conversion at 360°C under GHSV of 71,400h(-1). It was found that the grain size of TiO2 increased and the specific surface area reduced with the modulation of HF, which was not good for the adsorption of gas molecule. However, the modulation of HF exposed the high energy (001) facets of TiO2 and increased the surface chemisorbed oxygen concentration, oxygen storage capacity and Ce(3+) concentration of catalyst. In addition, the synergy of (101) and (001) facets was beneficial to the improvement of catalytic activity.

  4. Facile synthesis of Co3O4-CeO2 composite oxide nanotubes and their multifunctional applications for lithium ion batteries and CO oxidation.

    PubMed

    Yuan, Chenpei; Wang, Heng-Guo; Liu, Jiaqi; Wu, Qiong; Duan, Qian; Li, Yanhui

    2017-05-15

    In this study, Co3O4-CeO2 composite oxide nanotubes (CCONs) have been fabricated by using a simple electrospinning technique followed subsequent annealing and their multifunctional applications for lithium ion batteries and CO oxidation have also been investigated for the first time. When utilized as attractive anodes for lithium-ion batteries (LIBs), the CCONs exhibit good rate capability (497.3mAhg(-1) at 2Ag(-1)), high initial capacity (826.2mAhg(-1) at 0.05Ag(-1)) and improved cycling stability (1286.3mAhg(-1) after 180 cycles at 0.1Ag(-1) and 300.5mAhg(-1) with 63.5% retention after 1500 cycles at 1Ag(-1)). Furthermore, a preliminary CO catalytic oxidation study has demonstrated that the CCONs samples exhibit high catalytic activity. Thus, these properties endorse CCONs as attractive candidates for both LIBs and CO oxidation and this strategy might open new avenues for the design of a series of transition metal oxides with multicomponent for multifunctional applications.

  5. CeO2-Y2O3-ZrO2 Membrane with Enhanced Molten Salt Corrosion Resistance for Solid Oxide Membrane (SOM) Electrolysis Process

    NASA Astrophysics Data System (ADS)

    Zou, Xingli; Li, Xin; Shen, Bin; Lu, Xionggang; Xu, Qian; Zhou, Zhongfu; Ding, Weizhong

    2017-02-01

    Innovative CeO2-Y2O3-ZrO2 membrane has been successfully developed and used in the solid oxide membrane (SOM) electrolysis process for green metallic materials production. The x mol pct ceria/(8- x) mol pct yttria-costabilized zirconia ( xCe(8- x)YSZ, x = 0, 1, 4, or 7) membranes have been fabricated and investigated as the membrane-based inert anodes to control the SOM electroreduction process in molten salt. The characteristics of these fabricated xCe(8- x)YSZ membranes including their corrosion resistances in molten salt and their degradation mechanisms have been systematically investigated and compared. The results show that the addition of ceria in the YSZ-based membrane can inhibit the depletion of yttrium during the SOM electrolysis, which thus makes the ceria-reinforced YSZ-based membranes possess enhanced corrosion resistances to molten salt. The ceria/yttria-costabilized zirconia membranes can also provide reasonable oxygen ion conductivity during electrolysis. Further investigation shows that the newly modified 4Ce4YSZ ceramic membrane has the potential to be used as novel inert SOM anode for the facile and sustainable production of metals/alloys/composites materials such as Si, Ti5Si3, TiC, and Ti5Si3/TiC from their metal oxides precursors in molten CaCl2.

  6. High power density cell using nanostructured Sr-doped SmCoO3 and Sm-doped CeO2 composite powder synthesized by spray pyrolysis

    NASA Astrophysics Data System (ADS)

    Shimada, Hiroyuki; Yamaguchi, Toshiaki; Suzuki, Toshio; Sumi, Hirofumi; Hamamoto, Koichi; Fujishiro, Yoshinobu

    2016-01-01

    High power density solid oxide electrochemical cells were developed using nanostructure-controlled composite powder consisting of Sr-doped SmCoO3 (SSC) and Sm-doped CeO2 (SDC) for electrode material. The SSC-SDC nano-composite powder, which was synthesized by spray pyrolysis, had a narrow particle size distribution (D10, D50, and D90 of 0.59, 0.71, and 0.94 μm, respectively), and individual particles were spherical, composing of nano-size SSC and SDC fragments (approximately 10-15 nm). The application of the powder to a cathode for an anode-supported solid oxide fuel cell (SOFC) realized extremely fine cathode microstructure and excellent cell performance. The anode-supported SOFC with the SSC-SDC cathode achieved maximum power density of 3.65, 2.44, 1.43, and 0.76 W cm-2 at 800, 750, 700, and 650 °C, respectively, using humidified H2 as fuel and air as oxidant. This result could be explained by the extended electrochemically active region in the cathode induced by controlling the structure of the starting powder at the nano-order level.

  7. 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.

  8. Preparation of High-Jc YBa2Cu3O7-y Films on CeO2-Buffered Yttria-Stabilized Zirconia Substrates by Fluorine-Free Metalorganic Deposition

    NASA Astrophysics Data System (ADS)

    Tsukada, Kenichi; Furuse, Mitsuho; Sohma, Mitsugu; Manabe, Takaaki; Yamaguchi, Iwao; Kondo, Wakichi; Fuchino, Shuichiro; Kumagai, Toshiya

    2005-07-01

    Epitaxial YBa2Cu3O7-y (YBCO) films have successfully been prepared by fluorine-free metalorganic deposition on yttria-stabilized zirconia (YSZ) substrates with an evaporated CeO2 buffer layer. The YBCO films, prepared using a metal acetylacetonate-based coating solution, were highly (001)-oriented by X-ray diffraction θ-2θ scanning and φ scanning. The 0.21-μm-thick YBCO film demonstrated a high superconducting transition temperature, Tc=90.1 K, and high critical current densities with an average in excess of 4 MA/cm2 at 77 K using an inductive method. Transport critical current (Ic) was also measured by a standard four-terminal technique; the Ic value reached 185 A in a 2.5-cm-wide current path formed on a 5-cm-diameter film. These excellent properties are attributed to the small in-plane fluctuation due to high epitaxy of the YBCO films, which resulted from good matching of the crystal structure, lattice parameter and thermal expansion coefficient among the YBCO film, CeO2 buffer layer and YSZ substrate, as well as from the smooth and uniform surface morphology, i.e., average roughness = 0.34 nm, of the CeO2 buffer layer. The present deposition conditions, i.e., 700°C and p(O2)=4× 10-2 Pa, activated by radio frequency plasma at 20 W, are valid for the growth of such CeO2(100) buffer layers on YSZ substrates.

  9. Endurance and Cycle-to-cycle Uniformity Improvement in Tri-Layered CeO2/Ti/CeO2 Resistive Switching Devices by Changing Top Electrode Material

    PubMed Central

    Rana, Anwar Manzoor; Akbar, Tahira; Ismail, Muhammad; Ahmad, Ejaz; Hussain, Fayyaz; Talib, Ijaz; Imran, Muhammad; Mehmood, Khalid; Iqbal, Khalid; Nadeem, M. Younus

    2017-01-01

    Resistance switching characteristics of CeO2/Ti/CeO2 tri-layered films sandwiched between Pt bottom electrode and two different top electrodes (Ti and TaN) with different work functions have been investigated. RRAM memory cells composed of TaN/CeO2/Ti/CeO2/Pt reveal better resistive switching performance instead of Ti/CeO2/Ti/CeO2/Pt memory stacks. As compared to the Ti/CeO2 interface, much better ability of TaN/CeO2 interface to store and exchange plays a key role in the RS performance improvement, including lower forming/SET voltages, large memory window (~102) and no significant data degradation during endurance test of >104 switching cycles. The formation of TaON thinner interfacial layer between TaN TE and CeO2 film is found to be accountable for improved resistance switching behavior. Partial charge density of states is analyzed using density functional theory. It is found that the conductive filaments formed in CeO2 based devices is assisted by interstitial Ti dopant. Better stability and reproducibility in cycle-to-cycle (C2C) resistance distribution and Vset/Vreset uniformity were achieved due to the modulation of current conduction mechanism from Ohmic in low field region to Schottky emission in high field region. PMID:28079056

  10. 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.

  11. Effect of CeO2 on Cyclic Hot-Corrosion Behavior of Detonation-Gun Sprayed Cr3C2-NiCr Coatings on Ni-Based Superalloy

    NASA Astrophysics Data System (ADS)

    Saladi, Sekar; Menghani, Jyoti; Prakash, Satya

    2015-03-01

    The hot-corrosion behavior of detonation-gun sprayed Cr3C2-NiCr coatings with and without 0.4 wt.% CeO2 additive on Ni-based superalloy inconel-718 is comparatively discussed in the present study. Hot-corrosion studies were carried out at 900 °C for 100 cycles in Na2SO4-60%V2O5 molten salt environment under cyclic heating and cooling conditions on bare and coated superalloys. The thermo-gravimetric technique was used to establish kinetics of hot-corrosion. XRD, FESEM/EDAX, and EDX mapping techniques were used to analyze the corrosion products of bare and coated samples. The results indicate that Cr3C2-NiCr-CeO2-coated superalloy showed better hot-corrosion resistance as compared to bare and Cr3C2-NiCr-coated superalloys. The addition of CeO2 has improved micro-hardness, porosity, and surface roughness values of Cr3C2-NiCr-CeO2 coating. The overall weight gain and parabolic rate constant of Cr3C2-NiCr-CeO2-coated superalloy were found to be lowest in the present study signifying that the addition of CeO2 in Cr3C2-NiCr powder has contributed to the development of adherent and dense oxide scale on the coating at elevated temperature.

  12. Effect of CeO2 and Al2O3 on the activity of Pd/Co3O4/cordierite catalyst in the three-way catalysis reactions (CO/NO/CnHm).

    PubMed

    Soloviev, Sergiy O; Kyriienko, Pavlo I; Popovych, Nataliia O

    2012-01-01

    The present article studies the effect of CeO2 and Al2O3 on the activity of Pd/Co3O4/cordierite catalyst in conversion of NO, CO, CnHm. The catalysts were characterized by temperature programmed reduction with hydrogen, X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy. It is shown that the effect of CeO2 on the properties of Pd/Co3O4/cordierite catalyst depends on preparation method. The catalyst obtained by co-deposition of cerium and cobalt oxides has higher activity in CO oxidation (CO + O2 and CO + NO) and total hexane oxidation (C6H14 + O2). Such phenomenon is probably caused by more than stoichiometric amount of formed oxygen vacancies, an increase in both mobility of surface oxygen and dispersity of components in the catalytic composition. It is demonstrated that CeO2 addition promotes the SO2 resistance of Pd/Co3O4/cordierite. The second support decreases the activity of Pd/Co3O4/cordierite catalyst in the reactions of CO and C6H14 with oxygen because of CoAl2O4 formation.

  13. Endurance and Cycle-to-cycle Uniformity Improvement in Tri-Layered CeO2/Ti/CeO2 Resistive Switching Devices by Changing Top Electrode Material.

    PubMed

    Rana, Anwar Manzoor; Akbar, Tahira; Ismail, Muhammad; Ahmad, Ejaz; Hussain, Fayyaz; Talib, Ijaz; Imran, Muhammad; Mehmood, Khalid; Iqbal, Khalid; Nadeem, M Younus

    2017-01-12

    Resistance switching characteristics of CeO2/Ti/CeO2 tri-layered films sandwiched between Pt bottom electrode and two different top electrodes (Ti and TaN) with different work functions have been investigated. RRAM memory cells composed of TaN/CeO2/Ti/CeO2/Pt reveal better resistive switching performance instead of Ti/CeO2/Ti/CeO2/Pt memory stacks. As compared to the Ti/CeO2 interface, much better ability of TaN/CeO2 interface to store and exchange plays a key role in the RS performance improvement, including lower forming/SET voltages, large memory window (~10(2)) and no significant data degradation during endurance test of >10(4) switching cycles. The formation of TaON thinner interfacial layer between TaN TE and CeO2 film is found to be accountable for improved resistance switching behavior. Partial charge density of states is analyzed using density functional theory. It is found that the conductive filaments formed in CeO2 based devices is assisted by interstitial Ti dopant. Better stability and reproducibility in cycle-to-cycle (C2C) resistance distribution and Vset/Vreset uniformity were achieved due to the modulation of current conduction mechanism from Ohmic in low field region to Schottky emission in high field region.

  14. In situ defect annealing of swift heavy ion irradiated CeO 2 and ThO 2 using synchrotron X-ray diffraction and a hydrothermal diamond anvil cell

    DOE PAGES

    Palomares, Raul I.; Tracy, Cameron L.; Zhang, Fuxiang; ...

    2015-04-16

    Hydrothermal diamond anvil cells (HDACs) provide facile means for coupling synchrotron Xray techniques with pressure up to 10 GPa and temperature up to 1300 K. This manuscript reports on an application of the HDAC as an ambient-pressure sample environment for performing in situ defect annealing and thermal expansion studies of swift heavy ion irradiated CeO2 and ThO2 using synchrotron X-ray diffraction. The advantages of the in situ HDAC technique over conventional annealing methods include: rapid temperature ramping and quench times, high-resolution measurement capability, simultaneous annealing of multiple samples, and prolonged temperature- and apparatus stability at high temperatures. Isochronal annealing betweenmore » 300 K and 1100 K revealed 2-stage and 1-stage defect recovery processes for irradiated CeO2 and ThO2, respectively; indicating that the morphology of the defects produced by swift heavy ion irradiation of these two materials differs significantly. These results suggest that electronic configuration plays a major role in both the radiation-induced defect production and high temperature defect recovery mechanisms of CeO2 and ThO2.« less

  15. Endurance and Cycle-to-cycle Uniformity Improvement in Tri-Layered CeO2/Ti/CeO2 Resistive Switching Devices by Changing Top Electrode Material

    NASA Astrophysics Data System (ADS)

    Rana, Anwar Manzoor; Akbar, Tahira; Ismail, Muhammad; Ahmad, Ejaz; Hussain, Fayyaz; Talib, Ijaz; Imran, Muhammad; Mehmood, Khalid; Iqbal, Khalid; Nadeem, M. Younus

    2017-01-01

    Resistance switching characteristics of CeO2/Ti/CeO2 tri-layered films sandwiched between Pt bottom electrode and two different top electrodes (Ti and TaN) with different work functions have been investigated. RRAM memory cells composed of TaN/CeO2/Ti/CeO2/Pt reveal better resistive switching performance instead of Ti/CeO2/Ti/CeO2/Pt memory stacks. As compared to the Ti/CeO2 interface, much better ability of TaN/CeO2 interface to store and exchange plays a key role in the RS performance improvement, including lower forming/SET voltages, large memory window (~102) and no significant data degradation during endurance test of >104 switching cycles. The formation of TaON thinner interfacial layer between TaN TE and CeO2 film is found to be accountable for improved resistance switching behavior. Partial charge density of states is analyzed using density functional theory. It is found that the conductive filaments formed in CeO2 based devices is assisted by interstitial Ti dopant. Better stability and reproducibility in cycle-to-cycle (C2C) resistance distribution and Vset/Vreset uniformity were achieved due to the modulation of current conduction mechanism from Ohmic in low field region to Schottky emission in high field region.

  16. Dopant-induced modification of active site structure and surface bonding mode for high-performance nanocatalysts: CO oxidation on capping-free (110)-oriented CeO2:Ln (Ln = La-Lu) nanowires.

    PubMed

    Ke, Jun; Xiao, Jia-Wen; Zhu, Wei; Liu, Haichao; Si, Rui; Zhang, Ya-Wen; Yan, Chun-Hua

    2013-10-09

    Active center engineering at atomic level is a grand challenge for catalyst design and optimization in many industrial catalytic processes. Exploring new strategies to delicately tailor the structures of active centers and bonding modes of surface reactive intermediates for nanocatalysts is crucial to high-efficiency nanocatalysis that bridges heterogeneous and homogeneous catalysis. Here we demonstrate a robust approach to tune the CO oxidation activity over CeO2 nanowires (NWs) through the modulation of the local structure and surface state around Ln(Ce)' defect centers by doping other lanthanides (Ln), based on the continuous variation of the ionic radius of lanthanide dopants caused by the lanthanide contraction. Homogeneously doped (110)-oriented CeO2:Ln NWs with no residual capping agents were synthesized by controlling the redox chemistry of Ce(III)/Ce(IV) in a mild hydrothermal process. The CO oxidation reactivity over CeO2:Ln NWs was dependent on the Ln dopants, and the reactivity reached the maximum in turnover rates over Nd-doped samples. On the basis of the results obtained from combined experimentations and density functional theory simulations, the decisive factors of the modulation effect along the lanthanide dopant series were deduced as surface oxygen release capability and the bonding configuration of the surface adsorbed species (i.e., carbonates and bicarbonates) formed during catalytic process, which resulted in the existence of an optimal doping effect from the lanthanide with moderate ionic radius.

  17. 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

    2016-06-07

    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.

  18. 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

  19. 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.

  20. 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.

  1. 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.

  2. Identification and quantification of oxygen vacancies in CeO2 nanocrystals and their role in formation of F-centers

    NASA Astrophysics Data System (ADS)

    Jaffari, G. Hassnain; Imran, Ali; Bah, M.; Ali, Awais; Bhatti, Arshad S.; Qurashi, Umar Saeed; Ismat Shah, S.

    2017-02-01

    In this work we present synthesis and extensive characterization of Cerium oxide (CeO2) nanocrystals. Comparison between the properties of as-prepared and air annealed nanoparticles has been carried out, with a goal to clearly identify the effect of oxygen vacancies on crystal, electronic and band structure. Detail crystal and electronic structural analysis was employed to quantify oxygen vacancies. Structural analysis confirmed that the formation of single phase cubic Fluorite structure for both as-prepared and annealed samples. Crystal and electronic structural studies confirmed that Ce ions exists in two oxidation states, Ce+3 and Ce+4. Concentration of oxygen vacancies was larger in as-synthesis nanocrystal. A drastic decrease in oxygen vacancy concentration was observed for the sample annealed in air at 550 °C. For the as-prepared sample, the Raman allowed F2g mode shifted towards lower wavenumber, exhibiting mode softening with broader and asymmetric peak. Observation of absorption edge revealed presence of 4f band within the band gap. Absorption with different band edge, confirmed different energy position of 4f level for the sample possessing oxygen vacancies. Blue shift of the band edge for as-prepared sample has been discussed in terms of increase in lattice parameter, formation of Ce+3 ions, quantum confinement effect etc. Photoluminescence emission studies revealed presence of F-centers with corresponding energy level located below 4f band as a result of oxygen vacancies. It was found that within the measured experimental energy window, transitions associated by the F-center are mainly associated with 4f0 to 4f1, F++ to 4f1 and 4f0 to F+.

  3. Structural characterization of CeO(2)-ZrO(2)/TiO(2) and V(2)O(5)/CeO(2)-ZrO(2)/TiO(2) mixed oxide catalysts by XRD, Raman spectroscopy, HREM, and other techniques.

    PubMed

    Reddy, Benjaram M; Lakshmanan, Pandian; Khan, Ataullah; López-Cartes, Carlos; Rojas, Teresa C; Fernandez, Asunción

    2005-02-10

    Structural characteristics of CeO(2)-ZrO(2)/TiO(2) (CZ/T) and V(2)O(5)/CeO(2)-ZrO(2)/TiO(2) (V/CZ/T) mixed oxide catalysts have been investigated using X-ray diffraction (XRD), BET surface area, Raman spectroscopy (RS), and high-resolution transmission electron microscopy (HREM) techniques. The CeO(2)-ZrO(2) (1:1 mole ratio) solid solution was deposited over a finely powdered TiO(2) support by a deposition precipitation method. A nominal 5 wt % V(2)O(5) was impregnated over the calcined (773 K) CZ/T mixed oxide carrier by a wet impregnation technique. The obtained CZ/T and V/CZ/T samples were further subjected to thermal treatments from 773 to 1073 K to understand the dispersion and temperature stability of these materials. In the case of CZ/T samples, the XRD results suggest the formation of different cubic and tetragonal Ce-Zr-oxide phases, Ce(0.75)Zr(0.25)O(2), Ce(0.6)Zr(0.4)O(2), Ce(0.5)Zr(0.5)O(2), and Ce(0.16)Zr(0.84)O(2) in varying proportions depending on the treatment temperature. With increasing calcination temperature from 773 to 1073 K, the intensity of the lines pertaining to cubic Ce(0.6)Zr(0.4)O(2) and Ce(0.5)Zr(0.5)O(2) phases increased at the expense of cubic Ce(0.75)Zr(0.25)O(2), indicating more incorporation of zirconia into the ceria lattice. The TiO(2) was mainly in the anatase form whose crystallite size also increased with increasing treatment temperature. A better crystallization and more incorporation of zirconia into the ceria lattice was noted when CZ/T was impregnated with V(2)O(5). However, no crystalline V(2)O(5) could be seen from both XRD and RS measurements. In particular, a preferential formation of CeVO(4) compound and an intense tetragonal Ce(0.16)Zr(0.84)O(2) phase were noted beyond 873 K. The HREM results indicate, in the case of CZ/T samples, a well-dispersed Ce-Zr-oxide of the size approximately 5 nm over the bigger crystals ( approximately 40 nm) of TiO(2) when treated at 873 K. The exact structural features of these crystals as determined by digital diffraction analysis of experimental images reveal that the Ce-Zr-oxides are mainly in the cubic fluorite geometry and the TiO(2) is in anatase form. A better crystallization of Ce-Zr-oxides ( approximately 8 nm) over the surface of bigger crystals of TiO(2) was noted at 1073 K. A further enhancement in the crystallite size and zirconia-rich tetragonal phase was noted in the case of V/CZ/T samples. Further, the structure of CeVO(4) formed was also clearly identified in conformity with XRD and RS results.

  4. 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.

  5. An all chemical solution deposition approach for the growth of highly textured CeO2 cap layers on La2Zr2O7-buffered long lengths of biaxially textured Ni W substrates for YBCO-coated conductors

    NASA Astrophysics Data System (ADS)

    Engel, S.; Knoth, K.; Hühne, R.; Schultz, L.; Holzapfel, B.

    2005-10-01

    A reel-to-reel, dip coating process has been developed to continuously deposit epitaxial La2Zr2O7 (LZO) and CeO2 on 5 m long cube-textured {100} (001)Ni tapes. Recent results for La2Zr2O7 and CeO2 buffer layers deposited on long lengths of Ni substrate for the realization of YBa2Cu3O7-x (YBCO)-coated conductors are presented. The major achievement is the development of a new all chemical solution deposition (CSD) process leading to the formation of highly textured buffer layers at moderate annealing temperatures. Reproducible highly textured, dense and crack-free LZO buffer layers and CeO2 cap layers were obtained for annealing temperatures as low as 900 °C in a reducing atmosphere (Ar-5 at.%-H2). The thickness of the LZO buffer layers was determined to be (200 ± 10) nm per single coating; prepared cerium oxide layers showed a thickness of 60 nm ± 10 nm. Pulsed laser deposition (PLD) was used to grow YBCO films on these substrates. A Tc 0 of T = 90.5 K and ΔTc = 1.4 K was obtained on PLD-YBCO/CSD-CeO2 /CSD-LZO/Ni-5 at.% W, which shows the outstanding features of this new buffer layer architecture processed by CSD. The large layer thickness combined with low annealing temperatures is the main advantage of this new process for low-cost buffer layer deposition on Ni-RABiTS (rolling-assisted biaxially textured substrates).

  6. A novel magnetic nanoscaled Fe3O4/CeO2 composite prepared by oxidation-precipitation process and its application for degradation of orange G in aqueous solution as Fenton-like heterogeneous catalyst.

    PubMed

    Gan, Guoqiang; Liu, Juan; Zhu, Zhixi; Yang, Ziran; Zhang, Conglu; Hou, Xiaohong

    2017-02-01

    In this work, magnetic nanoparticles (MNPs) Fe3O4/CeO2 were firstly synthesized using three different preparation methods, including coprecipitation, impregnation oxidation-precipitation and impregnation reduction-precipitation, respectively. The catalytic activities of Fe3O4/CeO2 MNPs, prepared by above three methods, were compared systematically in terms of the degradation of orange G (OG). The impregnation oxidation-precipitation process was economical and maneuverable due to the usage of air, no need of nitrogen protection and higher utilization efficiency of iron. Response surface methodology based on central composite design were used to investigate the individual and interactive effects of three process parameters on the OG degradation, i.e. the initial pH of the solution, the dosage of H2O2 and the initial concentration of OG. Under the optimal conditions of pH 2.5, H2O2 30 mM, OG 50 mg L(-1), catalyst 2.0 g L(-1) and 35 °C, the degradation percentage of OG was 98.2% within 120 min, which agreed well with the modeling prediction (R(2) = 0.9984, and Adj-R(2) = 0.9969). And the degradation reaction well followed the first-order kinetic with R(2) = 0.9969. The Fe3O4/CeO2-OX MNPs showed high catalytic activity, stability and reusability in the degradation of OG.

  7. Development of Xe and Kr empirical potentials for CeO2, ThO2, UO2 and PuO2, combining DFT with high temperature MD

    DOE PAGES

    Cooper, M. W. D.; Kuganathan, N.; Burr, P. 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

  8. Core-Hole Effect in the Ce L3 X-Ray Absorption Spectra of CeO2 and CeFe2: New Examination by Using Resonant X-Ray Emission Spectroscopy

    NASA Astrophysics Data System (ADS)

    Kotani, A.

    2013-06-01

    We consider two different resonant X-ray emission spectra for Ce compounds: Ce 3d to 2p X-ray emission (denoted by 3d-RXES) and valence to 2p X-ray emission (v-RXES), both of which follow the Ce 2p to 5d resonant excitation. We propose that the comparison of the 3d- and v-RXES spectra is a new powerful method of directly detecting the core-hole effect in the final state of Ce L3 X-ray absorption spectra (XAS). We applied this method to recent experimental RXES spectra for CeO2 and CeFe2, and showed unambiguously that the core-hole effect should be essential in the XAS of both materials. This result is confirmed by theoretical calculations, which reproduce well the experimental RXES and XAS spectra. We conclude that the ground state of CeO2 is in the mixed state of 4f0 and 4f1_{L} configurations, where _{L} is a ligand hole, instead of a pure 4f0 configuration which was proposed recently by first-principles energy band calculations. Also, we conclude that the double peaks observed in L3 XAS of CeFe2 are caused by the 4f0 and 4f1 configurations, which are mixed in the ground state but separated in energy by the large core-hole potential in the final state of XAS.

  9. 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.

  10. 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.

  11. Catalytic ethanolysis and gasification of kraft lignin into aromatic alcohols and H2-rich gas over Rh supported on La2O3/CeO2-ZrO2.

    PubMed

    Yang, Jing; Zhao, Liang; Liu, Chunze; Wang, Yuanyuan; Dai, Liyi

    2016-10-01

    Efficient catalytic ethanolysis and gasification of kraft lignin were conducted over a versatile supported catalyst Rh/La2O3/CeO2-ZrO2 to give high-value aromatic alcohols and H2-rich gas. The removal of phenolic hydroxyl group was the most prevalent reaction, and importantly, almost no phenols, undesired char and saturating the aromatic ring were detected. Meanwhile, the feedstock and solvent both played key roles in H2 generation that contributed to the hydrodeoxygenation of liquid components and made the whole catalytic process out of H2 supply. Reusability tests of catalyst indicated that the crystalline phase transition and agglomeration of support, the loss of noble metal Rh and carbon deposition were the possible reasons for its deactivation in supercritical ethanol. Comparing with water, methanol and isopropanol system, ethanol was the only effective solvent for the depolymerization process.

  12. Facile conversion of layered Ruddlesden-Popper-related structure Y2O3-doped Sr2CeO4 into fast oxide ion-conducting fluorite-type Y2O3-doped CeO2.

    PubMed

    Gerlach, Ryan Georg; Bhella, Surinderjit Singh; Thangadurai, Venkataraman

    2009-01-05

    The present work shows a new solid- and gas-phase reaction technique for the preparation of a fast oxide-ion-conducting Y(2)O(3)-doped Ce(1-x)Y(x)O(2-delta) (x = 0.1, 0.2) (YCO), which involves the reaction of layered (Ruddlesden-Popper K(2)NiF(4)-type) structure Y(2)O(3)-doped Sr(2)CeO(4) (YSCO) with CO(2) at an elevated temperature and subsequent acid-washing. A powder X-ray diffraction study revealed the formation of a single-phase cubic fluorite-type YCO for the CO(2)-reacted and subsequent acid-washed product. Energy dispersive X-ray analysis showed the absence of Sr in the CO(2)-treated and subsequent acid-washed product, confirming the transformation of layered YSCO into YCO. The cubic lattice constant was found to decrease with increasing Y content in YCO, which is consistent with the other YCO samples reported in the literature. The scanning electron microscopy study showed smaller-sized particles for the product obtained after CO(2)- and acid-washed YCO samples, while the high-temperature sintered YCO and the precursor YSCO exhibit larger-sized particles. The bulk ionic conductivity of the present CO(2)-capture-method-prepared YCO exhibits about one and half orders of magnitude higher electrical conductivity than that of the undoped CeO(2) and was found to be comparable to those of ceramic- and wet-chemical-method synthesized rare-earth-doped CeO(2).

  13. 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.

  14. 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.

  15. 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.

  16. Enhancement of the chemical stability in confined δ-Bi2O3.

    PubMed

    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.

  17. 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.

  18. 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.

  19. 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.

  20. Removal of binary dyes mixtures with opposite and similar charges by adsorption, coagulation/flocculation and catalytic oxidation in the presence of CeO2/H2O2 Fenton-like system.

    PubMed

    Issa Hamoud, Houeida; Finqueneisel, Gisèle; Azambre, Bruno

    2016-08-25

    In this study, the removal of binary mixtures of dyes with similar (Orange II/Acid Green 25) or opposite charges (Orange II/Malachite Green) was investigated either by simple adsorption on ceria or by the heterogeneous Fenton reaction in presence of H2O2. First, the CeO2 nanocatalyst with high specific surface area (269 m(2)/g) and small crystal size (5 nm) was characterized using XRD, Raman spectroscopy and N2 physisorption at 77 K. The adsorption of single dyes was studied either from thermodynamic and kinetic viewpoints. It is shown that the adsorption of dyes on ceria surface is highly pH-dependent and followed a pseudo-second order kinetic model. Adsorption isotherms fit well the Langmuir model with a complete monolayer coverage and higher affinity towards Orange II at pH 3, compared to other dyes. For the (Orange II/Acid Green 25) mixture, both the amounts of dyes adsorbed on ceria surface and discoloration rates measured from Fenton experiments were decreased by comparison with single dyes. This is due to the adsorption competition existing onto the same surface Ce(x+) sites and the reaction competition with hydroxyl radicals, respectively. The behavior of the (Orange II/Malachite Green) mixture is markedly different. Dyes with opposite charges undergo paired adsorption on ceria as well as homogeneous and heterogeneous coagulation/flocculation processes, but can also be removed by heterogeneous Fenton process.

  1. Ni-doped (CeO2- δ )-YSZ mesoarchitectured with nanocrystalline framework: the effect of thermal treatment on structure, surface chemistry and catalytic properties in the partial oxidation of methane (CPOM)

    NASA Astrophysics Data System (ADS)

    Somacescu, Simona; Florea, Mihaela; Osiceanu, Petre; Calderon-Moreno, Jose Maria; Ghica, Corneliu; Serra, Jose Manuel

    2015-11-01

    Ni-doped (CeO2- δ )-YSZ (5 mol% Ni oxide, 10 mol% ceria) mesoarchitectures (MA) with nanocrystalline framework have been synthesized by an original, facile and cheap approach based on Triton X100 nonionic surfactant as template and water as solvent at a strong basic pH value. Following the hydrothermal treatment under autogenous pressure ( 18 bars), Ni, Ce, Y, and Zr were well ordered as MA with nanocrystalline framework, assuring thermal stability. A comprehensive investigation of structure, texture, morphology, and surface chemistry was performed by means of a variety of complementary techniques (X-Ray Diffraction, XRD; Raman Spectroscopy, RS; Brunauer—Emmett—Teller, BET; Temperature—Programmed Reduction, TPR; Transmission Electron Microscopy, TEM and DF-STEM; X-ray Photoelectron Spectroscopy, XPS; Catalytic activity and selectivity). N2 sorption measurements highlighted that the mesoporous structure is formed at 600 °C and remains stable at 800 °C. At 900 °C, the MA collapses, favoring the formation of macropores. The XRD and Raman Spectroscopy of all samples showed the presence of a pure, single phase with fluorite-type structure. At 900 °C, an increased tetragonal distortion of the cubic lattice was observed. The surface chemistry probed by XPS exhibits a mixture of oxidation states (Ce3+ + Ce4+) with high percentage of Ce3+ valence state 35 % and (Ni3+ and Ni2+) oxidation states induced by the thermal treatment. These nanoparticles assembled into MA show high stability and selectivity over time in catalytic partial oxidation of methane (CPOM). These promising performances suggest an interesting prospect for introduction as anode within IT-SOFC assemblies.

  2. Kinetics of valeric acid ketonization and ketenization in catalytic pyrolysis on nanosized SiO2, γ-Al2O3, CeO2/SiO2, Al2O3/SiO2 and TiO2/SiO2.

    PubMed

    Kulyk, Kostiantyn; Palianytsia, Borys; Alexander, John D; Azizova, Liana; Borysenko, Mykola; Kartel, Mykola; Larsson, Mats; Kulik, Tetiana

    2017-04-09

    Valeric acid is an important renewable platform chemical that can efficiently be produced from lignocellulosic biomass. Upgrading of valeric acid by catalytic pyrolysis has the potential to produce value added biofuels and chemicals on an industrial scale. Understanding the different mechanisms involved in the thermal transformations of valeric acid on the surface of nanosized oxides is important for the development of efficient heterogeneously-catalyzed pyrolytic conversion techniques. In this work, the thermal decomposition of valeric acid on the surface of nanoscale SiO2, γ-Al2O3, CeO2/SiO2, Al2O3/SiO2 and TiO2/SiO2 has been investigated by Temperature-Programmed Desorption Mass Spectrometry (TPD MS). Fourier transform infrared spectroscopy (FTIR) has been used to investigate the structure of valeric acid complexes on the oxide surfaces. Two main products of pyrolytic conversion were observed to be formed depending on the nano-catalyst used - dibutylketone and propylketene. The mechanisms of ketene and ketone formation from chemisorbed fragments of valeric acid are proposed and the kinetic parameters of the corresponding reactions were calculated. It was found that the activation energy of ketenization decreases in the order SiO2>γ-Al2O3>TiO2/SiO2>Al2O3/SiO2, and the activation energy of ketonization decreases in the order γ-Al2O3>CeO2/SiO2. Nano-oxide CeO2/SiO2 was found to selectively catalyze ketonization reaction.

  3. 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.

  4. Effect of Oxide Buffer Layer on the Thermochromic Properties of VO2 Thin Films

    NASA Astrophysics Data System (ADS)

    Koo, Hyun; Xu, Lu; Ko, Kyeong-Eun; Ahn, Seunghyun; Chang, Se-Hong; Park, Chan

    2013-12-01

    VO2 thin films were deposited on soda lime glass substrates with ZnO, TiO2, SnO2, and CeO2 thin films applied as buffer layers between the VO2 films and the substrates in order to investigate the effect of buffer layer on the formation and the thermochromic properties of VO2 film. Buffer layers with thicknesses over 50 nm were found to affect the formation of VO2 film, which was confirmed by XRD spectra. By using ZnO, TiO2, and SnO2 buffer layers, monoclinic VO2 (VO2(M)) film was successfully fabricated on soda lime glass at 370 °C. On the contrary, films of VO2(B), which is known to have no phase transition near room temperature, were formed rather than VO2(M) when the film was deposited on CeO2 buffer layer at the same film deposition temperature. The excellent thermochromic properties of the films deposited on ZnO, TiO2, and SnO2 buffer layers were confirmed from the temperature dependence of electrical resistivity from room temperature to 80 °C. Especially, due to the tendency of ZnO thin film to grow with a high degree of preferred orientation on soda lime glass at low temperature, the VO2 film deposited on ZnO buffer layer exhibits the best thermochromic properties compared to those on other buffer layer materials used in this study. These results suggest that deposition of VO2 films on soda lime glass at low temperature with excellent thermochromic properties can be achieved by considering the buffer layer material having structural similarity with VO2. Moreover, the degree of crystallization of buffer layer is also related with that of VO2 film, and thus ZnO can be one of the most effective buffer layer materials.

  5. Thin films of rare-earth (Y, La, Ce, Pr, Nd, Sm) oxides formed by the spray-ICP technique

    NASA Astrophysics Data System (ADS)

    Suzuki, M.; Kagawa, M.; Syono, Y.; Hirai, T.

    1991-07-01

    Thin films of Y 2O 3, La 2O 3, CeO 2, PrO 2, Nd 2O 3 and Sm 2O 3 were synthesized by injecting ultrasonically atomized metal nitrate solutions into a high temperature inductively coupled RF plasma above 5000 K generated under atmospheric pressure (the spray-ICP technique). Fused quartz plates and single crystal sapphire plates giving no background X-ray reflection peaks were used as substrates. About 0.4 μm thick transparent films could be prepared by 10 min of running. The films of CeO 2 and PrO 2, both belonging to the cubic flourite type, revealed (100) and (111) orientations, respectively. With the remaining oxides having A (hexagonal), B (monoclinic) and C (cubic) rare-earth structures, film orientations were A (001) for La 2O 3, A (001)+C (111) for Nd 2O 3, and C (111) for Y 2O 3. Sm 2O 3 films were composed of a phase with C (111) and an extra phase with an orientation close to (001) of A-Sm 2O 3 or its equivalent, (20 overline1) of B-Sm 2O 3.

  6. 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.

  7. 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.

  8. Thin Clouds

    Atmospheric Science Data Center

    2013-04-18

    ... one of a new generation of instruments flying aboard the NASA Earth Observing System's Terra satellite, views Earth with nine cameras ... of thin cirrus minutes after MISR imaged the cloud from space. At the same time, another NASA high-altitude jet, the WB-57, flew right ...

  9. 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.

  10. Over-current carrying characteristics of rectangular-shaped YBCO thin films prepared by MOD method

    NASA Astrophysics Data System (ADS)

    Hotta, N.; Yokomizu, Y.; Iioka, D.; Matsumura, T.; Kumagai, T.; Yamasaki, H.; Shibuya, M.; Nitta, T.

    2008-02-01

    A fault current limiter (FCL) may be manufactured at competitive qualities and prices by using rectangular-shaped YBCO films which are prepared by metal-organic deposition (MOD) method, because the MOD method can produce large size elements with a low-cost and non-vacuum technique. Prior to constructing a superconducting FCL (SFCL), AC over-current carrying experiments were conducted for 120 mm long elements where YBCO thin film of about 200 nm in thickness was coated on sapphire substrate with cerium oxide (CeO2) interlayer. In the experiments, only single cycle of the ac damping current of 50 Hz was applied to the pure YBCO element without protective metal coating or parallel resistor and the magnitude of the current was increased step by step until the breakdown phenomena occurred in the element. In each experiment, current waveforms flowing through the YBCO element and voltage waveform across the element were measured to get the voltage-current characteristics. The allowable over-current and generated voltage were successfully estimated for the pure YBCO films. It can be pointed out that the lower n-value trends to bring about the higher allowable over-current and the higher withstand voltage more than tens of volts. The YBCO film having higher n-value is sensitive to the over-current. Thus, some protective methods such as a metal coating should be employed for applying to the fault current limiter.

  11. AFM investigations of the morphology features and local mechanical properties of HTS YBCO thin films

    NASA Astrophysics Data System (ADS)

    Soifer, Yakov M.; Verdyan, Armen; Lapsker, Igor; Azoulay, Jacob

    2004-08-01

    In the paper presented here the application of the atomic force microscope (AFM) is considered for evaluation of hardness and Young's modulus of high Tc superconducting YBCO thin films of different thickness (from 0.05 to 1 μm) grown on unbuffered SrTiO 3 (film I) and on sapphire with a buffer layer of CeO 2 (film II). The best film features a transition temperature Tc of 90 K, critical current density Jc ( H=0) of 3 × 10 7 A/cm 2 at 4.2 K and 2 × 10 6 A/cm 2 at 77 K. The relationship between mechanical properties and microstructure of these films was investigated. It was found that all the films comprised well-defined Cu-rich precipitates of different size and with different density on their surface. For both type of films the hardness was measured to be in the range of 12-18 GPa. The Young's modulus of the films was about 180-200 GPa. The nanoindentation and nanoscratching measurements showed that the mechanical strength of the films studied was determined mainly by mechanical failure and surface defects (secondary phases).

  12. Adsorption and reaction of methanethiol on thin-film cerium oxide

    NASA Astrophysics Data System (ADS)

    Mullins, D. R.; McDonald, T. S.

    2008-03-01

    The adsorption and reaction of methanethiol, CH 3SH, have been studied on cerium oxide thin films that were vapor deposited on Ru(0 0 0 1). The behavior of the CH 3SH was examined as a function of the Ce oxidation state. CH 3SH weakly interacts with fully oxidized CeO 2(1 1 1) forming both chemisorbed CH 3SH and CH 3S + OH. OH forms through the reaction of the sulfhydrol H with the surface O. These species recombine and desorb near 180 K leaving the surface virtually clean. When the ceria is ca. 50% reduced, the chemisorbed CH 3SH desorbs near 150 K while the CH 3S + OH are stable to 400 K. These species react above 450 K to produce predominantly CH 4 and CH 3SH. A small amount of CH 2O and water are also formed through reaction with the O in the ceria. Atomic S is left on the surface. S 2p, C 1s and O 1s soft X-ray photoelectron spectroscopy were used to identify the nature of the chemisorbed species and the adsorption site of the CH 3S or S.

  13. Thin Sections

    PubMed Central

    Peachey, Lee D.

    1958-01-01

    Knowledge of the thickness of sections is important for proper interpretation of electron micrographs. Therefore, the thicknesses of sections of n-butyl methacrylate polymer were determined by ellipsometry, and correlated with the color shown in reflected light. The results are: gray, thinner than 60 mµ; silver, 60 to 90 mµ; gold, 90 to 150 mµ; purple, 150 to 190 mµ; blue, 190 to 240 mµ; green, 240 to 280 mµ; and yellow, 280 to 320 mµ. These results agree well with optical theory and with previous published data for thin films. Sections, after cutting, are 30 to 40 per cent shorter than the face of the block from which they were cut. Only a small improvement results from allowing the sections to remain in the collecting trough at room temperature. Heating above room temperature, however, reduces this shortening, with a corresponding improvement in dimensions and spatial relationships in the sections. When the thickness of the section is considered in interpreting electron micrographs instead of considering the section to be two-dimensional, a more accurate interpretation is possible. The consideration of electron micrographs as arising from projections of many profiles from throughout the whole thickness of the section explains the apparent lack of continuity often observed in serial sections. It is believed that serial sections are actually continuous, but that the change in size of structure through the thickness of one section and the consideration of only the largest profile shown in the micrograph can account for the lack of continuity previously observed. PMID:13549493

  14. 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.

  15. Microstructure of Thin Films

    DTIC Science & Technology

    1990-02-07

    optical properties ." (Final text in preparation). John Lehan, "Microstructural analysis of thin films by Rutherford Backscattering...correlation of optical properties and micro- Ion assisted deposition (IAD) is known to produce structure of IAD thin films with ion beam parameters thin films ...1.5-eV interband absorption. P (eV) R (%) P (, -V) R %) Optical properties of metal thin films in the spectral 0 98.3 0 88.8 range of

  16. 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.

  17. Tl 2Ba 2CaCu 2O 8 thin film high frequency filters on 3 inch sapphire substrates

    NASA Astrophysics Data System (ADS)

    Schneidewind, H.; Manzel, M.; Stelzner, T.

    2002-08-01

    Modern communication systems require densely packed frequency channels in the expensive frequency bands. Therefore high temperature superconducting (HTS) high frequency filters are of increasing importance, taking advantage of their outstanding properties namely steep filter skirts, low insertion loss, and furthermore reduced mass and volume compared to conventional cavity or dielectric resonator systems. Within the framework of a German BMBF pilot project a HTS equiped satellite repeater will be developed to demonstrate the performance advantage of HTS. For that purpose we prepare filters on double-sided Tl 2Ba 2CaCu 2O 8 thin films on CeO 2 buffered 3 inch sapphire substrates. The HTS films are prepared in the two-step process by sputtering an amorphous thallium free precursor and following oxythallination. The critical temperature and spatial distribution of critical current density at 77 K, both measured by inductive techniques, show values above 100 K or 1 MA/cm 2, respectively. We use a dielectric resonator technique at 3.9 GHz and power levels up to some mT to determine the films surface resistance. We present measurements of input filters made from our double-sided 3 inch films.

  18. Highly Oriented Growth of Piezoelectric Thin Films on Silicon Using Two-Dimensional Nanosheets as Growth Template Layer.

    PubMed

    Nguyen, Minh D; Yuan, Huiyu; Houwman, Evert P; Dekkers, Matthijn; Koster, Gertjan; Ten Elshof, Johan E; Rijnders, Guus

    2016-11-16

    Ca2Nb3O10 (CNOns) and Ti0.87O2 (TiOns) metal oxide nanosheets (ns) are used as a buffer layer for epitaxial growth of piezoelectric capacitor stacks on Si and Pt/Ti/SiO2/Si (Pt/Si) substrates. Highly (001)- and (110)-oriented Pb(Zr0.52Ti0.48)O3 (PZT) films are achieved by utilizing CNOns and TiOns, respectively. The piezoelectric capacitors are characterized by polarization and piezoelectric hysteresis loops and by fatigue measurements. The devices fabricated with SrRuO3 top and bottom electrodes directly on nanosheets/Si have ferroelectric and piezoelectric properties well comparable with devices that use more conventional oxide buffer layers (stacks) such as YSZ, CeO2/YSZ, or SrTiO3 on Si. The devices grown on nanosheets/Pt/Si with Pt top electrodes show significantly improved polarization fatigue properties over those of similar devices grown directly on Pt/Si. The differences in properties are ascribed to differences in the crystalline structures and the density of the films. These results show a route toward the fabrication of single crystal piezoelectric thin films and devices with high quality, long-lifetime piezoelectric capacitor structures on nonperovskite and even noncrystalline substrates such as glass or polished metal surfaces.

  19. The influence of external factors on the corrosion resistance of high temperature superconductor thin films against moisture

    NASA Astrophysics Data System (ADS)

    Murugesan, M.; Obara, H.; Yamasaki, H.; Kosaka, S.

    2006-12-01

    High temperature superconductor (HTS) thin films have been systematically investigated for their corrosion resistance against moisture by studying the role of external factors such as temperature (T), relative humidity (RH), and the type of substrates in the corrosion. In general, (i) the corrosion is progressed monotonously with increasing T as well as RH, (ii) a threshold level of water vapor is needed to cause degradation, and (iii) between T and RH, the influence of T is more dominant. HTS films on SrTiO3 and CeO2 buffered sapphire (cbs) substrates showed better corrosion stability and a low rate of degradation in the critical current density as compared to that of the film grown on MgO substrate. Between DyBa2Cu3Oz (DBCO) and YBa2Cu3Oz, the former is reproducibly found to have many fold higher corrosion resistance against moisture. This observed enhancement in the corrosion resistance in DBCO could be explained by the improved microstructure in the films and the better lattice matching with the substrate. Thus, the dual advantage of DBCO/cbs films, i.e., the enhanced corrosion stability of DBCO and the appropriate dielectric properties of sapphire, can be readily exploited for the use of DBCO/cbs films in the microwave and power devices.

  20. Thin film interference of colloidal thin films.

    PubMed

    Cong, Hailin; Cao, Weixiao

    2004-09-14

    A stairlike colloidal crystal thin film composed of poly(styrene-methyl methacrylate-acrylic acid) (P(St-MMA-AA)) monodispersed colloids was fabricated on an inclined silicon substrate. Different bright colors were observed on the various parts of the film with different layers as white light irradiated perpendicularly on it. The relationship between the colors and layers of the film was investigated and discussed according to the principle of thin film interference. On the basis of the phenomenon of thin film interference, a one-layer colloidal film having uniform color was researched and it would display diverse colors before and after swollen by styrene (St). A circular stairlike colloidal film was achieved to mimic the colors of the peacock tail feather.

  1. Mechanics of Thin Films

    DTIC Science & Technology

    1992-02-06

    S. Hwang, Thermal conductivity of thin films: measurement and microstructural effects, in Thin- film heat transfer, properties and processing, ed...thermal, electrical, optical and magnetic properties . As typical examples we mention microelectronics, optical coatings and multilayers for use in optical...interplay between mechanical properties (elastic moduli), thermal properties (thermal conductivity, thermal expansion coefficient), and optical

  2. Optical thin film devices

    NASA Astrophysics Data System (ADS)

    Mao, Shuzheng

    1991-11-01

    Thin film devices are applied to almost all modern scientific instruments, and these devices, especially optical thin film devices, play an essential role in the performances of the instruments, therefore, they are attracting more and more attention. Now there are numerous kinds of thin film devices and their applications are very diversified. The 300-page book, 'Thin Film Device and Applications,' by Prof. K. L. Chopra gives some general ideas, and my paper also outlines the designs, fabrication, and applications of some optical thin film devices made in my laboratory. Optical thin film devices have been greatly developed in the recent decades. Prof. A. Thelan has given a number of papers on the theory and techniques, Prof. H. A. Macleod's book, 'Thin Film Optical Filters,' has concisely concluded the important concepts of optical thin film devices, and Prof. J. A. Dobrowobski has proposed many successful designs for optical thin film devices. Recently, fully-automatic plants make it easier to produce thin film devices with various spectrum requirements, and some companies, such as Balzers, Leybold AG, Satis Vacuum AG, etc., have manufactured such kinds of coating plants for research or mass-production, and the successful example is the production of multilayer antireflection coatings with high stability and reproducibility. Therefore, it could be said that the design of optical thin film devices and coating plants is quite mature. However, we cannot expect that every problem has been solved, the R&D work still continues, the competition still continues, and new design concepts, new techniques, and new film materials are continually developed. Meanwhile, the high-price of fully-automatic coating plants makes unpopular, and automatic design of coating stacks is only the technique for optimizing the manual design according to the physical concepts and experience, in addition, not only the optical system, but also working environment should be taken into account when

  3. 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.

  4. 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).

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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 ...

  10. 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.

  11. 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.

  12. Thin film tritium dosimetry

    DOEpatents

    Moran, Paul R.

    1976-01-01

    The present invention provides a method for tritium dosimetry. A dosimeter comprising a thin film of a material having relatively sensitive RITAC-RITAP dosimetry properties is exposed to radiation from tritium, and after the dosimeter has been removed from the source of the radiation, the low energy electron dose deposited in the thin film is determined by radiation-induced, thermally-activated polarization dosimetry techniques.

  13. 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.

  14. Epitaxial thinning process

    NASA Technical Reports Server (NTRS)

    Siegel, C. M. (Inventor)

    1984-01-01

    A method is described for thinning an epitaxial layer of a wafer that is to be used in producing diodes having a specified breakdown voltage and which also facilitates the thinning process. Current is passed through the epitaxial layer, by connecting a current source between the substrate of the wafer and an electrolyte in which the wafer is immersed. When the wafer is initially immersed, the voltage across the wafer initially drops and then rises at a steep rate. When light is applied to the wafer the voltage drops, and when the light is interrupted the voltage rises again. These changes in voltage, each indicate the breakdown voltage of a Schottky diode that could be prepared from the wafer at that time. The epitaxial layer is thinned by continuing to apply current through the wafer while it is immersed and light is applied, to form an oxide film and when the oxide film is thick the wafer can then be cleaned of oxide and the testing and thinning continued. Uninterrupted thinning can be achieved by first forming an oxide film, and then using an electrolyte that dissolves the oxide about as fast as it is being formed, to limit the thickness of the oxide layer.

  15. 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.

  16. 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.

  17. Biomimetic thin film deposition

    NASA Astrophysics Data System (ADS)

    Rieke, P. C.; Campbell, A. A.; Tarasevich, B. J.; Fryxell, G. E.; Bentjen, S. B.

    1991-04-01

    Surfaces derivatized with organic functional groups were used to promote the deposition of thin films of inorganic minerals. These derivatized surfaces were designed to mimic the nucleation proteins that control mineral deposition during formation of bone, shell, and other hard tissues in living organisms. By the use of derivatized substrates control was obtained over the phase of mineral deposited, the orientation of the crystal lattice and the location of deposition. These features are of considerable importance in many technically important thin films, coatings, and composite materials. Methods of derivatizing surfaces are considered and examples of controlled mineral deposition are presented.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. Protein thin film machines.

    PubMed

    Federici, Stefania; Oliviero, Giulio; Hamad-Schifferli, Kimberly; Bergese, Paolo

    2010-12-01

    We report the first example of microcantilever beams that are reversibly driven by protein thin film machines fueled by cycling the salt concentration of the surrounding solution. We also show that upon the same salinity stimulus the drive can be completely reversed in its direction by introducing a surface coating ligand. Experimental results are throughout discussed within a general yet simple thermodynamic model.

  5. 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)

  6. 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.

  7. 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)

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. VACUUM DEPOSITION OF THIN FILMS,

    DTIC Science & Technology

    The book deals with methods of obtaining and processing thin films , methods of measuring the deposition rate and thickness of thin-film layers, and...the main fields of application of thin films . Vacuum requirements and the requirements for the composition of the residual medium in thermal...evaporation and cathode sputtering are given, and modern methods of producing and measuring vacuums and the equipment used in obtaining thin films are described. (Author)

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. Thin film composite electrolyte

    DOEpatents

    Schucker, Robert C.

    2007-08-14

    The invention is a thin film composite solid (and a means for making such) suitable for use as an electrolyte, having a first layer of a dense, non-porous conductive material; a second layer of a porous ionic conductive material; and a third layer of a dense non-porous conductive material, wherein the second layer has a Coefficient of thermal expansion within 5% of the coefficient of thermal expansion of the first and third layers.

  18. 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.

  19. Method for thinning specimen

    SciTech Connect

    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.

  20. Ureilite Thin Section Preparation

    NASA Technical Reports Server (NTRS)

    Harrington, R.; Righter, K.

    2014-01-01

    Preparing thin and thick sections of ureilite type meteorites is a challenge that can confound even the most experienced section preparer. A common characteristic of these samples is the presence of carbon phases, particularly nanodiamonds, in the matrix along silicate grain boundaries, fractures, and cleavage plains [1]. The extreme hardness of the nanodiamonds presents a challenge to the section preparer in the form of high surface relief on the section. This hard material also causes considerable wear and tear on equipment and materials that are used for making the sections. These issues will be discussed and potentially helpful measures will be presented.

  1. 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.

  2. 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.

  3. Ion-beam-induced texturing in oxide thin films and its applications

    NASA Astrophysics Data System (ADS)

    Wang, Pin-Chin Connie

    1999-11-01

    Ion-beam-assisted deposition (IBAD) has been demonstrated to be one of the most promising methods to artificially control thin films' texture. Recent years, much research has been conducted to try to control the in-plane alignment in oxide films for the high Tc superconductor YBa 2Cu3O7-x (HTS YBCO) power applications. The IBAD films deposited on engineering substrate can potentially replace the single crystal substrates, enabling large area and economical applications of the YBCO film. Thus far, the focus has been on IBAD YSZ and CeO2. However, both need to be thick to achieve good in-plane alignment. This requirement makes the IBAD process too costly for production. The IBAD MgO work started at Stanford several years ago. In contrast to YSZ, we demonstrated that the MgO texture started from the nucleation stage and we were able to obtain 7° in-plane alignment in a 100A IBAD MgO film. This reduces the processing cost by orders of magnitude as compared with IBAD YSZ. We studied the MgO texture development process using in-situ RHEED and ex-situ TEM and XRD. The results showed that the IBAD MgO film formed small rectangular islands, which coalesced to form a continuous film. We discussed the MgO texture as functions of key parameters, such as ion energy, ion angle, ion beam divergence, ion-to-molecule ratio, deposition temperature, etc. The ion angle study supported the differential sputtering yield/ion channeling type of ion-selecting-texture mechanism. The results of IBAD MgO were compared with that of the IBAD YSZ, suggesting that the different crystalline structures between the two materials can be used to explain the differences. This thesis also discusses our attempt to substitute single crystal substrates with the IBAD MgO in practical systems. In the HTS YBCO application, we obtained YBCO films on alpha-SiN coated poly-Alumina with in-plane misalignment less than 4° and Jc of 2.5MA/cm2. In the magnetic spin valve device applications, we obtained Ni

  4. 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

  5. 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.

  6. The thin eggshell problem

    USGS Publications Warehouse

    Stickel, L.F.; Rhodes, L.I.; Gillett, J.W.

    1970-01-01

    It has long been known that DDT and related chemicals can impair the reproduction of birds. In early years of organochlorine pesticide use, widespread mortality occurred immediately following heavy applications of these chemicals, and survivors contained substantial amounts of toxicant in their tissues. Repopulation from untreated areas tended to conceal the extent of the effects. DDT and dieldrin have become ubiquitous and the original source of the chemicals producing bird deaths often cannot be traced. The extent of sublethal effects cannot be fully appraised, although laboratory experiments continually reveal new and potentially deleterious physiological reactions. Thin eggshells have become prevalent among certain declining species of predatory birds. Shell thinning and associated reproductive effects have been produced experimentally in mallard ducks and in sparrow hawks. Coturnix quail fed dietary dosages of p,p'-DDT produced fewer eggs than did untreated birds and the eggs had thinner shells. Hatchability was not significantly altered. Comparisons between these results and those obtained in other studies indicate significant species differences.

  7. 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.

  8. Dewetting of Thin Polymer Films

    NASA Astrophysics Data System (ADS)

    Dixit, P. S.; Sorensen, J. L.; Kent, M.; Jeon, H. S.

    2001-03-01

    DEWETTING OF THIN POLYMER FILMS P. S. Dixit,(1) J. L. Sorensen,(2) M. Kent,(2) H. S. Jeon*(1) (1) Department of Petroleum and Chemical Engineering, New Mexico Institute of Mining and Technology, 801 Leroy Place, Socorro, NM 87801, jeon@nmt.edu (2) Department 1832, Sandia National Laboratories, Albuquerque, NM. Dewetting of thin polymer films is of technological importance for a variety of applications such as protective coatings, dielectric layers, and adhesives. Stable and smooth films are required for the above applications. Above the glass transition temperature (Tg) the instability of polymer thin films on a nonwettable substrate can be occurred. The dewetting mechanism and structure of polypropylene (Tg = -20 ^circC) and polystyrene (Tg = 100 ^circC) thin films is investigated as a function of film thickness (25 Åh < 250 Åand quenching temperature. Contact angle measurements are used in conjunction with optical microscope to check the surface homogeneity of the films. Uniform thin films are prepared by spin casting the polymer solutions onto silicon substrates with different contact angles. We found that the stable and unstable regions of the thin films as a function of the film thickness and quenching temperature, and then constructed a stability diagram for the dewetting of thin polymer films. We also found that the dewetting patterns of the thin films are affected substantially by the changes of film thickness and quenching temperature.

  9. Methods of Producing Thin Films,

    DTIC Science & Technology

    The report describes various methods of producing thin films , especially for microelectronics. In addition to the classical methods of forming thin ... films by vacuum vapor deposition, it also describes processes of diode sputtering and modern methods of cathode sputtering by means of a third

  10. 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.

  11. Magnetochromatic thin-film microplates.

    PubMed

    He, Le; Janner, Michael; Lu, Qipeng; Wang, Mingsheng; Ma, Hua; Yin, Yadong

    2015-01-07

    A new type of magnetochromatic material is developed based on thin-film interference of microplates self-assembled from super-paramagnetic nanocrystals. Dynamic optical tuning can be achieved through orientational manipulation of free-standing super-paramagnetic thin-film microplates using external magnetic fields.

  12. Thin Film Inorganic Electrochemical Systems.

    DTIC Science & Technology

    1995-07-01

    determined that thin film cathodes of LiCoO2 can be readily performed by either spray pyrolysis or spin coating . These cathodes are electrochemically...active. We have also determined that thin film anodes of Li4Ti5O12 can be prepared by spray pyrolysis or spin coating . These anodes are also

  13. Multilayer Thin-Film Microcapacitors

    NASA Technical Reports Server (NTRS)

    Thakoor, Sarita; Thakoor, Anil; Karmon, Dan

    1995-01-01

    Miniature capacitors containing multiple alternating thin-film dielectric and metal layers proposed, especially for use in integrated and hybrid electronic circuits. Because capacitance inversely proportional to thickness of dielectric layers, use of thin, high-quality dielectric layers affords capacitance and energy-storage densities much greater than now available. These devices much smaller and more reliable than state-of-art capacitors.

  14. Thin EFG octagons

    NASA Astrophysics Data System (ADS)

    Kalejs, J. P.

    1994-03-01

    This report describes work to advance the manufacturing line capabilities in crystal growth and laser cutting of Mobil Solar's unique edge-defined film-fed growth (EFG) octagon technology and to reduce the manufacturing costs of 10 cm x 10 cm polycrystalline silicon EFG wafers. The report summarizes the significant technical improvements in EFG technology achieved in the first 6 months of the PVMaT Phase 2 and the success in meeting program milestones. Technical results are reported for each of the three main pregrain areas: Task 5 -- Thin octagon growth (crystal growth) to reduce the thickness of the octagon to 200 microns; Task 6 -- Laser cutting-to improve the laser cutting process so as to produce wafers with decreased laser cutting damage at increased wafer throughput rates; and Task 7 -- Process control and product specification to implement advanced strategies in crystal growth process control and productivity designed to increase wafer yields.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. Thin wire pointing method

    NASA Technical Reports Server (NTRS)

    Green, G.; Mattauch, R. J. (Inventor)

    1983-01-01

    A method is described for forming sharp tips on thin wires, in particular phosphor bronze wires of diameters such as one-thousandth inch used to contact micron size Schottky barrier diodes, which enables close control of tip shape and which avoids the use of highly toxic solutions. The method includes dipping an end of a phosphor bronze wire into a dilute solution of sulfamic acid and applying a current through the wire to electrochemically etch it. The humidity in the room is controlled to a level of less than 50%, and the voltage applied between the wire and another electrode in the solutions is a half wave rectified voltage. The current through the wire is monitored, and the process is stopped when the current falls to a predetermined low level.

  20. 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.

  1. Holographic thin film analyzer

    NASA Technical Reports Server (NTRS)

    Williams, J. R.; Norden, B. N. (Inventor)

    1973-01-01

    A system for the analysis and measurement of thin films in which the light output of a laser is split into two beams is discribed. The first beam is focused to illuminate the entire area of a photographic plate and the second beam is colummated and directed through a relatively small portion of the photographic plate onto the sample with the film to be observed. The surface of the sample is positioned at a slight angle with respect to a plane normal to the second beam and the light reflected from the sample arrives back at the photographic plate in a region other than through which the second beam originally passes. By making two successive exposures during the deposition of material on the surface of the sample, holograms are recorded on the photographic plate. The plate is then developed and interference lines of the hologram provide a measurement of the film or material deposited between exposure.

  2. Thin θ -film optics

    NASA Astrophysics Data System (ADS)

    Huerta, Luis

    2016-12-01

    A Chern-Simons theory in 3D is accomplished by the so-called θ term in the action (θ /2 )∫F ∧F , which contributes only to observable effects on the boundaries of such a system. When electromagnetic radiation interacts with the system, the wave is reflected and its polarization is rotated at the interface, even when both the θ system and the environment are pure vacuum. These topics have been studied extensively. Here, we investigate the optical properties of a thin θ film, where multiple internal reflections could interfere coherently. The cases of pure vacuum and a material with magnetoelectric properties are analyzed. It is found that the film reflectance is enhanced compared to ordinary non-θ systems and the interplay between magnetoelectric properties and the θ parameter yield film opacity and polarization properties which could be interesting in the case of topological insulators, among other topological systems.

  3. 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

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. Impact of uniaxial strain and doping on oxygen diffusion in CeO2

    PubMed Central

    Rushton, M. J. D.; Chroneos, A.

    2014-01-01

    Doped ceria is an important electrolyte for solid oxide fuel cell applications. Molecular dynamics simulations have been used to investigate the impact of uniaxial strain along the <100> directions and rare-earth doping (Yb, Er, Ho, Dy, Gd, Sm, Nd, and La) on oxygen diffusion. We introduce a new potential model that is able to describe the thermal expansion and elastic properties of ceria to give excellent agreement with experimental data. We calculate the activation energy of oxygen migration in the temperature range 900–1900 K for both unstrained and rare-earth doped ceria systems under tensile strain. Uniaxial strain has a considerable effect in lowering the activation energies of oxygen migration. A more pronounced increase in oxygen diffusivities is predicted at the lower end of the temperature range for all the dopants considered. PMID:25317676

  11. 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.

  12. 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.

  13. Microstructure of YBCO thin films prepared by TFA-MOD method

    NASA Astrophysics Data System (ADS)

    Nagino, I.; Matsumoto, K.; Adachi, H.; Miyata, S.; Yoshizumi, M.; Izumi, T.; Shiohara, Y.

    2010-11-01

    The microstructure of the recently developed coated conductors was investigated by using electron back scatter diffraction pattern (EBSP). We prepared TFA (trifluoroacetates)-MOD (metal organic deposition) derived YBa2Cu3O7-x (YBCO) films on CeO2/LaMnO3/IBAD-MgO/Gd2Zr2O7/Hastelloy C276 substrates of 1 cm-width. The EBSP observation showed that there was a difference of surface microstructure between the midsection and the end of TFA-MOD YBCO film layer in the direction of width. This is attributed not to the local difference of the biaxial texture of CeO2 top layer but to the local difference of growth condition during TFA-MOD process.

  14. 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

  15. 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

  16. Chiral atomically thin films.

    PubMed

    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.

  17. 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.

  18. Thin film strain transducer

    NASA Astrophysics Data System (ADS)

    Rand, J. L.

    1981-01-01

    Previous attempts to develop an appropriate sensor for measuring the stress or strain of high altitude balloons during flight are reviewed as well as the various conditions that must be met by such a device. The design, development and calibration of a transducer which promises to satisfy the necessary design constraints are described. The thin film strain transducer has a low effective modulus so as not to interfere with the strain that would naturally occur in the balloon. In addition, the transducer has a high sensitivity to longitudinal strain (7.216 mV/V/unit strain) which is constant for all temperature from room temperature to -80 C and all strains from 5 percent compression to 10 percent tensile strain. At the same time, the sensor is relatively insensitive (0.27 percent) to transverse forces. The device has a standard 350 ohm impedance which is compatible with available bridge balance, amplification and telemetry instrumentation now available for balloon flight. Recommendations are included for improved coatings to provide passive thermal control as well as model, tethered and full scale flight testing.

  19. The thin film microwave iris

    NASA Technical Reports Server (NTRS)

    Ramey, R. L.; Landes, H. S.; Manus, E. A.

    1972-01-01

    Development of waveguide iris for microwave coupling applications using thin film techniques is discussed. Production process and installation of iris are described. Iris improves power transmission properties of waveguide window.

  20. Sealing micropores in thin castings

    NASA Technical Reports Server (NTRS)

    Mersereau, G. A.; Nitzschke, G. O.; Ochs, H. L.; Sutch, F. S.

    1981-01-01

    Microscopic pores in thin-walled aluminum castings are sealed by impregnation pretreatment. Technique was developed for investment castings used in hermetically sealed chassic for electronic circuitry. Excessively high leakage rates were previously measured in some chassis.

  1. 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)

  2. 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.

  3. Rotating thin-shell wormhole

    NASA Astrophysics Data System (ADS)

    Ovgun, A.

    2016-11-01

    We construct a rotating thin-shell wormhole using a Myers-Perry black hole in five dimensions, using the Darmois-Israel junction conditions. The stability of the wormhole is analyzed under perturbations. We find that exotic matter is required at the throat of the wormhole to keep it stable. Our analysis shows that stability of the rotating thin-shell wormhole is possible if suitable parameter values are chosen.

  4. Center for Thin Film Studies

    DTIC Science & Technology

    1991-01-22

    techniques for reducing roughness were developed and tested . Substrate Preparation We deposited Si films by sputtering on a variety of substrates, and...deposition," Mod. Phys. Lett. B 3, 1039 (1989). 41 42 Nd: YAG LASER ABLATION OF BaTiO 3 THIN FILMS *URSULA J. GIBSON, **J.A. RUFFNER,***J.J. MCNALLY...thin films of barium titanate onto a variety of substrates, using picosecond and nanosecond pulsed Nd: YAG lasers. The films were deposited from a hot

  5. 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.

  6. 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

  7. 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.

  8. 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.

  9. 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.

  10. Thin Film Solid Lubricant Development

    NASA Technical Reports Server (NTRS)

    Benoy, Patricia A.

    1997-01-01

    Tribological coatings for high temperature sliding applications are addressed. A sputter-deposited bilayer coating of gold and chromium is investigated as a potential solid lubricant for protection of alumina substrates during sliding at high temperature. Evaluation of the tribological properties of alumina pins sliding against thin sputtered gold films on alumina substrates is presented.

  11. Shear Thinning of Noncolloidal Suspensions

    NASA Astrophysics Data System (ADS)

    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.

  12. High Performance Thin Layer Chromatography.

    ERIC Educational Resources Information Center

    Costanzo, Samuel J.

    1984-01-01

    Clarifies where in the scheme of modern chromatography high performance thin layer chromatography (TLC) fits and why in some situations it is a viable alternative to gas and high performance liquid chromatography. New TLC plates, sample applications, plate development, and instrumental techniques are considered. (JN)

  13. New strategies for thinning peaches

    Technology Transfer Automated Retrieval System (TEKTRAN)

    An evaluation of two mechanical thinners was conducted in four commercial peach orchard blocks in 2007. A mechanical blossom thinner designed by a German grower for thinning apple trees that employed nylon cords (strings) to remove blossoms was tested on peach trees trained to either a perpendicula...

  14. Thin film polymeric gel electrolytes

    DOEpatents

    Derzon, Dora K.; Arnold, Jr., Charles; Delnick, Frank M.

    1996-01-01

    Novel hybrid thin film electrolyte, based on an organonitrile solvent system, which are compositionally stable, environmentally safe, can be produced efficiently in large quantity and which, because of their high conductivities .apprxeq.10.sup.-3 .OMEGA..sup.-1 cm.sup.-1 are useful as electrolytes for rechargeable lithium batteries.

  15. Thin film polymeric gel electrolytes

    DOEpatents

    Derzon, D.K.; Arnold, C. Jr.; Delnick, F.M.

    1996-12-31

    Novel hybrid thin film electrolytes, based on an organonitrile solvent system, which are compositionally stable, environmentally safe, can be produced efficiently in large quantity and which, because of their high conductivities {approx_equal}10{sup {minus}3}{Omega}{sup {minus}1} cm{sup {minus}1} are useful as electrolytes for rechargeable lithium batteries. 1 fig.

  16. Low work function, stable thin films

    DOEpatents

    Dinh, Long N.; McLean, II, William; Balooch, Mehdi; Fehring, Jr., Edward J.; Schildbach, Marcus A.

    2000-01-01

    Generation of low work function, stable compound thin films by laser ablation. Compound thin films with low work function can be synthesized by simultaneously laser ablating silicon, for example, and thermal evaporating an alkali metal into an oxygen environment. For example, the compound thin film may be composed of Si/Cs/O. The work functions of the thin films can be varied by changing the silicon/alkali metal/oxygen ratio. Low work functions of the compound thin films deposited on silicon substrates were confirmed by ultraviolet photoelectron spectroscopy (UPS). The compound thin films are stable up to 500.degree. C. as measured by x-ray photoelectron spectroscopy (XPS). Tests have established that for certain chemical compositions and annealing temperatures of the compound thin films, negative electron affinity (NEA) was detected. The low work function, stable compound thin films can be utilized in solar cells, field emission flat panel displays, electron guns, and cold cathode electron guns.

  17. On thinning of chains in MCMC

    USGS Publications Warehouse

    Link, William A.; Eaton, Mitchell J.

    2012-01-01

    4. We discuss the background and prevalence of thinning, illustrate its consequences, discuss circumstances when it might be regarded as a reasonable option and recommend against routine thinning of chains unless necessitated by computer memory limitations.

  18. Semiconductor-nanocrystal/conjugated polymer thin films

    DOEpatents

    Alivisatos, A. Paul; Dittmer, Janke J.; Huynh, Wendy U.; Milliron, Delia

    2014-06-17

    The invention described herein provides for thin films and methods of making comprising inorganic semiconductor-nanocrystals dispersed in semiconducting-polymers in high loading amounts. The invention also describes photovoltaic devices incorporating the thin films.

  19. Semiconductor-nanocrystal/conjugated polymer thin films

    DOEpatents

    Alivisatos, A. Paul; Dittmer, Janke J.; Huynh, Wendy U.; Milliron, Delia

    2010-08-17

    The invention described herein provides for thin films and methods of making comprising inorganic semiconductor-nanocrystals dispersed in semiconducting-polymers in high loading amounts. The invention also describes photovoltaic devices incorporating the thin films.

  20. Thin film-coated polymer webs

    DOEpatents

    Wenz, Robert P.; Weber, Michael F.; Arudi, Ravindra L.

    1992-02-04

    The present invention relates to thin film-coated polymer webs, and more particularly to thin film electronic devices supported upon a polymer web, wherein the polymer web is treated with a purifying amount of electron beam radiation.