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Sample records for gd2o3-doped ceo2 thin

  1. Synthesis and different optical properties of Gd2O3 doped sodium zinc tellurite glasses

    NASA Astrophysics Data System (ADS)

    Samanta, Buddhadev; Dutta, Dibakar; Ghosh, Subhankar

    2017-06-01

    A series of Gd2O3 doped sodium zinc tellurite [xGd2O3-(0.8-x) TeO2-0.1Na2O-0.1ZnO] glasses are prepared by the conventional melt quenching method and their optical properties have been studied. UV-vis spectrophotometric studies within the wavelength range from 230 nm-800 nm are carried out in the integrating sphere mode to study the effect of Gd2O3 doping on the optical band gap (Eg), refractive index (n), dielectric constant (εr) and susceptibility (χ). Other physical properties like molar volume, molar refraction, polarizability, metallization criterion, number density of rare-earth ions (N), polaron radius (rp), inter ionic distance (ri), molar cation polarizability (∑αi), number of oxide ions in chemical composition (NO2-), optical band gap based electronic oxide ion polarizability (αO2-) and optical basicity (Λ) of glass samples have been studied on the basis of UV-vis spectra and density profile of the different glasses.

  2. 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.

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

    NASA Astrophysics Data System (ADS)

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

    1993-06-01

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

  4. 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.

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

    NASA Astrophysics Data System (ADS)

    Kerman, Kian

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

  6. 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.

  7. Measurement of oxygen chemical potential in Gd 2O 3-doped ceria-Y 2O 3-stabilized zirconia bi-layer electrolyte, anode-supported solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Lim, Hyung-Tae; Virkar, Anil V.

    Solid oxide fuel cells (SOFC) were fabricated with gadolinia-doped ceria (GDC)-yttria stabilized zirconia (YSZ), thin bi-layer electrolytes supported on Ni + YSZ anodes. The GDC and YSZ layer thicknesses were 45 μm, and ∼5 μm, respectively. Two types of cells were made; YSZ layer between anode and GDC (GDC/YSZ) and YSZ layer between cathode and GDC (YSZ/GDC). Two platinum reference electrodes were embedded within the GDC layer. Cells were tested at 650 °C with hydrogen as fuel and air as oxidant. Electric potentials between embedded reference electrodes and anode and between cathode and anode were measured at open circuit, short circuit and under load. The electric potential was nearly constant through GDC in the cathode/YSZ/GDC/anode cells. By contrast, it varied monotonically through GDC in the cathode/GDC/YSZ/anode cells. Estimates of oxygen chemical potential, μO2 , variation through GDC were made. μO2 within the GDC layer in the cathode/GDC/YSZ/anode cell decreased as the current was increased. By contrast, μO2 within the GDC layer in the cathode/YSZ/GDC/anode cell increased as the current was increased. The cathode/YSZ/GDC/anode cell exhibited maximum power density of ∼0.52 W cm -2 at 650 °C while the cathode/GDC/YSZ/anode cell exhibited maximum power density of ∼0.14 W cm -2 for the same total electrolyte thickness.

  8. 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.

  9. 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

  10. 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

  11. The influence of Er3+ doping on the structural and optical properties of CeO2 thin films grown by PED

    NASA Astrophysics Data System (ADS)

    Tatar, B.; Gökdemir, F. P.; Pehlivan, E.; Urgen, M.

    2013-11-01

    Erbium doped CeO2 thin films were deposited on both Corning glass substrates and indium doped tin oxide (ITO) coated glass substrates by pulsed e-beam deposition (PED) method at room temperature. Structural features of Er doped CeO2 thin films were studied with X-ray diffraction (XRD) and micro-Raman spectra. The XRD patterns of all films showed polycrystalline nature and cubic crystalline structure. Raman active peaks for both undoped CeO2 and Er doped CeO2 films were determined at ˜465 cm-1. The Raman shift observed in this study can also be assigned to Raman active modes of CeO2 that are shifted from the original position due to different doping concentration. The optical properties of CeO2 films and Er doped CeO2 films, which were determined from transmittance and reflectance measurements at room temperature, were very similar in character. The refractive indices and extinction coefficients, which were calculated from 3.5 to 1.25 eV (300-1000 nm), were between 1.5-3 and 0.05-0.2, respectively. The optical band gaps were deduced from the absorption coefficient according to solid band theory. The electrochromic measurements revealed that 2% Er doped CeO2 films grown on ITO + WO3 substrates had highest charge density compared to the other samples. Long-time cyclic voltammetry (CV) and chronoamperometry (CA) measurements were carried out to investigate the stability of this film.

  12. 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.

  13. 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

  14. 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.

  15. Hg-based cuprate superconducting thin films prepared on CeO2 buffered R-plane sapphire substrate

    NASA Astrophysics Data System (ADS)

    Chromik, S.; Sin, A.; Strbík, V.; Plesch, G.; Odier, P.; Weiss, F.

    2001-10-01

    Hg-Ba-Ca-Cu-O films have been grown on CeO2/R-plane sapphire substrates using a two-step process. First, a 200 nm thick Ba-Ca-Cu-(O, F) precursor film was prepared by sequential evaporation, then Hg-Re-Ba-Ca-Cu-O pellets as a source of Hg-vapour were applied using heat treatment. The prepared films were continuous with sufficient adhesion to the substrate and a maximum zero-resistance critical temperature of TC0 = 118 K. The x-ray diffraction measurements of all the prepared films confirmed the Hg-1212 phase as well as the minor Hg-1223 phase in some cases. We found that the best results were obtained at the mercuration temperature of 775 °C and an optimal annealing time within the range 0.5-5 h. The superconducting properties of the films prepared under unsuitable conditions were mostly improved after annealing in oxygen atmosphere. Darker parts of the film exhibited a different surface morphology and the presence of the Hg-1223 phase in plate-like grains.

  16. Synthesis and characterization of Gd2O3 doped UO2 nanoparticles

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

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

  17. The optical band gap of Gd-doped CeO2 thin films as function of temperature and composition

    NASA Astrophysics Data System (ADS)

    Ruiz-Trejo, Enrique

    2013-04-01

    Thin films of Ce1-xGdxO2-x/2 (x=0, 0.1, 0.2, 0.3) were prepared by Pulse Laser Deposition and characterized at room temperature by SEM, XRD and Raman spectroscopy. The coefficient of absorption of the 200 nm thin films was measured between room and liquid nitrogen temperatures. The direct and indirect optical band gaps were estimated using Tauc plots. Substitution of Ce for Gd was found to have a significant effect on the coefficient of absorption, although there is a weak band gap dependence upon temperature. This was attributed to the poor overlap of the 4f orbitals of the lanthanides in gadolinia-doped ceria. An expression for the direct and indirect optical band gap of each gadolinia-doped ceria as a function of temperature is given. As an example, for ceria the direct optical band gap is 3.66±0.008 eV -1.25±0.05×10-4 eV K-1.

  18. 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.

  19. 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.

  20. Gd2O3-doped silica @ Au nanoparticles for in vitro imaging cancer biomarkers using surface-enhanced Raman scattering

    NASA Astrophysics Data System (ADS)

    Xiao, Lifu; Tian, Xiumei; Harihar, Sitaram; Li, Qifei; Li, Li; Welch, Danny R.; Zhou, Anhong

    2017-06-01

    There has been an interest in developing multimodal approaches to combine the advantages of individual imaging modalities, as well as to compensate for respective weaknesses. We previously reported a composite nano-system composed of gadolinium-doped mesoporous silica nanoparticle and gold nanoparticle (Gd-Au NPs) as an efficient MRI contrast agent for in vivo cancer imaging. However, MRI lacks sensitivity and is unsuitable for in vitro cancer detection. Thus, here we performed a study to use the Gd-Au NPs for detection and imaging of a widely recognized human cancer biomarker, epidermal growth factor receptor (EGFR), in individual human cancer cells with surface-enhanced Raman scattering (SERS). The Gd-Au NPs were sequentially conjugated with a monoclonal antibody recognizing EGFR and a Raman reporter molecule, 4-meraptobenzoic acid (MBA), to generate a characteristic SERS signal at 1075 cm- 1. By spatially mapping the SERS intensity at 1075 cm- 1, cellular distribution of EGFR and its relocalization on the plasma membrane were measured in situ. In addition, the EGFR expression levels in three human cancer cell lines (S18, A431 and A549) were measured using this SERS probe, which were consistent with the comparable measurements using immunoblotting and immunofluorescence. Our SERS results show that functionalized Gd-Au NPs successfully targeted EGFR molecules in three human cancer cell lines and monitored changes in single cell EGFR distribution in situ, demonstrating its potential to study cell activity under physiological conditions. This SERS study, combined with our previous MRI study, suggests the Gd-Au nanocomposite is a promising candidate contrast agent for multimodal cancer imaging.

  1. 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.

  2. 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.

  3. 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

  4. 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

  5. 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.

  6. 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

  7. 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.

  8. 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.

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

    PubMed Central

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

    2016-01-01

    In surface science and model catalysis, cerium oxide (ceria) is mostly grown as an ultra-thin film on a metal substrate in the ultra-high vacuum to understand fundamental mechanisms involved in diverse surface chemistry processes. However, such ultra-thin films do not have the contribution of a bulk ceria underneath, which is currently discussed to have a high impact on in particular surface redox processes. Here, we present a fully oxidized ceria thick film (180 nm) with a perfectly stoichiometric CeO2(111) surface exhibiting exceptionally large, atomically flat terraces. The film is well-suited for ceria model studies as well as a perfect substitute for CeO2 bulk material. PMID:26879800

  10. 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.

  11. 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.

  12. Unusual Compression Behavior of Nanocrystalline CeO2

    PubMed Central

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

    2014-01-01

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

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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

  19. 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.

  20. 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.

  1. Optical Properties Characterization of Gamma Irradiated CeO2 Nanoparticles Solution

    NASA Astrophysics Data System (ADS)

    Nurhasanah, I.; Luthfia, A.; Arifin, Z.

    2017-05-01

    Optical properties of CeO2 nanoparticles solution have been studied to explore the possibility of CeO2 nanoparticles as a liquid chemical dosimeter to measure gamma radiation in radiotherapy. CeO2 nanoparticles were synthesized by ultrasound irradiation of cerium nitrate solution. The CeO2 nanoparticles were characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). CeO2 nanoparticles solution with concentration of 2.5 x 10-4 g/ml was irradiated by 1.3 MV 60Co gamma rays with a dose of 1.0 to 2.5 Gy. The UV absorbance spectrum of unirradiated and irradiated CeO2 nanoparticles solution was measured by using UV-Vis spectrophotometer. The UV absorbance of CeO2 nanoparticles solution increased with increasing radiation dose and caused a change in the band gap. The change in optical properties of CeO2 nanoparticles solution is correlated to chemical reactions induced by gamma radiation. The obtained chemical yield was in the order of 103 mol/J indicates the sensitivity of CeO2 nanoparticles to gamma radiation. The results show the possibility of CeO2 nanoparticles for use as gamma radiation dosimeter.

  2. Preparation and photocatalytic property of CeO 2 lamellar

    NASA Astrophysics Data System (ADS)

    Chen, Fengjuan; Cao, Yali; Jia, Dianzeng

    2011-08-01

    A novel room temperature solid-state chemical synthesis was introduced to successfully fabricate CeO 2 samples, coupled by a polyethylene glycol 400 (PEG 400)/cetyl trimethylammonium bromide (CTAB)/sodium dodecyl sulfate (SDS). The as-prepared products were characterized by XRD, TEM, SEM, BET and UV. A study of photocatalytic degradation of the methylene blue MB under UV illumination has been carried out. It is indicated that the samples exhibit excellent photocatalytic activity. Besides, the samples assisted with surfactants possess higher photocatalytic activity than the sample without any surfactants, wherein the sample with SDS as an additive shows the highest photocatalytic activity, which is able to reach 89.6% MB degradation ratio within 60 min illumination. Moreover, the effects of important operational parameters such as initial MB concentration, catalyst loading and pH were also investigated. The above sample under the optimum conditions obtained the maximum MB degradation ratio up to 96.5%, which is higher than that of the commercial TiO 2 P25 under the same conditions. It can be concluded that CeO 2 will be a potential photocatalyst in the application of organic pollutant.

  3. 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. © 2013.

  4. Photocatalytic degradation of dye using CeO2/SCB composite catalysts

    NASA Astrophysics Data System (ADS)

    Channei, Duangdao; Nakaruk, Auppatham; Phanichphant, Sukon

    2017-08-01

    The main task of the present work is to enhance the photocatalytic degradation efficiency of methylene blue (MB) by using CeO2/sugarcane bagasse (SCB) composite catalysts. Homogeneous precipitation method was used to synthesis CeO2-SCB composite catalysts by adding SCB powder to precursor solution of Ce base-metal. The structural analytical data indicated the pure cubic fluorite structure of CeO2. Morphological images revealed the coating of CeO2 layer on high surface area of SCB core-shell. The chemical analysis presented spectrum of the Ce 3d in CeO2/SCB sample existed in the form of the Ce3 + and Ce4 + mixed- valence states. Optical spectra showed the shift of absorption edge towards longer visible region upon supporting CeO2 with SCB. The main chemical composition of the SCB was K, Ca, and Si. Furthermore, recombination of the photogenerated electrons and holes was identified by photoluminescence techniques (PL), the data suggested inhibition of electron-hole pairs recombination by the cations from SCB loaded in CeO2/SCB composite. Photocatalytic activity of CeO2/SCB catalyst was investigated via the degradation of MB under UV-A irradiation. Experimental kinetic data followed the pseudo-first order model. CeO2 supported with SCB adsorbent had higher photocatalytic activity in dye wastewater treatment compared to the pure CeO2. The proposed mechanism explaining the high photocatalytic efficiency of CeO2/SCB was associated with high surface properties and the suppression of recombination of the photogenerated electron-hole pairs by the SCB adsorbent.

  5. Reactive CeO2 nanofluids for UV protective films.

    PubMed

    Maniglia, Rafael; Reed, Kenneth J; Texter, John

    2017-11-15

    We investigate surface modification by organo-trimethoxysilanes of nano-ceria and if such surface-modified nano-ceria can be transformed into solvent-free nanofluids. We also examine whether simultaneous modification with ionic liquid salts and with acrylate groups yields nanofluids suitable for forming UV-protective films and clear coatings by UV-initiated polymerization. Nominally 3nm diameter CeO2 was successfully synthesized and surface decorated with an ionic liquid salt and with acrylate groups to produce a core/shell structured solvent-free nanofluid after ion exchange of chloride for a soft polyoxyethylene sulfonate anion. This room temperature nanofluid melts at about -10°C and exhibits a glass transition at about -71°C. The melting enthalpy, about 19J/g, corresponds approximately to the gain in surface free energy of such nanofluid particles upon transforming from the solid state to liquid state. Robust films were made by UV photoinitiation of this nanofluid in combination with ethylene glycol dimethacrylate and with a polyoxyethylene diacrylate to yield cross-linked films with absorption coefficients α350nm=6.6±0.8cm(2)/mg and α300nm=24.5±3.5cm(2)/mg. Average near UV protection over 300-350nm of 1-3 optical density units can be obtained with 0.065-0.19mg/cm(2) of CeO2. These materials appear almost three-fold more effective, per unit ceria, than previously reported clearcoats of nanoceria. Copyright © 2017 Elsevier Inc. All rights reserved.

  6. 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.

  7. 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

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. Phytotoxicity of CeO2 nanoparticles on radish plant (Raphanus sativus).

    PubMed

    Gui, Xin; Rui, Mengmeng; Song, Youhong; Ma, Yuhui; Rui, Yukui; Zhang, Peng; He, Xiao; Li, Yuanyuan; Zhang, Zhiyong; Liu, Liming

    2017-05-01

    Cerium oxide nanoparticles (CeO2 NPs) have been considered as one type of emerging contaminants that pose great potential risks to the environment and human health. The effect of CeO2 NPs on plant-edible parts and health evaluation remains is necessary and urgently to be developed. In this study, we cultivated radish in Sigma CeO2 NP (<25 nm)-amended soils across a series of concentration treatments, i.e., 0 mg/kg as the control and 10, 50, and 100 mg/kg CeO2 NPs. The results showed that CeO2 NPs accelerated the fresh biomass accumulation of radish plant; especially in the treatment of 50 mg/kg CeO2 NPs, root expansion was increased by 2.2 times as much as the control. In addition, the relative chlorophyll content enhanced by 12.5, 12.9, and 12.2% was compared to control on 40 cultivation days. CeO2 NPs were mainly absorbed by the root and improved the activity of antioxidant enzyme system to scavenge the damage of free radicals in radish root and leaf. In addition, this study also indicated that the nanoparticles might enter the food chain through the soil into the edible part of the plant, which will be a potential threat to human health.

  14. 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.

  15. 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.

  16. 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

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. Inverse CeO2sbnd Fe2O3 catalyst for superior low-temperature CO conversion efficiency

    NASA Astrophysics Data System (ADS)

    Luo, Yongming; Chen, Ran; Peng, Wen; Tang, Guangbei; Gao, Xiaoya

    2017-09-01

    The paper presents a rational design of highly efficient and affordable catalysts for CO oxidation with a low operating temperature. A series of ceria-iron catalysts were inversely built via a co-precipitation method. The catalytic activity of low-temperature CO oxidation was much higher with CeO2-modified Fe2O3 (CeO2sbnd Fe2O3) than with Fe2O3-modified CeO2 (Fe2O3sbnd CeO2). In particular, the 7.5% CeO2sbnd Fe2O3 catalyst had the highest activity, reaching 96.17% CO conversion at just 25 °C. Catalyst characterization was carried out to explore the cause of the significantly different CO conversion efficiencies between the Fe2O3sbnd CeO2 and Fe2O3sbnd CeO2 catalysts. HRTEM showed a significant inhomogeneous phase in 7.5% CeO2sbnd Fe2O3 with small CeO2 nanoparticles highly dispersed on the rod-shaped Fe2O3 surface. Furthermore, the 7.5% CeO2sbnd Fe2O3 composite catalyst exhibited the highest ratios of Fe2+/Fe3+ and Ce3+/Ce4+ as well as the largest pore volume. These properties are believed to benefit the CO conversion in 7.5% CeO2sbnd Fe2O3.

  5. 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.

  6. 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).

  7. 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. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. Catalytic hydrolysis of COS over CeO2 (110) surface: A density functional theory study

    NASA Astrophysics Data System (ADS)

    Song, Xin; Ning, Ping; Wang, Chi; Li, Kai; Tang, Lihong; Sun, Xin

    2017-08-01

    Density functional theory (DFT) calculations were performed to investigate the reaction pathways for catalytic hydrolysis of COS over CeO2 (110) surface using Dmol3 model. The thermodynamic stability analysis for the suggested routes of COS hydrolysis to CO2 and H2S was evaluated. The absolute values of adsorption energy of H2O-CeO2 are higher than that of COS-CeO2. Meanwhile, the adsorption energy and geometries show that H2O is easier adsorbed on the surface of CeO2 (110) than COS. H2O plays a role as a bridge in the process of joint adsorption. H2O forms more Cesbnd Osbnd H groups on the CeO2 (110) surface. CeO2 decreases the maximum energy barrier by 76.15 kcal/mol. The migration of H from H2O to COS is the key for the hydrolysis reaction. Csbnd O channel is easier to occur than Csbnd S channel. Experimental result shows that adding of CeO2 can increase COS removal rate and prolong the 100% COS removal rate from 180 min to 210 min. The difference between Fe2O3 and CeO2 for the hydrolysis of COS is characterized in the atomic charge transfer and the formation of Hsbnd O bond and Hsbnd S bond. The transfer effect of H in H2O to S in COS over CeO2 decreases the energy barriers of hydrolysis reaction, and enhances the reaction activity of COS hydrolysis.

  14. 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.

  15. 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

  16. Orientational control of CeO2 films on sapphire substrates grown by magnetron sputtering

    NASA Astrophysics Data System (ADS)

    Yamamoto, S.; Sugimoto, M.; Koshikawa, H.; Hakoda, T.; Yamaki, T.

    2017-06-01

    The effect of deposition temperature and post-annealing on the crystallographic orientation of cerium dioxide (CeO2) films on sapphire (α-Al2O3) substrates were investigated. CeO2 films, with thickness of 17 nm, were grown on c-plane and r-plane sapphire substrates by radiofrequency (rf) magnetron sputtering. Deposition temperatures between 150 and 500 °C were used with a sintered CeO2 target in an Ar-O2 gas mixture. The post-annealing treatment was performed in air at various temperatures ranging from 400 to 1000 °C. The films were characterized by X-ray diffraction, atomic force microscopy, and Rutherford backscattering spectroscopy. X-ray diffraction studies revealed that the orientation of the CeO2 films changed from (001) to mixed (001)/(111) and then to (111), with increasing deposition temperatures on both the c-plane and r-plane sapphire substrates. Post-annealing at 1000 °C improved the degree of crystallinity of the films, and formed rectangular grains. The results suggest that control of the deposition and post-annealing temperatures provides orientation-controlled CeO2 films on c- and r-plane sapphire substrates.

  17. 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)).

  18. 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.

  19. 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.

  20. 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. Copyright © 2014 Elsevier Inc. All rights reserved.

  1. 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.

  2. 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)

  3. 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.

  4. 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.

  5. 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.

  6. 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

  7. 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.

  8. Coadsorption of gold with chlorine on CeO2 (111) surfaces: A first principles study

    NASA Astrophysics Data System (ADS)

    Lu, Zhan-Sheng; He, Bing-Ling; Ma, Dong-Wei; Yang, Zong-Xian

    2015-02-01

    To investigate the effects of chlorine on the Au/ceria catalysts, the adsorption of gold or chlorine and their coadsorpiton on the stoichiometric and partially reduced CeO2 (111) surfaces are studied from the first principles. It is found that the adsorption of Au is significantly enhanced by the chlorine preadsorption on the stoichiometric CeO2 (111) surface; while on the partially reduced CeO2 (111) surface, the preadsorbed chlorine inhabits the oxygen vacancy (which is the preferred adsorption site for gold), leading to a CeOCl phase and the dramatical weakening of the Au adsorption. Therefore, chlorine on the CeO2 (111) surface can affect the Au adsorption thus the activity of the Au/CeO2 catalyst. Project supported by the National Natural Science Foundation of China (Grant Nos. 11174070, 51401078, and 11147006), the China Postdoctoral Science Foundation (Grant No. 2012M521399), the Postdoctoral Research Sponsorship in Henan Province, China (Grant No. 2011038), and the Foundation for the Key Young Teachers of Henan Normal University and Start-up Foundation for Doctors of Henan Normal University, China.

  9. Synthesis of CeO2 nanoparticles: Photocatalytic and antibacterial activities

    NASA Astrophysics Data System (ADS)

    Reddy Yadav, L. S.; Lingaraju, K.; Daruka Prasad, B.; Kavitha, C.; Banuprakash, G.; Nagaraju, G.

    2017-05-01

    We have successfully synthesized CeO2 nanoparticles (Nps) via the solution combustion method using sugarcane juice as a novel combustible fuel. The structural features, optical properties and morphology of the nanoparticles were characterized using XRD, FTIR, and Raman spectroscopy, UV-Vis, SEM and TEM. Structural characterization of the product shows cubic phase CeO2 . FTIR and Raman spectrum show characteristic peaks due to the presence of Ce-O vibration. SEM images show a porous structure and, from TEM images, the size of the nanoparticles were found to be ˜ 50 nm. The photocatalytic degradation of the methylene blue (MB) dye was examined using CeO2 Nps under solar irradiation as well as UV light irradiation and we studied the effect of p H, catalytic load and concentration on the degradation of the MB dye. Furthermore, the antibacterial properties of CeO2 Nps were investigated against Gram+ve and Gram- ve pathogenic bacterial strains using the agar well diffusion method.

  10. 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

  11. Surface-selective direct (17)O DNP NMR of CeO2 nanoparticles.

    PubMed

    Hope, Michael A; Halat, David M; Magusin, Pieter C M M; Paul, Subhradip; Peng, Luming; Grey, Clare P

    2017-02-09

    Surface-selective direct (17)O DNP has been demonstrated for the first time on CeO2 nanoparticles, for which the first three layers can be distinguished with high selectivity. Polarisation build-up curves show that the polarisation of the (sub-)surface sites builds up faster than the bulk, accounting for the remarkable surface selectivity.

  12. 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

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

    PubMed

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

    2016-05-25

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

  15. 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.

  16. 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.

  17. 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.

  18. 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 ...

  19. 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.

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

    EPA Science Inventory

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

  1. 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. Characterization and synergetic antibacterial properties of ZnO and CeO2 supported by halloysite

    NASA Astrophysics Data System (ADS)

    Shu, Zhan; Zhang, Yi; Ouyang, Jing; Yang, Huaming

    2017-10-01

    A novel antibacterial nanocomposite, CeO2-ZnO/HNTs was prepared by a homogeneous co-precipitation method in ethanol solution. ZnO and CeO2 nanoparticles with sizes of approximately 8 and 4 nm, respectively, were dispersively precipitated onto the surface of halloysite nanotubes (HNTs). HNTs served as a template for reducing the agglomeration of ZnO nanoparticles and improving the interface reactions between the nanocomposite and bacteria cells. CeO2 nanoparticles were introduced to suppress the recombination of electron-hole pairs, and narrow the energy gap of ZnO nanoparticles. The synergistic effects of ZnO, CeO2 nanoparticles and HNTs led to the superior antibacterial activity of the CeO2-ZnO/HNTs nanocomposite against gram-negative Escherichia coli.

  3. Xylem and Phloem Based Transport of CeO2 Nanoparticles in Hydroponic Cucumber Plants.

    PubMed

    Ma, Yuhui; He, Xiao; Zhang, Peng; Zhang, Zhiyong; Ding, Yayun; Zhang, Junzhe; Wang, Guohua; Xie, Changjian; Luo, Wenhe; Zhang, Jing; Zheng, Lirong; Chai, Zhifang; Yang, Ke

    2017-05-02

    Uptake and translocation of manufactured nanoparticles (NPs) in plants have drawn much attention due to their potential toxicity to the environment, including food webs. In this paper, the xylem and phloem based transport of CeO2 NPs in hydroponic cucumber plants was investigated using a split-root system. One half of the root system was treated with 200 or 2000 mg/L of CeO2 NPs for 3 days, whereas the other half remained untreated, with both halves sharing the same aerial part. The quantitative distribution and speciation of Ce in different plant tissues and xylem sap were analyzed by inductively coupled plasma-mass spectrometry, transmission electron microscope, X-ray absorption near edge structure, and X-ray fluorescence. Results show that about 15% of Ce was reduced from Ce(IV) to Ce(III) in the roots of the treated-side (TS), while almost all of Ce remained Ce(IV) in the blank-side (BS). The detection of CeO2 or its transformation products in the xylem sap, shoots, and BS roots indicates that Ce was transported as a mixture of Ce(IV) and Ce(III) from roots to shoots through xylem, while it was transported almost only in the form of CeO2 from shoots back to roots through phloem. To our knowledge, this is the first report of root-to-shoot-to-root redistribution after transformation of CeO2 NPs in plants, which has significant implications for food safety and human health.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. Magnetic ordered mesoporous Fe3O4/CeO2 composites with synergy of adsorption and Fenton catalysis

    NASA Astrophysics Data System (ADS)

    Li, Keyan; Zhao, Yongqin; Song, Chunshan; Guo, Xinwen

    2017-12-01

    Magnetic Fe3O4/CeO2 composites with highly ordered mesoporous structure and large surface area were synthesized by impregnation-calcination method, and the mesoporous CeO2 as support was synthesized via the hard template approach. The composition, morphology and physicochemical properties of the materials were characterized by XRD, SEM, TEM, XPS, Raman spectra and N2 adsorption/desorption analysis. The mesoporous Fe3O4/CeO2 composite played a dual-function role as both adsorbent and Fenton-like catalyst for removal of organic dye. The methylene blue (MB) removal efficiency of mesoporous Fe3O4/CeO2 was much higher than that of irregular porous Fe3O4/CeO2. The superior adsorption ability of mesoporous materials was attributed to the abundant oxygen vacancies on the surface of CeO2, high surface area and ordered mesoporous channels. The good oxidative degradation resulted from high Ce3+ content and the synergistic effect between Fe and Ce. The mesoporous Fe3O4/CeO2 composite presented low metal leaching (iron 0.22 mg L-1 and cerium 0.63 mg L-1), which could be ascribed to the strong metal-support interactions for dispersion and stabilization of Fe species. In addition, the composite can be easily separated from reaction solution with an external magnetic field due to its magnetic property, which is important to its practical applications.

  12. Protection of Photosynthetic Algae against Ultraviolet Radiation by One-Step CeO2 Shellization.

    PubMed

    Duan, Pengqiang; Huang, Tingting; Xiong, Wei; Shu, Lei; Yang, Yuling; Shao, Changyu; Xu, Xurong; Ma, Weimin; Tang, Ruikang

    2017-03-07

    Photosynthetic microalgae play an important role in solar-to-chemical energy conversion on Earth, but the increasing solar ultraviolet (UV) radiation seriously reduces the biological photosynthesis. Here, we developed a one-step approach to construct cell-in-shell hybrid structure by using direct adsorption of CeO2 nanoparticles onto cells. The engineered CeO2 nanoshell can efficiently protect the enclosed Chlorella cell due to its excellent UV filter property, which can also eliminate UV-induced oxidative stress. The experiments demonstrate that the resulted algae-CeO2 composites can guarantee their biological photosynthetic process and efficiency even under UV. This study follows a feasible strategy to protect living organisms by using functional nanomaterials to improve their biological functions.

  13. 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

  14. 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.

  15. Correlation among Channeling, Morphological and Micro-structural Properties in Epitaxial CeO2 Films

    SciTech Connect

    Saraf, Laxmikant V.; McCready, David E.; Shutthanandan, V.; Wang, Chong M.; Engelhard, Mark H.; Thevuthasan, Suntharampillai

    2006-03-20

    We report an evidence of a critical thickness at ~ 64 nm in epitaxial CeO2 films grown at 750 0C on YSZ substrates by dc magnetron sputtering where optimum ion channeling can be correlated with overall strain relaxation and film surface roughness. The occurrence of saturation in ion channeling yield, enhancement in the average surface roughness and relaxation in c-axis strain is clearly evident in thicker films beyond the critical thickness. Despite excellent surface smoothness and overall epitaxial growth, CeO2 films grown at 650 0C did not show optimum ion channeling properties due to high misfit dislocation and defect density. These results are discussed from a viewpoint of the need for such an optimum thickness to develop multilayers with smooth interfaces with relative overall lattice relaxation.

  16. 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.

  17. Intrinsic ferromagnetism in CeO2: dispelling the myth of vacancy site localization mediated superexchange

    NASA Astrophysics Data System (ADS)

    Keating, P. R. L.; Scanlon, D. O.; Watson, G. W.

    2009-10-01

    Intrinsic ferromagnetism in CeO2 is a source of controversy in the literature and has been linked to the excess electrons left over upon oxygen vacancy formation on Ce sites neighbouring the vacancy. A recent theoretical study (Han et al 2009 Phys. Rev. B 79 100403) concluded that increased vacancy concentration changes the localization behaviour of CeO2, resulting in some degree of charge localization in the vacancy site itself, which leads to superexchange and polarization effects that enhance the stability of ferromagnetism. In this report, we show conclusively that oxygen vacancy concentrations of up to 12.5% do not cause localization in the vacancy site, and that this is not responsible for any enhanced ferromagnetism. Investigation of oxygen vacancies on the (111), (110) and (100) low index surfaces also show no evidence for ferromagnetic preference.

  18. CeO2/CoPc Nanocomposite for Potential Applications in Electronics

    NASA Astrophysics Data System (ADS)

    Babitha, K. K.; Priyanka, K. P.; Hitha, H.; Rintu Mary, S.; Mohammed, E. M.; Sankararaman, S.; Varghese, Thomas

    2017-10-01

    This study reports the influence of cobalt phthalocyanine on the dielectric properties and electrical conductivity of CeO2 nanoparticles, at various temperatures. A CeO2/CoPc nanocomposite was synthesized using a standard procedure and characterized by x-ray diffraction. The surface morphology of the sintered samples was analyzed by scanning electron microscopy. The dielectric constant was calculated from the observed capacitance values in the frequency range of 100 Hz-10 MHz. It is found that the dielectric constant and dielectric loss vary as a function of frequency and have a strong dielectric response at low frequency. The occurrence of relaxation peaks in the electric modulus plot ( M ll versus log f) indicates that this nanocomposite sample is an ionic conductor. The a.c. conductivity of the nanocomposite increases with frequency. The desired structural and dielectric properties make it as a good candidate for potential applications in molecular electronics and high-frequency applications.

  19. Epitaxial CeO 2/MgO buffer layers on cubic textured Ni substrates for superconducting tapes

    NASA Astrophysics Data System (ADS)

    Yang, Jian; Gu, Hongwei; Hu, Guangyong; Shi, Kai; Yuan, Guansen

    Reported here is a novel epitaxial buffer layer configuration combined with MgO and CeO 2 on biaxially texture Ni substrates for high temperature superconducting (HTS) tapes. The hetero-epitaxial CeO 2/MgO/Ni structure was grown by magnetron sputtering method. After formation of the buffer layers, θ-2θ and Φ scans of x-ray diffraction were used to measure the film in-plane and out-plane orientation, respectively. The deposited CeO 2 and MgO buffer layers showed good in-plane alignment.

  20. 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

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. Synthesis of CeO2-based core/shell nanoparticles with high oxygen storage capacity

    NASA Astrophysics Data System (ADS)

    Uzunoglu, Aytekin; Kose, Dursun Ali; Stanciu, Lia A.

    2017-07-01

    Ceria plays a key role in various applications including sensing and catalysis owing to its high oxygen storage capacity (OSC). The aim of this work is to prepare novel MO x /CeO2 (M: Zr, Ti, Cu) metal oxide systems with core/shell structures using a facile two-step chemical precipitation method. The synthesized nanoparticles were characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), and N2 adsorption methods. The OSC property of the samples was evaluated using TGA analysis conducted at 600 °C under reductive (5% H2/Ar) and oxidative (synthetic air) environments. The OSCs of the samples were found to be 130, 253, and 2098 µmol-O2/g for ZrO2/CeO2, TiO2/CeO2, and CuO/CeO2, respectively. Effects of heat treatment on the physical and redox properties of the samples were also evaluated. In this regard, the samples were exposed to 500 °C for 5 h under ambient environment. It was observed that the heat treatment induced the formation of mixed metal oxide alloys and the BET surface area of the samples diminished significantly. The OSC of the samples, however, did not experience any significant chance, which was attributed to the compensation of the loss in the surface area by the alloy formation after the heat treatment.

  7. 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.

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

    PubMed

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

    2014-12-10

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

  9. Density functional analysis of fluorite-structured (Ce, Zr)O2/CeO2 interfaces [Density functional analysis of fluorite-structured (Ce, Zr)O2/CeO2 interfaces: Implications for catalysis and energy applications

    DOE PAGES

    Weck, Philippe F.; Juan, Pierre -Alexandre; Dingreville, Remi; ...

    2017-06-21

    The structures and properties of Ce1–xZrxO2 (x = 0–1) solid solutions, selected Ce1–xZrxO2 surfaces, and Ce1–xZrxO2/CeO2 interfaces were computed within the framework of density functional theory corrected for strong electron correlation (DFT+U). The calculated Debye temperature increases steadily with Zr content in (Ce, Zr)O2 phases, indicating a significant rise in microhardness from CeO2 to ZrO2, without appreciable loss in ductility as the interfacial stoichiometry changes. Surface energy calculations for the low-index CeO2(111) and (110) surfaces show limited sensitivity to strong 4f-electron correlation. The fracture energy of Ce1–xZrxO2(111)/CeO2(111) increases markedly with Zr content, with a significant decrease in energy for thickermore » Ce1–xZrxO2 films. These findings suggest the crucial role of Zr acting as a binder at the Ce1–xZrxO2/CeO2 interfaces, due to the more covalent character of Zr–O bonds compared to Ce–O. Finally, the impact of surface relaxation upon interface cracking was assessed and found to reach a maximum for Ce0.25Zr0.75O2/CeO2 interfaces.« less

  10. 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.

  11. 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.

  12. 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. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

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

    PubMed

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

    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, Cr23C6 and Ni3B 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.

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

    PubMed Central

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

    2008-01-01

    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, Cr23C6 and Ni3B 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. PMID:27877999

  15. 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.

  16. 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.

  17. 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

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. Different heat treatment of CeO2 nanoparticle composited with ZnO to enhance photocatalytic performance

    NASA Astrophysics Data System (ADS)

    Taufik, A.; Shabrany, H.; Saleh, R.

    2017-04-01

    In this study, ZnO/CeO2 nanocomposites were prepared with four variations of the molar ratio of ZnO to CeO2 nanoparticles. Both ZnO and CeO2 nanoparticles were synthesized using the sol-gel method at low temperature, followed by different heat treatments for CeO2 nanoparticles. Thermal phase transformation studies of the CeO2 nanoparticles were observed at annealing temperatures of 400-800°C. The complete crystalline structure of CeO2 nanoparticles was obtained at an annealing temperature of 800°C. The structural and optical properties of all samples were observed using several characterization techniques, such as X-ray diffraction (XRD), ultraviolet-visible diffuse reflectance spectroscopy, and Brunauer, Emmett, and Teller (BET) surface area analysis. The structural characterization results revealed that the prepared CeO2 nanoparticles were quite crystalline, with a cubic structure. The photocatalytic activities of all samples were tested under visible irradiation. The obtained results showed that ZnO/CeO2 nanocomposites with a molar ratio 1:0.3 exhibited the highest photocatalytic activity. Further understanding of the role of primary active species underlying the reaction mechanism involved in photocatalytic activity were carried out in controlled experiments by adding several scavengers. The detailed mechanism and its correlation with the properties of ZnO/CeO2 nanocomposites were discuss.

  3. 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

  4. 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.

  5. 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.

  6. 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.

  7. Exposure of agricultural crops to nanoparticle CeO2 in biochar-amended soil.

    PubMed

    Servin, Alia D; De la Torre-Roche, Roberto; Castillo-Michel, Hiram; Pagano, Luca; Hawthorne, Joseph; Musante, Craig; Pignatello, Joseph; Uchimiya, Minori; White, Jason C

    2017-01-01

    Biochar is seeing increased usage as an amendment in agricultural soils but the significance of nanoscale interactions between this additive and engineered nanoparticles (ENP) remains unknown. Corn, lettuce, soybean and zucchini were grown for 28 d in two different soils (agricultural, residential) amended with 0-2000 mg engineered nanoparticle (ENP) CeO2 kg(-1) and biochar (350 °C or 600 °C) at application rates of 0-5% (w/w). At harvest, plants were analyzed for biomass, Ce content, chlorophyll and lipid peroxidation. Biomass from the four species grown in residential soil varied with species and biochar type. However, biomass in the agricultural soil amended with biochar 600 °C was largely unaffected. Biochar co-exposure had minimal impact on Ce accumulation, with reduced or increased Ce content occurring at the highest (5%) biochar level. Soil-specific and biochar-specific effects on Ce accumulation were observed in the four species. For example, zucchini grown in agricultural soil with 2000 mg CeO2 kg(-1) and 350 °C biochar (0.5-5%) accumulated greater Ce than the control. However, for the 600 °C biochar, the opposite effect was evident, with decreased Ce content as biochar increased. A principal component analysis showed that biochar type accounted for 56-99% of the variance in chlorophyll and lipid peroxidation across the plants. SEM and μ-XRF showed Ce association with specific biochar and soil components, while μ-XANES analysis confirmed that after 28 d in soil, the Ce remained largely as CeO2. The current study demonstrates that biochar synthesis conditions significantly impact interactions with ENP, with subsequent effects on particle fate and effects. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

  8. 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

  9. 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.

  10. 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.

  11. Facile method for fabrication of surfactant-free concentrated CeO2 sols

    NASA Astrophysics Data System (ADS)

    Shcherbakov, Alexander B.; Teplonogova, Maria A.; Ivanova, Olga S.; Shekunova, Taisiya O.; Ivonin, Ivan V.; Baranchikov, Alexander Ye; Ivanov, Vladimir K.

    2017-05-01

    We report a facile method for fabrication of highly concentrated electrostatically stabilized colloidal solutions containing ultra-small cerium (IV) oxide crystallites having a narrow size distribution (3-5 nm according to x-ray diffraction, and 10-30 nm according to dynamic light scattering). The proposed method comprises hydrothermal treatment of ceric ammonium nitrate aqueous solutions having concentrations over 0.2 M, in the temperature range of 80-100 °C, and the formation of nanoceria sediments, which can be easily peptized in both protic (water, isopropanol) and aprotic (DMF) media, forming stable and transparent CeO2 sols.

  12. 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.

  13. Confined NaAlH4 nanoparticles inside CeO2 hollow nanotubes towards enhanced hydrogen storage.

    PubMed

    Gao, Qili; Xia, Guanglin; Yu, Xuebin

    2017-09-22

    NaAlH4 has been widely regarded as a potential hydrogen storage material due to its favorable thermodynamics and high energy density. The high activation energy barrier and high dehydrogenation temperature, however, significantly hinder its practical application. In this paper, CeO2 hollow nanotubes (HNTs) prepared by a simple electrospinning technique are adopted as functional scaffolds to support NaAlH4 nanoparticles (NPs) towards advanced hydrogen storage performance. The nanoconfined NaAlH4 inside CeO2 HNTs, synthesized via the infiltration of molten NaAlH4 into the CeO2 HNTs under high hydrogen pressure, exhibited significantly improved dehydrogenation properties compared with both bulk and ball-milled CeO2 HNTs-catalyzed NaAlH4. The onset dehydrogenation temperature of the NaAlH4@CeO2 composite was reduced to below 100 °C, with only one main dehydrogenation peak appearing at 130 °C, which is 120 °C and 50 °C lower than for its bulk counterpart and for the ball-milled CeO2 HNTs-catalyzed NaAlH4, respectively. Moreover, ∼5.09 wt% hydrogen could be released within 30 min at 180 °C, while only 1.6 wt% hydrogen was desorbed from the ball-milled NaAlH4 under the same conditions. This significant improvement is mainly attributed to the synergistic effects contributed by the CeO2 HNTs, which could act as not only a structural scaffold to fabricate and confine the NaAlH4 NPs, but also as an effective catalyst to enhance the hydrogen storage performance of NaAlH4.

  14. 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.

  15. 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.

  16. 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

  17. 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.

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

    DOE PAGES

    Marchbank, Huw R.; Clark, Adam H.; Hyde, Timothy I.; ...

    2016-08-29

    Here, the nature of nano-sized ceria, CeO2, systems were investigated using neutron and X-ray diffraction and X-ray absorption spectroscopy. Whilst both diffraction andtotal pair distribution functions (PDFs) revealed that in all the samples the occupancy of both Ce4+ and O2- are very close to the ideal stoichiometry, the analysis using reverse Monte Carlo technique revealedsignificant disorder around oxygen atoms in the nano sized ceria samples in comparison to the highly crystalline NIST standard.In addition, the analysis reveal that the main differences observed in the pair correlations from various X-ray and neutron diffraction techniques were attributed to the particle size ofmore » 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, are attributed to differences in particle size.« less

  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. 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.

  2. 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

  3. Near-infrared luminescence of Tm3+-doped CeO2 films based on silicon substrates

    NASA Astrophysics Data System (ADS)

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

    2016-02-01

    CeO2/Tm2O3 multilayer films were deposited on silicon substrates by electron-beam evaporation. Tm3+ ions were doped in CeO2 after the films were annealed in oxygen atmosphere at 1000 °C. The doping concentration of Tm3+ varies in the range of 0.1-3 mol%. A series of near-infrared emission peaks were observed under the excitation of 330 nm, which correspond to 1G4-3H5, 3H4-3H6, 1G4-3H4, 3H5-3H6, 3F2-3H5, 3H4-3F4, 1G4-3F3,2 and 3F4-3H6 transitions of Tm3+, respectively. The dominant transition of 3H4-3H6 near 805 nm was within optical transmission window. The luminescence properties and the crystal structure of CeO2:Tm3+ films were investigated by excitation and emission spectroscopy and X-ray diffraction. Meanwhile, the substitution process of Ce4+ by Tm3+ was illustrated, and lattice expansion of the matrix CeO2 gave rise to the increase in FWHM of CeO2 diffraction peaks. In addition, the effect of Tm3+ concentration on photoluminescence was also studied, and the optimal concentration of Tm3+ was 0.5 mol%.

  4. 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

  5. Aggregation kinetics of CeO2 nanoparticles in KCl and CaCl2 solutions: measurements and modeling

    NASA Astrophysics Data System (ADS)

    Li, Kungang; Zhang, Wen; Huang, Ying; Chen, Yongsheng

    2011-12-01

    To characterize the environmental transport and health risks of CeO2 nanoparticles (NPs), it is important to understand their aggregation behavior. This study investigates the aggregation kinetics of CeO2 NPs in KCl and CaCl2 solutions using time-resolved dynamic light scattering (TR-DLS). The initial hydrodynamic radius of CeO2 NPs measured by DLS was approximately 95 nm. Attachment efficiencies were derived both from aggregation data and predictions based on the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. The deviations of the DLVO predictions were corrected by employing the extended DLVO (EDLVO) theory. The critical coagulation concentration (CCC) of CeO2 NPs at pH = 5.6 is approximately 34 mM for KCl and 9.5 mM for CaCl2. Furthermore, based on the EDLVO theory and the von Smoluchowski's population balance equation, a model accounting for diffusion-limited aggregation (DLA) kinetics was established. For the reaction-limited aggregation (RLA) kinetics, a model that takes fractal geometry into account was established. The models fitted the experimental data well and proved to be useful for predicting the aggregation kinetics of CeO2 NPs.

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

    SciTech Connect

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

    2014-05-13

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

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

    PubMed

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

    2013-04-01

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

  9. Effect of CeO2 coprecipitation on the electrochemical performance of Li(Li,Ni,Mn,Co)O2-CeO2-C composite cathode materials

    NASA Astrophysics Data System (ADS)

    Kurilenko, K. A.; Shlyakhtin, O. A.; Petukhov, D. I.; Garshev, A. V.

    2017-06-01

    Composite electrode materials Li[Li0.13Ni0.2Mn0.47Co0.2]O2 (LNMC)-CeO2-C are obtained by the coprecipitation of Co, Ni, Mn and Ce hydroxides followed by the coating of LNMC-CeO2 composites with pyrolytic carbon. The introduction of 5% CeO2 promotes the reduction of LNMC grain size from 190-230 to 100-170 nm and the corresponding increase in the electrochemical capacity of LNMC-CeO2 composite. The pyrolytic coating consists of the network of 2-5 nm polymer-carbon particles at the surface of LNMC crystallites. The electrochemical impedance spectroscopy data, which was performed after the galvanostatic cycling, demonstrated considerably lower charge transfer resistance of the carbon-coated composites compared to the bare LNMC and the LNMC-CeO2 composites. The values of the discharge capacity of LNMC-CeO2-C composites are superior to the capacity of LMNC-CeO2 and LMNC-C composites at all discharge rates (C/10 - 5C). The increase of the upper boundary of potentials to 4.8 V after cycling at 5C (U - 2÷4.6 V) promotes the increase of low rate electrochemical capacity of LNMC-CeO2-C composite to 220 mAh g-1.

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

    NASA Astrophysics Data System (ADS)

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

    2013-11-01

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

  11. Interchange core/shell assembly of diluted magnetic semiconductor CeO2 and ferromagnetic ferrite Fe3O4 for microwave absorption

    NASA Astrophysics Data System (ADS)

    Wang, Jiaheng; Zhu, Pengfei; Wang, Jiaqi; Or, Siu Wing; Ho, S. L.; Tan, Jun

    2017-05-01

    Core/shell-structured CeO2/Fe3O4 and Fe3O4/CeO2 nanocapsules are prepared by interchange assembly of diluted magnetic semiconductor CeO2 and ferromagnetic ferrite Fe3O4 as the core and the shell, and vice versa, using a facile two-step polar solvothermal method in order to utilize the room-temperature ferromagnetism and abundant O-vacancies in CeO2, the large natural resonance in Fe3O4, and the O-vacancy-enhanced interfacial polarization between CeO2 and Fe3O4 for new generation microwave absorbers. Comparing to Fe3O4/CeO2 nanocapsules, the CeO2/Fe3O4 nanocapsules show an improved real permittivity of 3-10% and an enhanced dielectric resonance of 1.5 times at 15.3 GHz due to the increased O-vacancy concentration in the CeO2 cores of larger grains as well as the O-vacancy-induced enhancement in interfacial polarization between the CeO2 cores and the Fe3O4 shells, respectively. Both nanocapsules exhibit relatively high permeability in the low-frequency S and C microwave bands as a result of the bi-magnetic core/shell combination of CeO2 and Fe3O4. The CeO2/Fe3O4 nanocapsules effectively enhance permittivity and permeability in the high-frequency Ku band with interfacial polarization and natural resonance at ˜15 GHz, thereby improving absorption with a large reflection loss of -28.9 dB at 15.3 GHz. Experimental and theoretical comparisons with CeO2 and Fe3O4 nanoparticles are also made.

  12. 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.

  13. 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.

  14. 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).

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  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. 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

  3. 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.

  4. High-field magnetization and magnetic phase transition in CeOs2Al10

    NASA Astrophysics Data System (ADS)

    Kondo, Akihiro; Wang, Junfeng; Kindo, Koichi; Ogane, Yuta; Kawamura, Yukihiro; Tanimoto, Sakiyo; Nishioka, Takashi; Tanaka, Daiki; Tanida, Hiroshi; Sera, Masafumi

    2011-05-01

    We have studied the magnetization of CeOs2Al10 in high magnetic fields up to 55 T for H∥a and constructed the magnetic phase diagram for H∥a. The magnetization curve shows a concave H dependence below Tmax~40 K, which is higher than the transition temperature T0~29 K. The magnetic susceptibility along the a axis, χa, shows a smooth and continuous decrease down to ~20 K below Tmax~40 K without showing an anomaly at T0. From these two results, a Kondo singlet is formed below Tmax and coexists with the antiferromagnetic order below T0. We also propose that the larger suppression of the spin degrees of freedom along the a axis than along the c axis below Tmax is associated with the origin of the antiferromagnetic component.

  5. 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.

  6. Dilution effects on the antiferromagnetic Kondo semiconductor CeOs2Al10

    NASA Astrophysics Data System (ADS)

    Okada, Y.; Kawabata, J.; Yamada, Y.; Muro, Y.; Takabatake, T.

    2017-04-01

    We have studied the effects of dilution of Ce sublattice on the unusual antiferromagnetic (AFM) order in the Kondo semiconductor CeOs2Al10 at 28.5 K by the magnetic, transport and specific-heat measurements of single crystals of Ce1-zLazOs2Al10. The effective magnetic moment and paramagnetic Curie temperature hardly change with z up to 0.5, indicating that the 4f state remains unchanged at high temperatures. The suppression of the Néel temperature TN is much weaker than that in 5d hole doped system, Ce(Os1-yRey)2Al10. Therefore, the AFM interaction is robust against the violation of the coherent Ce sublattice. The activation energy in the resistivity decreases in parallel with TN, confirming the argument that the presence of the c-f hybridization gap is a requisite for the unusual AFM order in this system.

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

  8. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2011-12-01

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

  10. 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.

  11. Regulating the active species of Ni(OH)2 using CeO2: 3D CeO2/Ni(OH)2/carbon foam as an efficient electrode for the oxygen evolution reaction.

    PubMed

    Liu, Zhengqing; Li, Na; Zhao, Hongyang; Zhang, Yi; Huang, Yunhui; Yin, Zongyou; Du, Yaping

    2017-04-01

    Three dimensional (3D) N, O and S doped carbon foam (NOSCF) is prepared as a substrate for in situ vertically grown Ni(OH)2 nanosheets. As designed Ni(OH)2/NOSCF possesses strong electrostatic interactions with OH(-) ions due to many C 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 O groups existing in NOSCF, which can facilitate the formation of crucial NiOOH intermediates during the OER process. CeO2 nanoparticles (NPs) of ∼3.3 nm in size are decorated on Ni(OH)2 nanosheets to design a highly efficient CeO2/Ni(OH)2/NOSCF electrocatalyst for the oxygen evolution reaction (OER). The CeO2 NP decorated Ni(OH)2/NOSCF not only exhibits a remarkably improved OER performance with an onset potential of 240 mV, outperforming most reported non-noble metal based OER electrocatalysts, but also possesses a small Tafel slope of 57 mV dec(-1) and excellent stability under different overpotentials. The synergistic effect of producing more active species of Ni(III/IV) and accelerating the charge transfer for Ni(OH)2/NOSCF by the introduction of CeO2 NPs is also investigated. These results demonstrate the possibility of designing energy efficient OER catalysts with the assistance of earth abundant CeO2-based catalysts.

  12. 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.

  13. 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.

  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. Atomic and electronic structure of unreduced and reduced CeO2 surfaces: a first-principles study.

    PubMed

    Yang, Zongxian; Woo, Tom K; Baudin, Micael; Hermansson, Kersti

    2004-04-22

    The atomic and electronic structure of (111), (110), and (100) surfaces of ceria (CeO2) were studied using density-functional theory within the generalized gradient approximation. Both stoichiometric surfaces and surfaces with oxygen vacancies (unreduced and reduced surfaces, respectively) have been examined. It is found that the (111) surface is the most stable among the considered surfaces, followed by (110) and (100) surfaces, in agreement with experimental observations and previous theoretical results. Different features of relaxation are found for the three surfaces. While the (111) surface undergoes very small relaxation, considerably larger relaxations are found for the (110) and (100) surfaces. The formation of an oxygen vacancy is closely related to the surface structure and occurs more easily for the (110) surface than for (111). The preferred vacancy location is in the surface layer for CeO2(110) and in the subsurface layer (the second O-atomic layer) for CeO2(111). For both surfaces, the O vacancy forms more readily than in the bulk. An interesting oscillatory behavior is found for the vacancy formation energy in the upper three layers of CeO2(111). Analysis of the reduced surfaces suggests that the additional charge resulting from the formation of the oxygen vacancies is localized in the first three layers of the surface. Furthermore, they are not only trapped in the 4f states of cerium. (c) 2004 American Institute of Physics

  16. 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.

  17. 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.

  18. 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.

  19. 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

  20. 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...

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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...

  9. 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.

  10. 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.

  11. 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

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

    NASA Astrophysics Data System (ADS)

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

    2017-07-01

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

  13. 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.

  14. Unveiling the Role of CeO2 Atomic Layer Deposition Coatings on LiMn2O4 Cathode Materials: An Experimental and Theoretical Study.

    PubMed

    Sarkar, Susmita; Patel, Rajankumar L; Liang, Xinhua; Park, Jonghyun

    2017-09-13

    An atomic layer deposition (ALD) coating on active materials of a lithium ion battery is a more effective strategy for improving battery performance than other coating technologies. However, substantial uncertainty still remains about the underlying physics and role of the ALD coating in improving battery performance. Although improvement in the stability and capacity of CeO2 thin film coated particles for batteries has been reported, a detailed and accurate description of the mechanism has not been provided. We have developed a multiphysics-based model that takes into consideration stress mechanics, diffusion of lithium ion, and dissolution of transition-metal ions of spinel LiMn2O4 cathode. The model analyzes how different coating thicknesses affect diffusion-induced stress generation and, ultimately, crack propagation. Experimentally measured diffusivity and dissolution rates were incorporated into the model to account for a trade-off between delayed transport and prevention of side reactions. Along with experimental results, density functional theory results are used to explain how a change in volume, due to dissolution of active material, can affect battery performance. The predicted behavior from the model is well-matched with experimental results obtained on coated and uncoated LiMn2O4-Li foil cells. The proposed approach and explanations will serve as important guidelines for thin film coating strategies for various battery materials.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. Systematic study of the physical origin of ferromagnetism in CeO2 -δ nanoparticles

    NASA Astrophysics Data System (ADS)

    Ribeiro, A. N.; Ferreira, N. S.

    2017-04-01

    We have carried out a Schrieffer-Wolff transformation on a general tight-binding Hamiltonian and obtained a 4 f -one-band effective Hubbard Hamiltonian to study the physical origin of ferromagnetism in CeO2 -δ nanoparticle systems. For a low temperature regime and low concentrations of oxygen vacancies, isolated vacancies have previously been showed to form on the {100 } and {110 } surfaces and our studies indicate these will be in singlet and triplet states, respectively. This is sustained by a superexchange interaction between the 4 f electrons of the two cerium atoms, which are the nearest neighbors of the vacancy, and ferromagnetism and antiferromagnetism can coexist. Moreover, increasing the vacancy concentration we found that pairs of vacancies, which have been previously shown to form on the {111 } surfaces, produce Nagaoka ferromagnetism and isolated vacancies in the bulk produce an antiferromagnetic sign. Furthermore, further oxygen vacancy increases are previously known to favor the formation of oxygen vacancy clusters. In this case, our results showed a weakening of the magnetic correlations with respect to temperature. Thus, at a fixed temperature, the magnetic moment is reduced when the concentration of vacancies is increased, which is in agreement with experimental results reported in the literature. Interestingly, at a room-temperature regime, the antiferromagnetic order is destroyed and only the ferromagnetic couplings, produced mainly by isolated vacancies on the {110 } surfaces, survive. Finally, as temperature is increased further, the paramagnetic behavior of 4 f electrons dominates.

  1. 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.

  2. 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.

  3. Stability and Temperature-Induced Agglomeration of Rh Nanoparticles Supported by CeO2.

    PubMed

    Varga, Erika; Pusztai, Péter; Oszkó, Albert; Baán, Kornélia; Erdőhelyi, András; Kónya, Zoltán; Kiss, János

    2016-03-22

    The effects of reduction by H2 and by heat treatment in vacuum and in O2 flow on Rh particle size changes of Rh/CeO2 samples were studied by X-ray photoelectron spectroscopy (XPS), high-resolution electron microscopy (HRTEM), and CO adsorption followed by diffuse reflectance infrared spectroscopy (DRIFTS). Low-temperature (373-423 K) reduction of Rh without agglomeration is demonstrated. An average particle size of 2.3 ± 1.1 nm was measured by HRTEM regardless of the metal loading (1-5%). On Rh/CeO2, a significant particle size increase of the Rh particles was detected on heating (773 K). In this work, we suggest that the temperature-induced surface decrease resulting from the sintering of Rh is favored only for well-dispersed particles. XP spectra revealed that the mobile oxygens of CeO2 fundamentally determine the oxidation state of the supported metals. At elevated temperature, the oxidation of the reduced support surface as well as the metal component takes place because of the segregation of ceria oxygens. When the aggregated particles were reoxidized, the redispersion of Rh was observed probably because of the formation of Rh-O-Ce bonds.

  4. Structural modification and metamagnetic anomaly in the ordered state of CeOs2Al10

    NASA Astrophysics Data System (ADS)

    Muro, Yuji; Kajino, Jumpei; Umeo, Kazunori; Nishimoto, Kazue; Tamura, Ryuji; Takabatake, Toshiro

    2010-06-01

    A caged compound CeOs2Al10 , crystallizing in the orthorhombic YbFe2Al10 -type structure, undergoes a mysterious phase transition at T0=29K . We report the results of electron diffraction, magnetization, and magnetoresistance for single crystals. Superlattice reflections characterized by a wave vector q=(0,-2/3,2/3) observed at 15 K indicate a structural modification in the ordered state. Activation-type behavior of the electrical resistivity along the three principal axes below 50 K suggests gap opening in the conduction band. The magnetic susceptibility χ=M/B is highly anisotropic, χa>χc>χb , all of which sharply decrease on cooling below T0 . Furthermore, a metamagnetic anomaly in the magnetization and a step in the magnetoresistance occur at B=6-8T only when the magnetic field is applied parallel to the orthorhombic c axis. However, T0 hardly changes under magnetic fields up to 14 T, irrespective of the field direction. By using these data, we present a B-T phase diagram and discuss several scenarios for the mysterious transition.

  5. 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.

  6. Tuning surface grafting density of CeO2 nanocrystals with near- and supercritical solvent characteristics.

    PubMed

    Giroire, B; Slostowski, C; Marre, S; Aymonier, C; Aida, T; Hojo, D; Aoki, N; Takami, S; Adschiri, T

    2016-01-21

    In this work, the solvent effect on the synthesis of CeO2 nanocrystals synthesized in near- and supercritical alcohols is discussed. The materials prepared displayed a unique morphology of small nanocrystals (<10 nm) aggregated into larger nanospheres (∼100-200 nm). In such syntheses, alcohol molecules directly interact with the nanocrystal surface through alkoxide and carboxylate bondings. The grafting density was quantified from the weight loss measured using thermogravimetric analysis. A direct correlation between the grafting density and the alcohol chain length can be established. It was demonstrated that the shorter the alcohol chain length (i.e. methanol), the higher the surface coverage is. This trend is independent of the synthesis mode (batch or continuous). Additionally, an influence of the grafting density on the resulting nanocrystal size was established. It is suggested that the surface coverage has a high influence on the early stages of the nucleation and growth. Indeed, when high surface coverages are reached, all surface active sites are blocked, limiting the growth step and therefore leading to smaller particles. This effect was noticed with the materials prepared in the continuous mode where shorter reaction time was performed.

  7. 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.

  8. 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.

  9. 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.

  10. Photo-, sono-, and sonophotocatalytic activity of metal oxide nanocomposites TiO2/CeO2 for degradation of dye

    NASA Astrophysics Data System (ADS)

    Tju, H.; Muzakki, A. T.; Taufik, A.; Saleh, R.

    2017-07-01

    In present study, TiO2 nanoparticles was modified by the addition of CeO2 to increase efficiency and improve catalytic activity under visible light, ultrasonic irradiation, and combination of both irradiation. The as-prepared CeO2 nanoparticles have been incorporated to mixture of TiO2 with various molar ratio (x)TiO2:(1-x)CeO2 = 0.25:0.75 ; 0.5:0.5 and 0.75:0.25). Then the pristine TiO2, CeO2 and TiO2/CeO2 nanocomposites were identified by X-ray Diffraction (XRD) and the surface area was measured using Brunner-Emett teller (BET) measurement. The XRD results indicated that the CeO2 was a face centered cubic structure and the TiO2 was anatas structures. The as-prepared samples exhibit a good catalytic for the decolorization of methylene blue (MB) under visible light, ultrasonic irradiation, and combination of visible light and ultrasonic irradiation. The enhanced performance might be due to the lower recombination of charge carriers and surface properties of TiO2/CeO2. To further studies the catalytic mechanism the scavenger and initial solution experiment were also tested. Moreover, TiO2/CeO2 nanocomposites shows good cycle stability toward continuous four cycles runs of catalytic experiment for the degradation of MB.

  11. 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.

  12. 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.

  13. 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.

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

    PubMed

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

    2016-11-15

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

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

    PubMed Central

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

    2015-01-01

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

  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. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2017-04-01

    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.

  19. 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.

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

    PubMed Central

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

    2017-01-01

    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. PMID:28406231

  1. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

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

  3. 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.

  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. 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

  6. 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.

  7. High-temperature ferromagnetism in Co-doped CeO2 synthesized by the coprecipitation technique.

    PubMed

    Colis, S; Bouaine, A; Schmerber, G; Ulhaq-Bouillet, C; Dinia, A; Choua, S; Turek, P

    2012-05-28

    The aim of the present study is to check the influence of annealing under vacuum and a mixture of N(2)-H(2) atmosphere on the magnetic properties of polycrystalline Co-doped CeO(2) diluted magnetic oxides (DMOs) with Co concentrations of 5 at% synthesized using the coprecipitation technique. X-Ray diffraction (XRD) patterns and transmission electron microscopy (TEM) showed for all samples the expected CeO(2) cubic fluorite-type structure and that Co ions are uniformly distributed inside the samples. Room-temperature Raman and photoluminescence (PL) spectroscopies indicate an increase in the concentration of oxygen vacancies upon Co doping and further annealing. Field dependent magnetization measurements revealed a paramagnetic behavior for as-prepared Co-doped CeO(2), while a ferromagnetic behavior appears when the same samples are annealed under vacuum or N(2)-H(2) atmosphere. Temperature dependent magnetization measurements suggest that the observed ferromagnetism is due to the presence of metallic Co clusters with nanometric size and broad size distribution. These results are supported by electron paramagnetic resonance studies.

  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. 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.

  10. 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.

  11. 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.

  12. 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.

  13. A comparative interlaboratory study on photocatalytic activity of commercial ZnO and CeO2 nanoparticles

    NASA Astrophysics Data System (ADS)

    Yin, Hong; Tsuzuki, Takuya; Millington, Keith R.; Casey, Philip S.

    2014-10-01

    Photocatalytic activity (PCA) was one of a number of physicochemical end points identified by the Organisation for Economic Cooperation and Development (OECD) as relevant to environmental safety and human health as part of their Sponsorship Programme for the Testing of Manufactured Nanomaterial. Photoactive surfaces can produce reactive oxygen species including free radicals which have the potential to cause oxidative stress in tissue or even oxidative damage to DNA. Here we report a study that involved three laboratories in Australia that independently characterised the PCA of commercially available ZnO and CeO2 NPs provided by the OECD programme. This inter-laboratory comparison found that PCA is a stable characteristic of NPs which was insensitive to variations in interlaboratory protocols and with ZnO NPs being more photoactive (by an order of magnitude) than CeO2 NPs. Comparisons were made between NPs of different sizes and the effect of the presence or absence of a surface coating on PCA. Because the competition between surface and volume effects determined PCA, a critical particle size was found for CeO2 NPs to achieve maximum PCA. The presence of a surface coating appeared to significantly mitigate, but not eliminate PCA.

  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. Broadband near ultra violet sensitization of 1 μm luminescence in Yb3+-doped CeO2 crystal

    NASA Astrophysics Data System (ADS)

    Ueda, Jumpei; Tanabe, Setsuhisa

    2011-10-01

    Broadband spectral modification of near ultra violet (UV) light to infra-red (IR) light is investigated in Yb3+-doped CeO2 polycrystalline ceramics sintered in different atmospheres (air, oxygen, and 95%N2-5%H2). The intense Yb3+ photoluminescence (PL) peaked at 970 nm was observed by the UV excitation at around 390 nm in the samples except those sintered under N2-H2. A broad photoluminescence excitation (PLE) band of Yb3+ luminescence peaked at 390 nm corresponds to the absorption band and the photocurrent excitation band in the non-doped CeO2 crystal, which are also in accordance with the PLE band of Eu3+ luminescence in the Eu3+-doped CeO2. Judging from these results, the PLE band is attributed to the charge transfer (CT) band from O2- to Ce4+, but not to the CT from O2- to Yb3+. From the sintering atmosphere dependence of the PL and PLE, we found that the oxygen vacancies and Ce3+ impurities are not responsible for the 390 nm-absorption band but they work as a quenching center for the Yb3+ luminescence.

  16. 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.

  17. Sonocatalytic and sonophotocatalytic activity of ternary Fe3O4/CeO2/ZnO for waste water removal

    NASA Astrophysics Data System (ADS)

    Harno, F. F.; Taufik, A.; Saleh, R.

    2017-07-01

    In this study, CeO2 nanoparticles were modified by Fe3O4 and ZnO to enhance their sono- and sonophotocatalytic activity for degrading Methylene Blue dye pollutant. The molar ratio between Fe3O4, CeO2, and ZnO was 0.05:1:1, 0.1:1:1, 0.3:1:1, 0.5:1:1. The ternary Fe3O4/CeO2/ZnO nanocomposites with various molar ratios were fabricated by the sol-gel method. The structure of ternary Fe3O4/CeO2/ZnO nanocomposites was investigated by XRD Diffraction, while the surface area was investigated by Brunauer-Emmett-Teller (BET). The conditions such as the molar ratio, catalyst dosage, and scavengers were investigated to see the degradation of Methylene Blue under ultrasonic and combination of ultrasonic and ultraviolet irradiations, simultaneously.

  18. 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.

  19. Stress Response and Tolerance of Zea mays to CeO2 Nanoparticles: Cross Talk among H2O2, Heat Shock Protein and Lipid Peroxidation

    PubMed Central

    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.

    2014-01-01

    The rapid development of nanotechnology will inevitably release nanoparticles (NPs) into the environment with unidentified consequences. In addition, the potential toxicity of CeO2 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 CeO2 NPs at 400 or 800 mg/kg. Stress related parameters, such as: H2O2, catalase (CAT) and ascorbate peroxidase (APX) activity, heat shock protein 70 (HSP 70), 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 H2O2 distribution in corn leaves. Results showed that the CeO2 NP treatments increased accumulation of H2O2, 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 H2O2 levels. Both 400 and 800 mg/kg CeO2 NPs triggered the up regulation of the HSP 70 in roots, indicating a systemic stress response. None of the CeO2 NPs increased the level of thiobarbituric acid reacting substances, indicating that no lipid peroxidation occurred. CeO2 NPs, at both concentrations, did not induce ion leakage in either roots or shoots, suggesting membrane integrity was not compromised. Leaf net photosynthetic rate, transpiration, and stomatal conductance were not affected by CeO2 NPs. Our results suggest that the CAT, APX and HSP 70 might help the plants defend against CeO2 NPs induced oxidative injury and survive NP exposure. PMID:23050848

  20. 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.

  1. 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.

  2. 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.

  3. A facile growth process of CeO2-Co3O4 composite nanotubes and its catalytic stability for CO oxidation

    NASA Astrophysics Data System (ADS)

    Oh, Hyerim; Kim, Il Hee; Lee, Nam-Suk; Dok Kim, Young; Kim, Myung Hwa

    2017-08-01

    Hybrid cerium dioxide (CeO2)-cobalt oxide (Co3O4) composite nanotubes were successfully prepared by a combination of electrospinning and thermal annealing using CeO2 and Co3O4 precursors for the first time. Electrospun CeO2-Co3O4 composite nanotubes represent relatively porous surface texture with small dimensions between 80 and 150 nm in the outer diameter. The microscopic investigations indicate that the nanoparticle like crystalline structures of CeO2 and Co3O4 are homogenously distributed and continuously connected to form the shape of nanotube in the length of a few micrometers during thermal annealing. It is expected that the different evaporation behaviors of solvents and matrix polymer between the core and the shell in as-spun nanofibers in the course of thermal annealing could be reasonably responsible for the formation of well-defined CeO2/Co3O4 hybrid nanotubes. Additionally, the general catalytic activities of electrospun CeO2/Co3O4 hybrid nanotubes toward the oxidation of carbon monoxide (CO) were carefully examined by a continuous flow system, resulting in favorable catalytic activity as well as catalytic stability for CO oxidation between 150 °C and 200 °C without the deactivation of the catalyst with time stems from accumulation of reaction intermediates such as carbonate species.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. Incineration of a Commercial Coating with Nano CeO2

    NASA Astrophysics Data System (ADS)

    Le Bihan, Olivier; Ounoughene, Ghania; Meunier, Laurent; Debray, Bruno; Aguerre-Chariol, Olivier

    2017-06-01

    The potential environmental risk arising from the incineration of waste containing nanomaterials is a new field which deserves further attention. Some recent studies have begun to focus on this topic but the data are incomplete. In addition, there is a need to consider real life waste. The present study gives some insight into the fate and behavior of a commercial coating containing a commercial additive (7% w/w) based on nano-CeO2 (aggregates of 10 to 40 nm, with elemental particles of 2-3 nm). The tests have been conducted with a system developed in the frame of the NanoFlueGas project. The test protocol was designed to respect the regulatory criteria of a good combustion in incineration plants (temperature around 850°C, highly ventilated combustion, at least 2 s residence time for the combustion gas in a post-combustion chamber at 850°C, and high oxygen/fuel contact). Time tracking by electric low pressure impaction (ELPI) shows that the incineration produces aerosol with number concentration dominated by sub-100 nm particles. Cerium is observed by TEM and EDS analysis but as a minor compound of a sub-group of particles. No nanoCeO2 particles have been observed in the aerosol. ICP-MS analysis indicates that the residual material consists mainly of CeO2 (60% of the mass). Observation by TEM establishes that this material is in the form of aggregates with individual particle of 40-200 nm and suggests that sintering occurred during incineration. As a conclusion, the lab scale incineration study led mainly to the release of nano-CeO2 in the residual material, as the major component. Its size distribution is different than the one of the nano-CeO2 observed in the initial sample before incineration. Additional research is needed to improve the understanding of nanoCeO2 behavior, and to integrate experiments at lab and real scale.

  9. 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.)

  10. 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.

  11. 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.

  12. 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. Copyright © 2014 Elsevier Ltd. All rights reserved.

  13. 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.

  14. 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.

  15. 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

  16. 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.

  17. 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.

  18. Emission and Performance Analysis of ZrO2 And CeO2 Coated Piston Using Refined Vegetable Oils

    NASA Astrophysics Data System (ADS)

    Hemanandh, J.; Narayanan, K. V.; Manoj, Vemuri

    2017-05-01

    Increase in global warming and pollution leads to look for an alternative fuel. The aim of this paper to improve the performance and to reduce the emissions in DI diesel engine. The 80% of ZrO2 and 20% of CeO2 were mixed and coated on the piston head using plasma spray method. The B10 fuel of various refined vegetable oil methyl esters were used as fuel. The test was conducted in the 4-stroke DI diesel engine at a constant speed of 1500 rpm. The results show that the brake thermal efficiency, NOx and BSFC was increased. The CO and HC were decreased.

  19. Initial Reduction of CO2 on Pd-, Ru-, and Cu-Doped CeO2(111) Surfaces: Effects of Surface Modification on Catalytic Activity and Selectivity.

    PubMed

    Guo, Chen; Wei, Shuxian; Zhou, Sainan; Zhang, Tian; Wang, Zhaojie; Ng, Siu-Pang; Lu, Xiaoqing; Wu, Chi-Man Lawrence; Guo, Wenyue

    2017-08-09

    Surface modification by metal doping is an effective treatment technique for improving surface properties for CO2 reduction. Herein, the effects of doped Pd, Ru, and Cu on the adsorption, activation, and reduction selectivity of CO2 on CeO2(111) were investigated by periodic density functional theory. The doped metals distorted the configuration of a perfect CeO2(111) by weakening the adjacent Ce-O bond strength, and Pd doping was beneficial for generating a highly active O vacancy. The analyses of adsorption energy, charge density difference, and density of states confirmed that the doped metals were conducive for enhancing CO2 adsorption, especially for Cu/CeO2(111). The initial reductive dissociation CO2 → CO* + O* on metal-doped CeO2(111) followed the sequence of Cu- > perfect > Pd- > Ru-doped CeO2(111); the reductive hydrogenation CO2 + H → COOH* followed the sequence of Cu- > perfect > Ru- > Pd-doped CeO2(111), in which the most competitive route on Cu/CeO2(111) was exothermic by 0.52 eV with an energy barrier of 0.16 eV; the reductive hydrogenation CO2 + H → HCOO* followed the sequence of Ru- > perfect > Pd-doped CeO2(111). Energy barrier decomposition analyses were performed to identify the governing factors of bond activation and scission along the initial CO2 reduction routes. Results of this study provided deep insights into the effect of surface modification on the initial reduction mechanisms of CO2 on metal-doped CeO2(111) surfaces.

  20. 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

  1. 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.

  2. 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.

  3. 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.

  4. 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. Copyright © 2013 Elsevier B.V. All rights reserved.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. [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.

  12. 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.

  13. 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.

  14. 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.

  15. High pressure behavior of nano-crystalline CeO2 up to 35 GPa: a Raman investigation

    NASA Astrophysics Data System (ADS)

    Dogra, Sugandha; Dilawar Sharma, Nita; Singh, Jasveer; Poswal, Himanshu Kumar; Sharma, S. M.; Bandyopadhyay, A. K.

    2011-06-01

    The present paper reports the results of in situ Raman studies carried out on nano-crystalline CeO2 up to a pressure of 35 GPa at room temperature. The material was characterized at ambient conditions using X-ray diffraction and Raman spectroscopy and was found to have a cubic structure. We observed the Raman peak at ambient at 465 cm-1, which is characteristic of the cubic structure of the material. The sample was pressurized using a diamond anvil cell using ruby fluorescence as the pressure monitor, and the phase evolution was tracked by Raman spectroscopy. With an increase in the applied pressure, the cubic band was seen to steadily shift to higher wavenumbers. However, we observed the appearance of a number of new peaks around a pressure of about 34.7 GPa. CeO2 was found to undergo a phase transition to an orthorhombic α -PbCl2-type structure at this pressure. With the release of the applied pressure, the observed peaks steadily shift to lower wavenumbers. On decompression, the high pressure phase existed down to a total release of pressure.

  16. 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.

  17. 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.

  18. 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.

  19. A Simple Descriptor to Rapidly Screen CO Oxidation Activity on Rare-Earth Metal-Doped CeO2: From Experiment to First-Principles.

    PubMed

    Kim, Kyeounghak; Yoo, Jeong Do; Lee, Siwon; Bae, Minseok; Bae, Joongmyeon; Jung, WooChul; Han, Jeong Woo

    2017-05-10

    Ceria (CeO2) is an attractive catalyst because of its unique properties, such as facile redoxability and high stability. Thus, many researchers have examined a wide range of catalytic reactions on ceria nanoparticles (NPs). Among those contributions are the reports of the dopant-dependent catalytic activity of ceria. On the other hand, there have been few mechanistic studies of the effects of a range of dopants on the chemical reactivity of ceria NPs. In this study, we examined the catalytic activities of pure and Pr, Nd, and Sm-doped CeO2 (PDC, NDC, and SDC, respectively) NPs on carbon monoxide (CO) oxidation. Density functional theory (DFT) calculations were also performed to elucidate the reaction mechanism on rare-earth (RE)-doped CeO2(111). The experimental results showed that the catalytic activities of CO oxidation were in the order of CeO2 > PDC > NDC > SDC. This is consistent with the DFT results, where the reaction is explained by the Mars-van Krevelen mechanism. On the basis of the theoretical interpretation of the experimental results, the ionic radius of the RE dopant can be used as a simple descriptor to predict the energy barrier at the rate-determining step, thereby predicting the entire reaction activity. Using the descriptor, a wide range of RE dopants on CeO2(111) were screened for CO oxidation. These results provide useful insights to unravel the CO oxidation activity on various oxide catalysts.

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

    PubMed Central

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

    2014-01-01

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

  1. 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.

  2. 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.

  3. 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+). Copyright © 2016. Published by Elsevier Inc.

  4. 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.

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

    PubMed

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

    2016-03-01

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

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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

    A systematic study by reversible and hysteretic electrochemical strain microscopy (ESM) in samples of Cerium oxide with different Sm content and in several working conditions allows disclosing the microscopic mechanism underlying the difference in electrical conduction mechanism and related surface activity, such as water adsorption and dissociation with subsequent proton liberation. We measure the behavior of the reversible hysteresis loops by changing temperature and humidity, both in standard ESM configuration and using the first order reversal curve method. The measurements have been performed at much lower temperature ranges with respect to alternative measuring techniques. Complementing our study with hard x-ray photoemission spectroscopy and irreversible scanning probe measurements 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 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 electrical conductivity. The defect concentrations determine the type of the prevalent charge carrier in a doping dependent manner.

  11. 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.

  12. 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.

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

    PubMed

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

    2011-09-15

    Increasing use of nanomaterials necessitates an improved understanding of their potential impact on environment health. This study evaluated the cytotoxicity of nanosized HfO(2), SiO(2), Al(2)O(3) and CeO(2) towards the eukaryotic model organism Saccharomyces cerevisiae, and characterized their state of dispersion in bioassay medium. Nanotoxicity was assessed by monitoring oxygen consumption in batch cultures and by analysis of cell membrane integrity. CeO(2), Al(2)O(3), and HfO(2) nanoparticles were highly unstable in yeast medium and formed micron-sized, settleable agglomerates. A non-toxic polyacrylate dispersant (Dispex A40) was used to improve nanoparticle stability and determine the impact of enhanced dispersion on toxicity. None of the NPs tested without dispersant inhibited O(2) uptake by yeast at concentrations as high as 1000 mg/L. Dispersant supplementation only enhanced the toxicity of CeO(2) (47% at 1000 mg/L). Dispersed SiO(2) and Al(2)O(3) (1000 mg/L) caused cell membrane damage, whereas dispersed HfO(2) and CeO(2) did not cause significant disruption of membrane integrity at the same concentration. These results suggest that the O(2) uptake inhibition observed with dispersed CeO(2) NPs was not due to reduced cell viability. This is the first study evaluating toxicity of nanoscale HfO(2), SiO(2), Al(2)O(3) and CeO(2) to S. cerevisiae. Overall the results obtained demonstrate that these nanomaterials display low or no toxicity to yeast. Copyright © 2011 Elsevier B.V. All rights reserved.

  14. Construction of g-C3N4/CeO2/ZnO ternary photocatalysts with enhanced photocatalytic performance

    NASA Astrophysics Data System (ADS)

    Yuan, Yuan; Huang, Gui-Fang; Hu, Wang-Yu; Xiong, Dan-Ni; Zhou, Bing-Xin; Chang, Shengli; Huang, Wei-Qing

    2017-07-01

    Promoting the spatial separation of photoexcited charge carriers is of paramount significance for photocatalysis. In this work, binary g-C3N4/CeO2 nanosheets are first prepared by pyrolysis and subsequent exfoliation method, then decorated with ZnO nanoparticles to construct g-C3N4/CeO2/ZnO ternary nanocomposites with multi-heterointerfaces. Notably, the type-II staggered band alignments existing between any two of the constituents, as well as the efficient three-level transfer of electron-holes in unique g-C3N4/CeO2/ZnO ternary composites, leads to the robust separation of photoexcited charge carriers, as verified by its photocurrent increased by 8 times under visible light irradiation. The resulting g-C3N4/CeO2/ZnO ternary nanocomposites unveil appreciably increased photocatalytic activity, faster than that of pure g-C3N4, ZnO and g-C3N4/CeO2 by a factor of 11, 4.6 and 3.7, respectively, and good stability toward methylene blue (MB) degradation. The remarkably enhanced photocatalytic activity of g-C3N4/CeO2/ZnO ternary heterostructures can be interpreted in terms of lots of active sites of nanosheet shapes and the efficient charge separation owing to the resulting type-II band alignment with more than one heterointerface and the efficient three-level electron-hole transfer. A plausible mechanism is also elucidated via active species trapping experiments with various scavengers, which indicating that the photogenerated holes and •OH radicals play a crucial role in photodegradation reaction under visible light irradiation. This work suggest that the rational design and construction of type II multi-heterostructures is powerful for developing highly efficient and reusable visible-light photocatalysts for environmental purification and energy conversion.

  15. 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).

  16. 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.

  17. 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.

  18. Communication: different behavior of Young's modulus and fracture strength of CeO2: density functional theory calculations.

    PubMed

    Sakanoi, Ryota; Shimazaki, Tomomi; Xu, Jingxiang; Higuchi, Yuji; Ozawa, Nobuki; Sato, Kazuhisa; Hashida, Toshiyuki; Kubo, Momoji

    2014-03-28

    In this Communication, we use density functional theory (DFT) to examine the fracture properties of ceria (CeO2), which is a promising electrolyte material for lowering the working temperature of solid oxide fuel cells. We estimate the stress-strain curve by fitting the energy density calculated by DFT. The calculated Young's modulus of 221.8 GPa is of the same order as the experimental value, whereas the fracture strength of 22.7 GPa is two orders of magnitude larger than the experimental value. Next, we combine DFT and Griffith theory to estimate the fracture strength as a function of a crack length. This method produces an estimated fracture strength of 0.467 GPa, which is of the same order as the experimental value. Therefore, the fracture strength is very sensitive to the crack length, whereas the Young's modulus is not.

  19. 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.

  20. 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

  1. Atomic resolution study of the interfacial bonding at Si3N4/CeO2-δ grain boundaries

    NASA Astrophysics Data System (ADS)

    Walkosz, W.; Klie, R. F.; Öǧüt, S.; Borisevich, A.; Becher, P. F.; Pennycook, S. J.; Idrobo, J. C.

    2008-08-01

    Using a combination of atomic-resolution Z-contrast imaging and electron energy-loss spectroscopy (EELS) in the scanning transmission electron microscope, we examine the atomic and electronic structures at the interface between Si3N4 (101¯0) and CeO2-d intergranular film (IGF). Ce atoms are observed to segregate to the interface in a two-layer periodic arrangement, which is significantly different from the structure observed in a previous study. Our EELS experiments show (i) oxygen in direct contact with the terminating Si3N4 open-ring structures, (ii) a change in the Ce valence from a nominal oxidation state of +3 to almost +4 moving from the interface into the IGF, and (iii) a uniform concentration of Si in the film.

  2. Kinetic Monte Carlo simulations of fluorine and vacancies concentration at the CeO2(111) surface

    NASA Astrophysics Data System (ADS)

    Mattiello, S.; Kolling, S.; Heiliger, C.

    2017-09-01

    Recently, a new identification of the experimental depressions of scanning tunnelling microscopy images on the {{CeO}}2(111) surface as fluorine impurities has been proposed in Kullgren et al (2014 Phys. Rev. Lett. 112 156102). In particular, the high immobility of the depressions seems to be in contradiction with the low diffusion barrier for the oxygen vacancies. Consequently, the oxygen vacancies concentration has to disappear. The first aim of this paper is to confirm dynamically the recent interpretation of the experimental finding. For this purpose, we investigate the competition between fluorine and oxygen vacancies using two dimensional kinetic Monte Carlo simulations (kMC) as compared to an appropriate Langmuir model. We calculate the concentration of the vacancies and of the fluorine for the surface (111) of {{CeO}}2 for a UHV condition as a function of the fluorine-oxygen mixture in the gas phase as well as of the binding energies of fluorine and oxygen. We found that at a temperature of T=573 {{K}}, at which the experimental measurements were conducted, vacancies cannot exist. This confirms the possibility of fluorine impurities in Kullgren et al (2014 Phys. Rev. Lett. 112 156102). The second aim of the present paper is to perform a first dynamical estimation of the fluorine binding energy value {E}{Fl} that allows one to describe the experimental data in Pieper et al (2012 Phys. Chem. Chem. Phys. 14 15361). Using 2D-kMC simulations, we found {E}{Fl}\\in [-5.53,-5.27] {eV} which can be used for comparison to density functional theory calculations in further works.

  3. 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

  4. 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.

  5. Efficient degradation of chlorobenzene in a non-thermal plasma catalytic reactor supported on CeO2/HZSM-5 catalysts.

    PubMed

    Jiang, Liying; Nie, Guofeng; Zhu, Runye; Wang, Jiade; Chen, Jianmeng; Mao, Yubo; Cheng, Zhuowei; Anderson, Willam A

    2017-05-01

    Chlorobenzene removal was investigated in a non-thermal plasma reactor using CeO2/HZSM-5 catalysts. The performance of catalysts was evaluated in terms of removal and energy efficiency. The decomposition products of chlorobenzene were analyzed. The results show that CeO2/HZSM-5 exhibited a good catalytic activity, which resulted in enhancements of chlorobenzene removal, energy efficiency, and the formation of lower amounts of by-products. With regards to CO2 selectivity, the presence of catalysts favors the oxidation of by-products, leading to a higher CO2 selectivity. With respect to ozone, which is considered as an unavoidable by-product in air plasma reactors, a noticeable decrease in its concentration was observed in the presence of catalysts. Furthermore, the stability of the catalyst was investigated by analyzing the evolution of conversion in time. The experiment results indicated that CeO2/HZSM-5 catalysts have excellent stability: chlorobenzene conversion only decreased from 78% to 60% after 75hr, which means that the CeO2/HZSM-5 suffered a slight deactivation. Some organic compounds and chlorinated intermediates were adsorbed or deposited on the catalysts surface as shown by the results of Fourier Transform Infrared (FT-IR) spectroscopy, scanning electron microscope (SEM) and energy dispersive X-ray spectroscopy (EDS) analyses of the catalyst before and after the reaction, revealing the cause of catalyst deactivation. Copyright © 2016. Published by Elsevier B.V.

  6. 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...

  7. 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.

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

    PubMed

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

    2015-01-01

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

  9. 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.

  10. 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.

  11. 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.

  12. 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 ...

  13. 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 ...

  14. 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...

  15. Strongly coupled CeO2/Co3O4/poly(3,4-ethylenedioxythiophene) nanofibers with enhanced nanozyme activity for highly sensitive colorimetric detection

    NASA Astrophysics Data System (ADS)

    Chi, Maoqiang; Zhu, Yun; Yang, Zezhou; Gao, Mu; Chen, Sihui; Song, Na; Wang, Ce; Lu, Xiaofeng

    2017-07-01

    In this work, we have prepared CeO2/Co3O4 composite nanofibers via an electrospinning technique followed by a calcination process. Then core-shell structured CeO2/Co3O4/poly(3,4-ethylenedioxythiophene) (PEDOT) composite nanofibers were fabricated through a redox reaction between the 3,4-ethylenedioxythiophene (EDOT) monomer and Co3O4 on the surface of CeO2/Co3O4 composite nanofibers. The morphology and composition of the two composite nanofibers were confirmed by field-emission scanning electron microscopy, transmission electron microscopy, x-ray diffraction, Fourier transform infrared spectroscopy, and x-ray photoelectron spectra measurements. Due to the synergistic effect between CeO2 and Co3O4, the catalytic activity was enhanced compared to that of independent oxide nanofibers. After the growth of PEDOT, the catalytic activity process was further improved, having achieved a secondary synergistic effect. Application of the two prepared composite nanofibers as peroxidase-like catalysts for the colorimetric detection of H2O2 was investigated. It is anticipated that this work can inspire researchers to develop various novel functional nanocomposites for applications in biosensing and environmental monitoring.

  16. [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.

  17. 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.

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

    PubMed

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

    2015-03-01

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

  19. 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.

  20. 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.

  1. [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.

  2. 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.

  3. 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.

  4. 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.

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

    PubMed

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

    2017-08-01

    Nanomaterials of CeO2 with A. vera were synthesized by using simple chemical method. Grapes drops are used as an oxidizing agent. Structural and morphological studies of nanomaterials of cerium oxide (CeO2), were studied for combustion method of preparation. The precursor solution was initialized by a hydrothermal reaction. Cerium hydroxyl carbonate precursors which involves cerium (III) nitrate Ce(NO3)3. 6 H2O with (1.0M) of seashell powder, 3% A. vera, extracts, grapes and pomegranate drops and this complex solution was used to produce the CeO2 powder particles. We have prepared another sample with 5% of Aloe vera extract and found that 3% Aloe vera extract has lesser grain size and enhanced band gap values, so the article explained the sample analysis of combination with 3% extract of Aloe vera. The product has the rod pattern which was the unusual features appear to originate from the unique crystal chemistry aspects. From the optical absorption spectrum, it has been shown that the CeO2 rods have 3.847eV of direct band gap energy. The minimum inhibitory concentration (MIC) values of the synthesized compounds exhibited activity towards various microbial pathogens such as B. subtilis (15μg/mL), S. aureus (50μg/mL), S. epidermidis (20μg/mL), E. faecalis (25μg/mL) and towards E. coli (100μg/mL), K. pneumoniae (50μg/mL) and P. aeruginosa (75μg/mL) respectively. The tests on bacterial activities confirmed that the CeO2 rods are suitable hand for the biological applications. The seashell structure and the phytochemical contents of A. vera might enhance its bacterial activities. Copyright © 2017 Elsevier B.V. All rights reserved.

  6. 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.

  7. Robust Strategy for Crafting Li5Cr7Ti6O25@CeO2 Composites as High-Performance Anode Material for Lithium-Ion Battery.

    PubMed

    Mei, Jie; Yi, Ting-Feng; Li, Xin-Yuan; Zhu, Yan-Rong; Xie, Ying; Zhang, Chao-Feng

    2017-07-19

    A facile strategy was developed to prepare Li5Cr7Ti6O25@CeO2 composites as a high-performance anode material. X-ray diffraction (XRD) and Rietveld refinement results show that the CeO2 coating does not alter the structure of Li5Cr7Ti6O25 but increases the lattice parameter. Scanning electron microscopy (SEM) indicates that all samples have similar morphologies with a homogeneous particle distribution in the range of 100-500 nm. Energy-dispersive spectroscopy (EDS) mapping and high-resolution transmission electron microscopy (HRTEM) prove that CeO2 layer successfully formed a coating layer on a surface of Li5Cr7Ti6O25 particles and supplied a good conductive connection between the Li5Cr7Ti6O25 particles. The electrochemical characterization reveals that Li5Cr7Ti6O25@CeO2 (3 wt %) electrode shows the highest reversibility of the insertion and deinsertion behavior of Li ion, the smallest electrochemical polarization, the best lithium-ion mobility among all electrodes, and a better electrochemical activity than the pristine one. Therefore, Li5Cr7Ti6O25@CeO2 (3 wt %) electrode indicates the highest delithiation and lithiation capacities at each rate. At 5 C charge-discharge rate, the pristine Li5Cr7Ti6O25 only delivers an initial delithiation capacity of ∼94.7 mAh g(-1), and the delithiation capacity merely achieves 87.4 mAh g(-1) even after 100 cycles. However, Li5Cr7Ti6O25@CeO2 (3 wt %) delivers an initial delithiation capacity of 107.5 mAh·g(-1), and the delithiation capacity also reaches 100.5 mAh g(-1) even after 100 cycles. The cerium dioxide modification is a direct and efficient approach to improve the delithiation and lithiation capacities and cycle property of Li5Cr7Ti6O25 at large current densities.

  8. Role of CeO2 promoter in NiO/α-Al2O3 catalyst for dry reforming of methane

    NASA Astrophysics Data System (ADS)

    Loc, Luu Cam; Phuong, Phan Hong; Tri, Nguyen

    2017-09-01

    A series of Ni/α-Al2O3 (NiAl) catalysts promoted by CeO2 was prepared by co-impregnation methods with content of (NiO+CeO2) being in the range of 10-30 wt%. The NiO:CeO2 weight ratio was fluctuated at 1:1, 1:2 and 1:3. Several techniques, including X-ray powder diffraction (XRD), Hydrogen temperature-programmed reduction (H2-TPR), and transmission electron microscopy (TEM) were used to investigate catalysts' physico-chemical properties. The activity of these catalysts in dry reforming of CH4 was investigated at temperature range of 550-800 °C. The results revealed that the most suitable CeO2 promoted Ni catalyst contained 20 wt% of (NiO+CeO2) and NiO:CeO2 weight ratio of 1:2. The best catalytic performance of catalyst [20(1Ni2Ce)Al] due to a better reducibility resulted in a higher amount of free small particle NiO. At 700 °C and CH4:CO2 molar ratio of 1:1, the conversion of CH4 and CO2 on the most suitable CeO2 promoted Ni catalyst reached 86% and 67%, respectively; H2 and CO selectivity of 90% and H2:CO molar ratio of 1.15 were obtained. Being similar to MgO [1], promoter CeO2 could improve catalytic activity of Ni/α-Al2O3 catalyst at a lower range of temperature. Besides, both MgO and CeO2 had a great impact on improving coke resistance of Ni catalysts. At higher temperature, the role of CeO2 as well as MgO in preventing coke formation on catalyst was clarified by temperature-programmed oxidation (TPO) technique. Coke amount formed after 30-h TOS on 20(1Ni2Ce) catalyst was found to be 22.18 mgC/gcat, being less than on non-promoted catalyst (36.75 mgC/gcat), but more than on 20(1Ni2Mg)Al one (5.25 mgC/gcat).

  9. Electrochemical reduction of CerMet fuels for transmutation using surrogate CeO2-Mo pellets

    NASA Astrophysics Data System (ADS)

    Claux, B.; Souček, P.; Malmbeck, R.; Rodrigues, A.; Glatz, J.-P.

    2017-08-01

    One of the concepts chosen for the transmutation of minor actinides in Accelerator Driven Systems or fast reactors proposes the use of fuels and targets containing minor actinides oxides embedded in an inert matrix either composed of molybdenum metal (CerMet fuel) or of ceramic magnesium oxide (CerCer fuel). Since the sufficient transmutation cannot be achieved in a single step, it requires multi-recycling of the fuel including recovery of the not transmuted minor actinides. In the present work, a pyrochemical process for treatment of Mo metal inert matrix based CerMet fuels is studied, particularly the electroreduction in molten chloride salt as a head-end step required prior the main separation process. At the initial stage, different inactive pellets simulating the fuel containing CeO2 as minor actinide surrogates were examined. The main studied parameters of the process efficiency were the porosity and composition of the pellets and the process parameters as current density and passed charge. The results indicated the feasibility of the process, gave insight into its limiting parameters and defined the parameters for the future experiment on minor actinide containing material.

  10. Equilibrium oxygen storage capacity of ultrathin CeO2-δ depends non-monotonically on large biaxial strain

    DOE PAGES

    Gopal, Chirranjeevi Balaji; Garcia-Melchor, Max; Lee, Sang Chul; ...

    2017-05-18

    Elastic strain is being increasingly employed to enhance the catalytic properties of mixed ion–electron conducting oxides. However, its effect on oxygen storage capacity is not well established. Here, we fabricate ultrathin, coherently strained films of CeO2-δ between 5.6% biaxial compression and 2.1% tension. In situ ambient pressure X-ray photoelectron spectroscopy reveals up to a fourfold enhancement in equilibrium oxygen storage capacity under both compression and tension. This non-monotonic variation with strain departs from the conventional wisdom based on a chemical expansion dominated behaviour. Through depth profiling, film thickness variations and a coupled photoemission–thermodynamic analysis of space-charge effects, we show thatmore » the enhanced reducibility is not dominated by interfacial effects. On the basis of ab initio calculations of oxygen vacancy formation incorporating defect interactions and vibrational contributions, we suggest that the non-monotonicity arises from the tetragonal distortion under large biaxial strain. Finally, these results may guide the rational engineering of multilayer and core–shell oxide nanomaterials.« less

  11. ROS mediated malignancy cure performance of morphological, optical, and electrically tuned Sn doped CeO2 nanostructures

    NASA Astrophysics Data System (ADS)

    Abbas, Fazal; Iqbal, Javed; Maqbool, Qaisar; Jan, Tariq; Ullah, Muhammad Obaid; Nawaz, Bushra; Nazar, Mudassar; Naqvi, M. S. Hussain; Ahmad, Ishaq

    2017-09-01

    To grapple with cancer, implementation of differentially cytotoxic nanomedicines have gained prime attention of the researchers across the globe. Now, ceria (CeO2) at nanoscale has emerged as a cut out therapeutic agent for malignancy treatment. Keeping this in view, we have fabricated SnxCe1-xO2 nanostructures by facile, eco-friendly, and biocompatible hydrothermal method. Structural examinations via XRD and FT-IR spectroscopy have revealed single phase cubic-fluorite morphology while SEM analysis has depicted particle size ranging 30-50nm for pristine and doped nanostructures. UV-Vis spectroscopy investigation explored that Sn doping significantly tuned the band gap (eV) energies of SnxCe1-xO2 nanostructures which set up the base for tremendous cellular reactive oxygen species (ROS) generations involved in cancer cells' death. To observe cytotoxicity, synthesized nanostructures were found selectively more toxic to neuroblastoma cell lines as compared to HEK-293 healthy cells. This study anticipates that SnxCe1-xO2 nanostructures, in future, might be used as nanomedicine for safer cancer therapy.

  12. 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.

  13. Equilibrium oxygen storage capacity of ultrathin CeO2-δ depends non-monotonically on large biaxial strain

    NASA Astrophysics Data System (ADS)

    Balaji Gopal, Chirranjeevi; García-Melchor, Max; Lee, Sang Chul; Shi, Yezhou; Shavorskiy, Andrey; Monti, Matteo; Guan, Zixuan; Sinclair, Robert; Bluhm, Hendrik; Vojvodic, Aleksandra; Chueh, William C.

    2017-05-01

    Elastic strain is being increasingly employed to enhance the catalytic properties of mixed ion-electron conducting oxides. However, its effect on oxygen storage capacity is not well established. Here, we fabricate ultrathin, coherently strained films of CeO2-δ between 5.6% biaxial compression and 2.1% tension. In situ ambient pressure X-ray photoelectron spectroscopy reveals up to a fourfold enhancement in equilibrium oxygen storage capacity under both compression and tension. This non-monotonic variation with strain departs from the conventional wisdom based on a chemical expansion dominated behaviour. Through depth profiling, film thickness variations and a coupled photoemission-thermodynamic analysis of space-charge effects, we show that the enhanced reducibility is not dominated by interfacial effects. On the basis of ab initio calculations of oxygen vacancy formation incorporating defect interactions and vibrational contributions, we suggest that the non-monotonicity arises from the tetragonal distortion under large biaxial strain. These results may guide the rational engineering of multilayer and core-shell oxide nanomaterials.

  14. Synthesis of monodisperse CeO2-ZrO2 particles exhibiting cyclic superelasticity over hundreds of cycles

    DOE PAGES

    Du, Zehui; Ye, Pengcheng; Zeng, Xiao Mei; ...

    2017-05-09

    Nano- and microscale CeO2–ZrO2 (CZ) shape memory ceramics are promising materials for smart micro-electro-mechanical systems (MEMS), sensing, actuation and energy damping applications, but the processing science for scalable production of such small volume ceramics has not yet been established. Herein, we report a modified sol-gel method to synthesize highly monodisperse spherical CZ particles with diameters in the range of ~0.8-3.0 μm. Synchrotron X-ray micro-diffraction (μSXRD) confirmed that most of the particles are single crystal after annealing at 1450°C. Having a monocrystalline structure and a small specimen length scale, the particles exhibit significantly enhanced shape memory and superelasticity properties with upmore » to ~4.7% compression being completely recoverable. Highly reproducible superelasticity through over five hundred strain cycles, with dissipated energy up to ~40 MJ/m3 per cycle, is achieved in the CZ particles containing 16 mol% ceria. This cycling capability is enhanced by ten times compared with our first demonstration using micropillars (only 50 cycles in Lai et al, Science, 2013, 341, 1505). Furthermore, the effects of cycling and testing temperature (in 25°C-400°C) on superelasticity have been investigated.« less

  15. Atomic Resolution Study of the Interfacial Bonding at Si3N4/CeO2-δ Grain Boundaries

    NASA Astrophysics Data System (ADS)

    Klie, Robert F.; Walkosz, Weronika; Ogut, Serdar; Borisevich, A.; Becher, Paul F.; Pennycook, Steve J.; Idrobo, Juan C.

    2008-03-01

    Using a combination of atomic resolution Z-contrast imaging and electron energy-loss spectroscopy (EELS) in the scanning transmission electron microscope, we examine the atomic and electronic structures at the interface between Si3N4 (10 10) and CeO2-δ inter-granular film (IGF). Ce atoms are observed to segregate to the interface in a two-layer periodic arrangement, which is significantly different compared to the structure observed in a previous study. Our EELS experiments show that (i) oxygen is present at the interface in direct contact with the terminating Si3N4 open-ring structures, (ii) the Ce valence state changes from +3 to +4 in going from the interface into the IGF, and (iii) while the N concentration decreases away from the Si3N4 grains into the IGF, the Si concentration remains uniform across the whole width of the IGF. Possible reasons for these observed structural and electronic variations at the interface and their implications for future studies on Si3N4/rare-earth oxide interfaces are briefly discussed.

  16. Equilibrium oxygen storage capacity of ultrathin CeO2-δ depends non-monotonically on large biaxial strain

    PubMed Central

    Balaji Gopal, Chirranjeevi; García-Melchor, Max; Lee, Sang Chul; Shi, Yezhou; Shavorskiy, Andrey; Monti, Matteo; Guan, Zixuan; Sinclair, Robert; Bluhm, Hendrik; Vojvodic, Aleksandra; Chueh, William C.

    2017-01-01

    Elastic strain is being increasingly employed to enhance the catalytic properties of mixed ion–electron conducting oxides. However, its effect on oxygen storage capacity is not well established. Here, we fabricate ultrathin, coherently strained films of CeO2-δ between 5.6% biaxial compression and 2.1% tension. In situ ambient pressure X-ray photoelectron spectroscopy reveals up to a fourfold enhancement in equilibrium oxygen storage capacity under both compression and tension. This non-monotonic variation with strain departs from the conventional wisdom based on a chemical expansion dominated behaviour. Through depth profiling, film thickness variations and a coupled photoemission–thermodynamic analysis of space-charge effects, we show that the enhanced reducibility is not dominated by interfacial effects. On the basis of ab initio calculations of oxygen vacancy formation incorporating defect interactions and vibrational contributions, we suggest that the non-monotonicity arises from the tetragonal distortion under large biaxial strain. These results may guide the rational engineering of multilayer and core–shell oxide nanomaterials. PMID:28516915

  17. Effects of Sm doping content on the ionic conduction of CeO2 in SOFCs from first principles

    NASA Astrophysics Data System (ADS)

    Fu, Zhaoming; Sun, Qian; Ma, Dongwei; Zhang, Na; An, Yipeng; Yang, Zongxian

    2017-07-01

    Sm-doping effects on ionic conduction of the CeO2 electrolyte in solid oxide fuel cells (SOFCs) are investigated using the first-principles calculations. We focus on the influence of the Sm content on ionic conductivity in Sm-doped ceria (SDC). In previous studies, the Sm-doping effects are attributed to the increase in the oxygen vacancies induced by Sm3+. However, our investigations reveal that Sm doping contents play multiple roles in affecting the ionic conductivity. First, the activity of oxygen migration can be controlled by the Sm concentration. Second, the association energy between the dopant and oxygen vacancies, which is very important for O conductivity in SDC, can also be tuned by changing the dopant content. In addition, oxygen-rich and oxygen-poor conditions will significantly modify the band structures of SDC. Our work is helpful to understand the mechanism of high ionic conductivity in the electrolyte of Sm-doped ceria in SOFCs.

  18. 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.

  19. 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.

  20. 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

  1. 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

  2. Inverse CeO2/CuO catalyst as an alternative to classical direct configurations for preferential oxidation of CO in hydrogen-rich stream.

    PubMed

    Hornés, A; Hungría, A B; Bera, P; López Cámara, A; Fernández-García, M; Martínez-Arias, A; Barrio, L; Estrella, M; Zhou, G; Fonseca, J J; Hanson, J C; Rodriguez, J A

    2010-01-13

    A novel inverse CeO(2)/CuO catalyst for preferential oxidation of CO in H(2)-rich stream (CO-PROX) has been developed on the basis of a hypothesis extracted from previous work of the group (JACS 2007, 129, 12064). Possible separation of the two competing oxidation reactions involved in the process (of CO and H(2), respectively) is the key to modulation of overall CO-PROX activity and is based on involvement of different sites as most active ones for each of the two reactions. Achievement of large size CuO particles and adequate CeO(2)-CuO interfacial configurations in the inverse catalyst apparently allows appreciable enhancement of the catalytic properties of this kind of system for CO-PROX, constituting an interesting alternative to classic direct configurations so far explored for this process. Reasons for such behavior are analyzed on the basis of operando-XRD, -XAFS, and -DRIFTS studies.

  3. 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.

  4. 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...

  5. 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.

  6. 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.

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

    PubMed

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

    2016-09-01

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

  8. 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.

  9. 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...

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

  11. 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.

  12. 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.

  13. Single particle ICP-MS method development for the determination of plant uptake and accumulation of CeO2 nanoparticles.

    PubMed

    Dan, Yongbo; Ma, Xingmao; Zhang, Weilan; Liu, Kun; Stephan, Chady; Shi, Honglan

    2016-07-01

    Cerium dioxide nanoparticles (CeO2NPs) are among the most broadly used engineered nanoparticles that will be increasingly released into the environment. Thus, understanding their uptake, transportation, and transformation in plants, especially food crops, is critical because it represents a potential pathway for human consumption. One of the primary challenges for the endeavor is the inadequacy of current analytical methodologies to characterize and quantify the nanomaterial in complex biological samples at environmentally relevant concentrations. Herein, a method was developed using single particle-inductively coupled plasma-mass spectrometry (SP-ICP-MS) technology to simultaneously detect the size and size distribution of particulate Ce, particle concentration, and dissolved cerium in the shoots of four plant species including cucumber, tomato, soybean, and pumpkin. An enzymatic digestion method with Macerozyme R-10 enzyme previously used for gold nanoparticle extraction from the tomato plant was adapted successfully for CeO2NP extraction from all four plant species. This study is the first to report and demonstrate the presence of dissolved cerium in plant seedling shoots exposed to CeO2NPs hydroponically. The extent of plant uptake and accumulation appears to be dependent on the plant species, requiring further systematic investigation of the mechanisms.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. Microstructure and wear properties of Al2O3-CeO2/Ni-base alloy composite coatings on aluminum alloys by plasma spray

    NASA Astrophysics Data System (ADS)

    He, Long; Tan, Yefa; Wang, Xiaolong; Xu, Ting; Hong, Xiang

    2014-09-01

    Al2O3 and CeO2 particles reinforced Ni-base alloy composite coatings were prepared on aluminum alloy 7005 by plasma spray. The microstructure, microhardness, fracture toughness, critical bonding force and the wear behavior and mechanisms of the composite coatings were investigated. It is found that CeO2 particles can refine crystal grains, reduce porosity and unmelted Al2O3 particles in the composite coatings. The microhardness, fracture toughness, critical bonding force and wear resistance of the composite coatings are enhanced due to synergistic strengthening effects of Al2O3 and CeO2 particles. The friction coefficients and wear losses increase as loads increase. At the loads of 3-6 N, the composite coatings experience local plastic deformation and micro-cutting wear. At the loads in the range of 9-12 N, the calculated maximum contact stress and maximum tensile stress on friction surfaces increase leading to plastic deformation induced working hardening. The wear mechanisms change into micro-brittle fracture wear and slight oxidative wear.

  19. Strain-level bacterial identification by CeO2-catalyzed MALDI-TOF MS fatty acid analysis and comparison to commercial protein-based methods.

    PubMed

    Cox, C R; Jensen, K R; Saichek, N R; Voorhees, K J

    2015-07-20

    Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) has emerged as a rapid approach for clinical bacterial identification. However, current protein-based commercial bacterial ID methods fall short when differentiating closely related species/strains. To address this shortcoming, we employed CeO2-catalyzed fragmentation of lipids to produce fatty acids using the energy inherent to the MALDI laser as a novel alternative to protein profiling. Fatty acid profiles collected from Enterobacteriaceae, Acinetobacter, and Listeria using CeO2-catalyzed metal oxide laser ionization (MOLI MS), processed by principal component analysis, and validated by leave-one-out cross-validation (CV), showed 100% correct classification at the species level and 98% at the strain level. In comparison, protein profile data from the same bacteria yielded 32%, 54% and 67% mean species-level accuracy using two MALDI-TOF MS platforms, respectively. In addition, several pathogens were misidentified by protein profiling as non-pathogens and vice versa. These results suggest novel CeO2-catalyzed lipid fragmentation readily produced (i) taxonomically tractable fatty acid profiles by MOLI MS, (ii) highly accurate bacterial classification and (iii) consistent strain-level ID for bacteria that were routinely misidentified by protein-based methods.

  20. 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.

  1. 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

  2. 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

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. Synthesis and room-temperature ferromagnetism of CeO2 nanocrystals with nonmagnetic Ca2+ doping

    NASA Astrophysics Data System (ADS)

    Chen, Xiaobo; Li, Guangshe; Su, Yiguo; Qiu, Xiaoqing; Li, Liping; Zou, Zhigang

    2009-03-01

    This work initiates an investigation on the creation of room-temperature ferromagnetism in diamagnetic solid via a nonmagnetic doping. CeO2 is taken as a prototype compound. A series of Ce1-xCaxO2-δ solid solutions with x = 0-0.25 were prepared by a solution combustion method using L-glutamic acid as the fuel. Sample characterization indicates that all as-prepared samples crystallized in a pure face-centered cubic fluorite structure with crystallite sizes smaller than 10 nm. On increasing the dopant content, the crystallite size decreased from about 8 to 4 nm, while the lattice parameter increased systematically. At room temperature, all samples are ferromagnetic admixed with an apparent diamagnetic component, as composed to a mixture of paramagnetic and antiferromagnetic behaviors or the absence of the ferromagnetism reported in the literature (Bouaine et al 2007 J. Phys. Chem. C 111 2924-8 Ney et al 2008 Phys. Rev. Lett. 100 157201) for magnetically doped semiconductors such as Sn1-xCoxO2 and Zn1-xCoxO. The coercivity and saturation magnetization for x = 0 are 110 Oe and 2.01 × 10-4 emu g-1, respectively, which slightly increased to 148 Oe and 2.26 × 10-4 emu g-1 on increasing the dopant content to x = 0.10. Upon annealing the as-prepared samples at 800 °C for 2 h, these magnetic parameters were weakened. This observation was interpreted in terms of the mixed valence state of Ce3+/Ce4+ and the doping effects. Finally, the nature of the room-temperature ferromagnetism is discussed by taking into account the oxygen vacancies and defects at the surface/interfaces that act as the electron and hole traps.

  10. 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

  11. 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).

  12. Strain-level Staphylococcus differentiation by CeO2-metal oxide laser ionization mass spectrometry fatty acid profiling.

    PubMed

    Saichek, Nicholas R; Cox, Christopher R; Kim, Seungki; Harrington, Peter B; Stambach, Nicholas R; Voorhees, Kent J

    2016-04-23

    The Staphylococcus genus is composed of 44 species, with S. aureus being the most pathogenic. Isolates of S. aureus are generally susceptible to β-lactam antibiotics, but extensive use of this class of drugs has led to increasing emergence of resistant strains. Increased occurrence of coagulase-negative staphylococci as well as S. aureus infections, some with resistance to multiple classes of antibiotics, has driven the necessity for innovative options for treatment and infection control. Despite these increasing needs, current methods still only possess species-level capabilities and require secondary testing to determine antibiotic resistance. This study describes the use of metal oxide laser ionization mass spectrometry fatty acid (FA) profiling as a rapid, simultaneous Staphylococcus identification and antibiotic resistance determination method. Principal component analysis was used to classify 50 Staphyloccocus isolates. Leave-one-spectrum-out cross-validation indicated 100 % correct assignment at the species and strain level. Fuzzy rule building expert system classification and self-optimizing partial least squares discriminant analysis, with more rigorous evaluations, also consistently achieved greater than 94 and 84 % accuracy, respectively. Preliminary analysis differentiating MRSA from MSSA demonstrated the feasibility of simultaneous determination of strain identification and antibiotic resistance. The utility of CeO2-MOLI MS FA profiling coupled with multivariate statistical analysis for performing strain-level differentiation of various Staphylococcus species proved to be a fast and reliable tool for identification. The simultaneous strain-level detection and antibiotic resistance determination achieved with this method should greatly improve outcomes and reduce clinical costs for therapeutic management and infection control.

  13. 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

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. Chemical solution deposition (CSD) of CeO2 and La2Zr2O7 buffer layers on cube textured NiW substrates

    NASA Astrophysics Data System (ADS)

    Kotzyba, G.; Obst, B.; Nast, R.; Goldacker, W.; Holzapfel, B.

    2006-06-01

    We present results of crack free layers of CeO2 and La2Zr2O7 deposited by means of CSD on cube textured Ni-4 at.% W substrates. EBSD-data show histograms with very good inplane- and out-of-plane textures and were used to simulate the critical current density in the YBCO layer. The surface roughness, a sensitive feature for good deposition results, was analyzed with a profilometer. In the CSD process we applied, the 2, 4-pentanedionates of the metal cations in glacial acetic acid and methanol served as starting substances.

  19. 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.

  20. 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

  1. 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.

  2. Nanostructured LnBaCo2O6-𝜹 (Ln = Sm, Gd) with layered structure for intermediate temperature solid oxide fuel cell cathodes

    NASA Astrophysics Data System (ADS)

    Mejía Gómez, Augusto E.; Lamas, Diego G.; Leyva, Ana Gabriela; Sacanell, Joaquín

    2017-04-01

    In this work, we present the combination of two characteristics that are beneficial for solid oxide fuel cell (SOFC) cathodic performance in one material. We developed and evaluated for the first time nanostructured layered perovskites of formulae LnBaCo2O6-d with Ln = Sm and Gd (SBCO and GBCO, respectively) as SOFC cathodes, finding promising electrochemical properties in the intermediate temperature range. We obtained those nanostructures by using porous templates to confine the chemical reagents in regions of 200-800 nm. The performance of nanostructured SBCO and GBCO cathodes was analyzed by electrochemical impedance spectroscopy technique under different operating conditions using Gd2O3-doped CeO2 as electrolyte. We found that SBCO cathodes displayed lower area-specific resistance than GBCO ones, because bulk diffusion of oxide ions is enhanced in the former. We also found that cathodes synthesized using smaller template pores exhibited better performance.

  3. 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.

  4. 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.

  5. Study of CeO2 Modified AlNi Mixed Pillared Clays Supported Palladium Catalysts for Benzene Adsorption/Desorption-Catalytic Combustion

    PubMed Central

    Li, Jingrong; Yang, Peng; Qi, Chenze

    2017-01-01

    A new functional AlNi-pillared clays (AlNi-PILC) with a large surface area and pore volume was synthesized. The performance of adsorption/desorption-catalytic combustion over CeO2-modified Pd/AlNi-PILC catalysts was also studied. The results showed that the d001-value and specific surface area (SBET) of AlNi-PILC reached 2.11 nm and 374.8 m2/g, respectively. The large SBET and the d001-value improved the high capacity for benzene adsorption. Also, the strong interaction between PdCe mixed oxides and AlNi-PILC led to the high dispersion of PdO and CeO2 on the support, which was responsible for the high catalytic performance. Especially, 0.2% Pd/12.5% Ce/AlNi-PILC presented high performance for benzene combustion at 240 °C and high CO2 selectivity. Also, the combustion temperatures were lower compared to the desorption temperatures, which demonstrated that it could accomplish benzene combustion during the desorption process. Furthermore, its activity did not decrease after continuous reaction for 1000 h in dry air, and it also displayed good resistance to water and the chlorinated compound, making it a promising catalytic material for the elimination of volatile organic compounds. PMID:28809809

  6. 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.

  7. Effect of template post-annealing on Y(Dy)BaCuO nucleation on CeO2 buffered metallic tapes

    NASA Astrophysics Data System (ADS)

    Hu, Xuefeng; Zhong, Yun; Zhong, Huaxiao; Fan, Feng; Sang, Lina; Li, Mengyao; Fang, Qiang; Zheng, Jiahui; Song, Haoyu; Lu, Yuming; Liu, Zhiyong; Bai, Chuanyi; Guo, Yanqun; Cai, Chuanbing

    2017-08-01

    Substrate engineering is very significant in the synthesis of the high-temperature superconductor (HTS) coated conductor. Here we design and synthesize several distinct and stable Cerium oxide (CeO2) surface reconstructions which are used to grow epitaxial films of the HTS YBa2Cu3O7-δ (YBCO). To identify the influence of annealing and post-annealing surroundings on the nature of nucleation centers, including Ar/5%H2, humid Ar/5%H2 and O2 in high temperature annealing process, we study the well-controlled structure, surface morphology, crystal constants and surface redox processes of the ceria buffers by using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and field-emission scanning electronic microscopy (FE-SEM), respectively. The ceria film post-annealed under humid Ar/5%H2 gas shows the best buffer layer properties. Furthermore, the film absorbs more oxygen ions, which appears to contribute to oxygenation of superconductor film. The film is well-suited for ceria model studies as well as a perfect substitute for CeO2 bulk material.

  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. 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.

  10. 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.

  11. Estimation of Ce 4f-5d Interaction by Analysis of Partial Fluorescence Yield at the Ce L3 Edge of CeO2

    NASA Astrophysics Data System (ADS)

    Tonai, Hironori; Sasabe, Norimasa; Uozumi, Takayuki; Kawamura, Naomi; Mizumaki, Masaichiro

    2017-09-01

    Partial fluorescence yield (PFY) spectroscopy, which corresponds to a high-resolution version of the X-ray absorption spectroscopy (XAS), is experimentally performed at the Ce L3 edge of CeO2, and the result is theoretically analyzed using an impurity Anderson model (IAM). In order to estimate the Ce 4f-5d interaction Ufd, we employ a semi-empirical IAM framework based on the local density approximation+U method; Slater-Koster parameters describing the valence of CeO2 are estimated by band mapping within the linear combination of atomic orbitals scheme, and the resulting realistic valence structure is considered in the IAM analysis. The global structure of the PFY-XAS result, which consists of the Ce 2p3/2 → 5d dipole transition and the Ce 2p3/2 → 4f quadrupole transition, is excellently reproduced by the calculation. The Ufd value is estimated to be 3.0 eV. We emphasize that the sensitivity of PFY-XAS to Ufd makes it a good ruler for obtaining the Ufd values of Ce compounds.

  12. 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.

  13. 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.

  14. 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.

  15. 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. Copyright 2010 Elsevier Inc. All rights reserved.

  16. 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.

  17. One-pot synthesis of La0.7Sr0.3MnO3 supported on flower-like CeO2 as electrocatalyst for oxygen reduction reaction in aluminum-air batteries

    NASA Astrophysics Data System (ADS)

    Xue, Yejian; Huang, Heran; Miao, He; Sun, Shanshan; Wang, Qin; Li, Shihua; Liu, Zhaoping

    2017-08-01

    A novel La0.7Sr0.3MnO3-CeO2 (LSM-CeO2) hybrid catalyst for oxygen reduction reaction (ORR) has been synthesized by a facile one-pot method. The flower-like CeO2 with the diameter of about 3 μm is formed by the agglomeration of nanosheets with the thickness of about 40 nm. The LSM particles with the diameter of about 150 nm are well distributed on the flower-like CeO2, thus the interaction between LSM and CeO2 is built. Therefore, the LSM-CeO2 composite catalyst exhibits the much higher catalytic activity toward ORR with the direct four-electron transfer mechanism in alkaline solution than LSM or CeO2. Furthermore, the stability of LSM-CeO2 is superior to that of Pt/C, and the current retention is 93% after 100000 s. The maximum power density of the aluminum-air battery using LSM-CeO2 as the ORRC can reach 238 mW cm-2, which is about 29% higher than that with LSM (184 mW cm-2). It indicates that LSM-CeO2 composite material is a promising cathodic electrocatalyst for metal-air batteries.

  18. 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.

  19. Synthesis of mesoporous ceria/titania thin films for self-cleaning applications.

    PubMed

    Ismail, Adel A; Bouzid, Houcine

    2013-08-15

    CeO2/TiO2 thin films with a three-dimensional (3D) cubic structure were synthesized. Firstly, mesostructured 3D TiO2 films with high surface area and thermally stable have been prepared. Secondly, CeO2 was deposited on 3D mesoporous TiO2 film by two pathways: (i) cerium nitrate sol in presence of poly(ethylene glycol) was deposited on the prepared mesoporous TiO2 films by spin-coating to obtain 1, 3, and 5 layers CeO2/TiO2 and (ii) the second pathway, for thick CeO2, the prepared mesoporous TiO2 films were suspended into the high concentration of cerium nitrate in presence of poly(ethylene glycol) for 24h with magnetic stirring. FE-SEM images of the mesoporous CeO2/TiO2 films were crack-free and indicated a random worm-like network of the mesopores. The XRD patterns show for all prepared samples only TiO2 anatase phase. At five layers CeO2/TiO2, a weak and diffuse diffraction peak arises, corresponding to (111) plane of cubic CeO2. Methylene blue degradation was conducted to characterize the photocatalytic activity of films and compared with that of commercially available Pilkington Activ™ glass by the determination of their photonic efficiencies. Photonic efficiency of mesoporous TiO2~3.39% is higher than Pilkington Activ™ glass~10 times, probably due to the much larger surface area of the mesoporous films and its high crystallinity. Five layers CeO2/TiO2 films showed two times higher photoactivity for MB oxidation than mesoporous TiO2 film, and its photonic efficiency was found to be ~20 times higher than Pilkington Activ™ glass. Five layers CeO2/TiO2 was fixed after being used repetitively for five times. Copyright © 2013 Elsevier Inc. All rights reserved.

  20. 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).

  1. 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.

  2. Stabilizing new bismuth compounds in thin film form [Stabilizing new thin film materials in bismuth compounds

    DOE PAGES

    Chen, Aiping; Zhou, Honghui; Zhu, Yuanyuan; ...

    2016-11-10

    Growth of unexpected phases from a composite target of BiFeO3:BiMnO3 and/or BiFeO3:BiCrO3 has been explored using pulsed laser deposition. The Bi2FeMnO6 tetragonal phase can be grown directly on SrTiO3 (STO) substrate, while two phases (S1 and S2) were found to grow on LaAlO3 (LAO) substrates with narrow growth windows. However, introducing a thin CeO2 buffer layer effectively broadens the growth window for the pure S1 phase, regardless of the substrate. Moreover, we discovered two new phases (X1 and X2) when growing on STO substrates using a BiFeO3:BiCrO3 target. Pure X2 phase can be obtained on CeO2-buffered STO and LAO substrates.more » This work demonstrates that some unexpected phases can be stabilized in a thin film form by using composite perovskite BiRO3 (R = Cr, Mn, Fe, Co, Ni) targets. Moreover, it also indicates that CeO2 can serve as a general template for the growth of bismuth compounds with potential room-temperature multiferroicity.« less

  3. Toxicity evaluation of manufactured CeO2 nanoparticles before and after alteration: combined physicochemical and whole-genome expression analysis in Caco-2 cells.

    PubMed

    Fisichella, Matthieu; Berenguer, Frederic; Steinmetz, Gerard; Auffan, Melanie; Rose, Jerome; Prat, Odette

    2014-08-21

    Engineered nanomaterials may release nanosized residues, by degradation, throughout their life cycle. These residues may be a threat for living organisms. They may be ingested by humans through food and water. Although the toxicity of pristine CeO2 nanoparticles (NPs) has been documented, there is a lack of studies on manufactured nanoparticles, which are often surface modified. Here, we investigated the potential adverse effects of CeO2 Nanobyk 3810™ NPs, used in wood care, and their residues, altered by light or acid. Human intestinal Caco-2 cells were exposed to residues degraded by daylight or in a medium simulating gastric acidity. Size and zeta potential were determined by dynamic light scattering. The surface structure and redox state of cerium were analyzed by transmission electronic microscopy (TEM) and X-ray absorption spectroscopy, respectively. Viability tests were performed in Caco-2 cells exposed to NPs. Cell morphology was imaged with scanning electronic microscopy. Gene expression profiles obtained from cells exposed to NPs before and after their alteration were compared, to highlight differences in cellular functions.No change in the cerium redox state was observed for altered NPs. All CeO2 NPs suspended in the culture medium became microsized. Cytotoxicity tests showed no toxicity after Caco-2 cell exposure to these various NPs up to 170 μg/mL (24 h and 72 h). Nevertheless, a more-sensitive whole-gene-expression study, based on a pathway-driven analysis, highlighted a modification of metabolic activity, especially mitochondrial function, by altered Nanobyk 3810™. The down-regulation of key genes of this pathway was validated by qRT-PCR. Conversely, Nanobyk 3810™ coated with ammonium citrate did not display any adverse effect at the same concentration. The degraded nanoparticles were more toxic than their coated counterparts. Desorption of the outside layer was the most likely cause of this discrepancy in toxicity. It can be assumed that the safe design of engineered nanoparticles could include robust protective layers conferring on them greater resistance to alteration during their life cycle.

  4. Cube textured CeO2, BaZrO3 and LaAlO3 buffer layers on Ni based Substrates

    NASA Astrophysics Data System (ADS)

    Deinhofer, C.; Gritzner, G.

    2006-06-01

    CeO2, BaZrO3 as well as LaAlO3 buffer layers were deposited on {100}<001> Ni + 5 weight-% W substrates by a wet chemical technique. The solutions were prepared by dissolving the metal nitrates or acetates and zirconiumacetylacetonate, respectively, in mixtures of acetic acid, methanol and water. The solutions were applied by dip- or spincoating, dried at 135 °C and annealed at temperatures between 900 and 1 400 °C depending on the buffer layer for 15 min. under Ar-5% H2 gas flow. Pole-figure measurements proved the exact texture of each buffer layer. Electron microscopy showed dense and smooth buffer layers.

  5. 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.

  6. 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.

  7. 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.

  8. Ultrasonic, FTIR and thermal investigations of SiO2-Na2O-CaO-P2O5 glasses doped with CeO2

    NASA Astrophysics Data System (ADS)

    Marzouk, Samir Y.

    2010-11-01

    The longitudinal and shear ultrasonic wave velocities for different compositions of SiO2-Na2O-CaO-P2O5 glasses were measured at room temperature (305 K) using a pulse-echo method at a frequency of 4 MHz. The elastic moduli, Poisson's ratio, microhardness, Debye temperature and other ultrasonic parameters were obtained from experimental data and analyzed using bond compression theory. By calculating the number of network bonds per unit volume, the average stretching constant, and the average ring size, information about the structure of the glass can be deduced. Structural changes after doping with CeO2 were investigated by FTIR spectroscopy, and by measurements of the thermal expansion coefficient, glass transition and softening temperature to throw more light on the characterization of these glasses.

  9. 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.

  10. Unconventional interplay between heterovalent dopant elements: Switch-and-modulator band-gap engineering in (Y, Co)-Codoped CeO2 nanocrystals

    PubMed Central

    Wu, T. S.; Li, H. D.; Chen, Y. W.; Chen, S. F.; Su, Y. S.; Chu, C. H.; Pao, C. W.; Lee, J. F.; Lai, C. H.; Jeng, H. T.; Chang, S. L.; Soo, Y. L.

    2015-01-01

    We report the experimental observation and theoretical explanation of an unconventional interplay between divalent Co and trivalent Y dopants, both of which incur oxygen vacancies in the CeO2 host that has predominantly tetravalent Ce cations. The Co dopant atoms were experimentally found to act as a switch that turns on the dormant effect of Y-modulated band-gap reduction. As revealed by density functional theory (DFT) calculations with structures verified by synchrotron-radiation x-ray measurements, a Co 3d band that hybridizes with Ce 4f band was lowered due to reduced O 2p repulsion arising from oxygen vacancies incurred by Y doping and therefore gave rise to the observed band-gap narrowing effect. Such switch-and-modulator scheme for band-gap engineering in nanocrystal materials can lead to important applications in environmental protection and solar energy harvesting technologies. PMID:26486721

  11. 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.

  12. 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.

  13. Effect of transition metal Fe adsorption on CeO2 (110) surface in the methane activation and oxygen vacancy formation: A density functional theory study

    NASA Astrophysics Data System (ADS)

    Tian, Dong; Zeng, Chunhua; Wang, Hua; Cheng, Xianming; Zheng, Yane; Xiang, Chao; Wei, Yonggang; Li, Kongzhai; Zhu, Xing

    2017-09-01

    Methane activation and oxygen vacancy formation over transition metal Fe adsorption on CeO2 (110) are studied by using the method of density functional theory (DFT) + U method. A set of model configurations are generated by placing Fe at five surface sites, viz., O-top site, O-bridge site, Ce-bridge site, Ce-top and double oxygen-bridge sites. The study shows that the energetically most favorable configuration is Fe adsorption at the double oxygen-bridge site. Based on the calculated surface, subsurface and the second oxygen vacancies formation energy with (or without) Fe adsorption, it shows that the Fe adsorption is in favor of the surface, subsurface and second oxygen vacancies formation. For the surface and subsurface oxygen vacancy on the Fe/CeO2 (110) surface, the main factor responsible for lowering of Evac is that the adsorption induces structural distortions, whereas, for the second oxygen vacancy, half can be attributed to the large structural relaxation, half can be attributed to the electronic effects. After calculating and discussing about the CH4 activation on CeO2 (110) and Fe/CeO2 (110) surface with (or without) the surface or subsurface oxygen vacancies at the possible adsorption sites, the results show that when the CH4 adsorbed on the Fe/CeO2 (110) with the surface oxygen vacancy at the Ce1 and Ce2 sites, the CH4 decomposed into the CH(ads) and H(ads), its belongs to the chemical absorption, whereas, when the CH4 adsorbed on the other possible sites, the mentioned phenomenon is not occurred, its belongs to the physical absorption. This study reveals the correlation between surface reducibility and catalytic activity for methane oxidation on cerium-based materials, which might be beneficial in developing improved catalysts for methane combustion.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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

  3. The role of charge transfer in the oxidation state change of Ce atoms in the TM13-CeO2(111) systems (TM = Pd, Ag, Pt, Au): a DFT + U investigation.

    PubMed

    Tereshchuk, Polina; Freire, Rafael L H; Ungureanu, Crina G; Seminovski, Yohanna; Kiejna, Adam; Da Silva, Juarez L F

    2015-05-28

    Despite extensive studies of transition metal (TM) clusters supported on ceria (CeO2), fundamental issues such as the role of the TM atoms in the change in the oxidation state of Ce atoms are still not well understood. In this work, we report a theoretical investigation based on static and ab initio molecular dynamics density functional theory calculations of the interaction of 13-atom TM clusters (TM = Pd, Ag, Pt, Au) with the unreduced CeO2(111) surface represented by a large surface unit cell and employing Hubbard corrections for the strong on-site Coulomb correlation in the Ce f-electrons. We found that the TM13 clusters form pyramidal-like structures on CeO2(111) in the lowest energy configurations with the following stacking sequence, TM/TM4/TM8/CeO2(111), while TM13 adopts two-dimensional structures at high energy structures. TM13 induces a change in the oxidation state of few Ce atoms (3 of 16) located in the topmost Ce layer from Ce(IV) (itinerant Ce f-states) to Ce(III) (localized Ce f-states). There is a charge flow from the TM atoms to the CeO2(111) surface, which can be explained by the electronegativity difference between the TM (Pd, Ag, Pt, Au) and O atoms, however, the charge is not uniformly distributed on the topmost O layer due to the pressure induced by the TM13 clusters on the underlying O ions, which yields a decrease in the ionic charge of the O ions located below the cluster and an increase in the remaining O ions. Due to the charge flow mainly from the TM8-layer to the topmost O-layer, the charge cannot flow from the Ce(IV) atoms to the O atoms with the same magnitude as in the clean CeO2(111) surface. Consequently, the effective cationic charge decreases mainly for the Ce atoms that have a bond with the O atoms not located below the cluster, and hence, those Ce atoms change their oxidation state from IV to III. This increases the size of the Ce(III) compared with the Ce(IV) cations, which builds-in a strain within the topmost Ce layer, and hence, also affecting the location of the Ce(III) cations and the structure of the TM13 clusters.

  4. Novel Recovery of Nano-Structured Ceria (CeO2) from Ce(III)-Benzoxazine Dimer Complexes via Thermal Decomposition

    PubMed Central

    Veranitisagul, Chatchai; Kaewvilai, Attaphon; Sangngern, Sarawut; Wattanathana, Worawat; Suramitr, Songwut; Koonsaeng, Nattamon; Laobuthee, Apirat

    2011-01-01

    N,N-bis(2-hydroxybenzyl)alkylamines, benzoxazine dimers, are the major product produced from benzoxazine monomers on mono-functional phenol by the one step ring opening reaction. Due to the metal responsive property of benzoxazine dimers, in this present work, N,N-bis(5-methyl-2-hydroxybenzyl)methylamine (MMD), N,N-bis (5-ethyl-2-hydroxybenzyl)methylamine (EMD), and N,N-bis(5-methoxy-2-hydroxybenzyl) methyl amine (MeMD), are considered as novel ligands for rare earth metal ion, such as cerium(III) ion. The complex formed when the clear and colorless solutions of cerium nitrate and benzoxazine dimers were mixed, results in a brown colored solution. The metal-ligand ratios determined by the molar ratio and the Job’s methods were found to be in a ratio of 1:6. To clarify the evidence of the complex formation mechanism, the interactions among protons in benzoxazine dimers both prior to and after the formation of complexes were determined by means of 1H-NMR, 2D-NMR and a computational simulation. The single phase ceria (CeO2) was successfully prepared by thermal decomposition of the Ce(III)-benzoxazine dimer complexes at 600 °C for 2 h, was then characterized using XRD. In addition, the ceria powder investigated by TEM is spherical with an average diameter of 20 nm. PMID:21845083

  5. 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.

  6. 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.

  7. 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.

  8. Co3O4/Sm-Doped CeO2/Co3O4 Trilayer Coating on AISI 441 Interconnect for Solid Oxide Fuel Cells.

    PubMed

    Shen, Fengyu; Lu, Kathy

    2017-02-22

    In this work, a novel Co/Sm-doped CeO2 (SDC)/Co trilayer of ∼6 μm is deposited by alternating electrodeposition and electrophoresis and oxidized to a Co3O4/SDC/Co3O4 trilayer structure. This coating is unique and effective in the following aspects: (1) The area specific resistance of the coated interconnect is more stable and lower than that of the uncoated interconnect after thermal treatment at 800 °C for 400 h. (2) The Co3O4/SDC/Co3O4 coating layer can effectively inhibit Cr diffusion and evaporation and significantly slow the oxidation rate of the interconnect. (3) The Sm0.5Sr0.5Co0.2Fe0.8O3 cathode in the electrolyte/cathode/interconnect half-cell retains its initial stoichiometry after 100 h of the thermal treatment. Subsequently, the ohmic resistance RΩ, high frequency polarization resistance RH, and low frequency polarization resistance RL of the half-cell with the Co3O4/SDC/Co3O4 coated interconnect are all smaller than those of the half-cell with the bare interconnect. The Co3O4/SDC/Co3O4 coating layer has great advantages to be used as a protective layer for the metallic interconnect in solid oxide fuel cells to improve cell performance, stability, and durability.

  9. 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.

  10. 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.

  11. 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.

  12. Alkali metal poisoning of a CeO2-WO3 catalyst used in the selective catalytic reduction of NOx with NH3: an experimental and theoretical study.

    PubMed

    Peng, Yue; Li, Junhua; Chen, Liang; Chen, Jinghuan; Han, Jian; Zhang, He; Han, Wei

    2012-03-06

    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.

  13. 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.

  14. Fe-doped CeO2 solid solutions: Substituting-site doping versus interstitial-site doping, bulk doping versus surface doping

    NASA Astrophysics Data System (ADS)

    Bao, Huizhi; Qian, Kun; Fang, Jun; Huang, Weixin

    2017-08-01

    Doping CeO2 cubic fluorite with transitional metal ions can effectively improve its redox behavior, oxygen storage capacity and catalytic performance, but the relevant fundamental understanding of the promotion effect is still insufficient due to the difficulty on determining the distribution of dopant. We herein demonstrate an effective approach to determine this dopant distribution by combining X-ray absorption spectroscopy and selective chemisorption. Cubic CexFe1-xO2 fluorite solid solutions (x ≥ 0.70) were prepared by co-precipitation method. With the increasing of Fe molar ratio in CexFe1-xO2, Fe3+ initially substitutes Ce4+ and/or occupy intersitial sites with x ≥ 0.80, and then transfers to form sub-Fe2O3 structure in fluorite lattice as more Fe3+ are present; meanwhile, the Fe3+ doping initially occurs only in the bulk with x ≥ 0.96 and then extends to the surface with 0.87 ≤ x < 0.96. Low calcinations temperature facilitates the doping of Fe3+ in the bulk of cubic CexFe1-xO2 solid solutions. These results reveal the structures of CexFe1-xO2 fluorite solid solutions at the molecular level that are of great importance for the fundamental understanding of their properties.

  15. 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.

  16. Construction of NiO/MnO2/CeO2 hybrid nanoflake arrays as platform for electrochemical energy storage

    NASA Astrophysics Data System (ADS)

    Cui, Lihua; Cui, Jiewu; Zheng, Hongmei; Wang, Yan; Qin, Yongqiang; Shu, Xia; Liu, Jiaqin; Zhang, Yong; Wu, Yucheng

    2017-09-01

    Rational design and fabrication of novel electrode materials are of great importance for developing supercapacitors with remarkable capacitance and enhanced cycling stability. In this paper, we present a simple one-pot hydrothermal deposition followed by calcinations process for the in situ construction of homogeneous NiO/MnO2/CeO2 (NMC) nanoflake arrays on Ni foam substrate, which could be directly adopted as the binder-free electrode materials for high performance supercapacitors. The field-emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and energy-dispersive X-ray spectroscopy (EDX) are carried out to investigate the morphology, microstructure and composition of NMC nanoflake arrays. As-prepared hierarchical NMC nanoflake arrays exhibit the specific capacitance of 1027.8 F g-1 at a current density of 3.1 A g-1 and excellent cycling stability of 97.8% after 5000 charge/discharge cycles. This facile, cost-effective and controllable fabrication route and the robust supercapacitive activity suggest that the ordered NMC nanoflake arrays could be promising candidate electrode materials for high performance electrochemical energy storage devices.

  17. 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

  18. 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.

  19. Facile synthesis of Co(3)O(4)-CeO(2) 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. Copyright © 2017 Elsevier Inc. All rights reserved.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. Development and experimental study for hydrogen production from the thermochemical two-step water splitting cycles with a CeO2 coated new foam device design using solar furnace system

    NASA Astrophysics Data System (ADS)

    Cho, Hyun seok; Kodama, Tatsuya; Gokon, Nobuyuki; Kim, Jong kyu; Lee, Sang nam; Kang, Yong heack

    2017-06-01

    A solar reactor containing a CeO2-coated reactive foam device for producing hydrogen via a thermochemical two-step water splitting cycle was proposed and experimentally tested. Modeling of the optical properties of the 40 kWth KIER (Korea Institute of Energy Research) solar furnace was performed to design and prepare the optimized foam matrix shape and the new solar reactor. Solar demonstration of the solar reactor was accomplished in the KIER 40 kWth solar furnace and hydrogen was produced successfully during the water decomposition step. The conical shape foam device was suggested and tested the temperature gradients and hydrogen productivity. Finally, five cyclic test was conducted with the conical shape CeO2-coated foam device, the total hydrogen production was 1394.32 Ncm3 during the five cycles and the average hydrogen production per cycle was 278.86 Ncm3.

  7. Dielectric and piezoelectric properties of CeO2-added nonstoichiometric (Na0.5K0.5)0.97(Nb0.96Sb0.04)O3 ceramics for piezoelectric energy harvesting device applications.

    PubMed

    Oh, Youngkwang; Noh, Jungrae; Yoo, Juhyun; Kang, Jinhee; Hwang, Larkhoon; Hong, Jaeil

    2011-09-01

    In this study, nonstoichiometric (Na(0.5)K(0.5))(0.97)(Nb(0.96)Sb(0.04))O(3) ceramics were fabricated and their dielectric and piezoelectric properties were investigated according to the CeO(2) addition. In this ceramic composition, CeO(2) addition improved sinterability, electromechanical coupling factor k(p), mechanical quality factor Q(m), piezoelectric constant d(33), and g(33). At the sintering temperature of 1100°C, for the 0.2wt% CeO(2) added specimen, the optimum values of density = 4.359 g/cm(3), k(p) = 0.443, Q(m) = 588, ε(r) = 444, d(33) = 159 pC/N, and g(33) = 35 × 10(-3) V·m/N, were obtained. A piezoelectric energy harvesting device using 0.2 wt% CeO(2)- added lead-free (K(0.5)Na(0.5))(0.97)(Nb(0.96)Sb(0.04))O(3) ceramics and a rectifying circuit for energy harvesting were fabricated and their electrical characteristics were investigated. Under an external vibration acceleration of 0.7 g, when the mass, the frequency of vibration generator, and matching load resistance were 2.4 g, 70 Hz, and 721 Ω, respectively, output voltage and power of piezoelectric harvesting device indicated the optimum values of 24.6 mV(rms) and 0.839 μW, respectively-suitable for application as the electric power source of a ubiquitous sensor network (USN) sensor node.

  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

    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.

  10. 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.

  11. 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

  12. Identification of the nano/micro structure of CeO2(rod) and the essential role of interfacial copper-ceria interaction in CuCe(rod) for selective oxidation of CO in H2-rich streams

    NASA Astrophysics Data System (ADS)

    Guo, Xiaolin; Zhou, Renxian

    2017-09-01

    CeO2(rod) has been found to be exposed four {111} planes and two {100} planes with a hexangular cross section, and the growth mechanism follows to the oriented attachment of the cube-like basic grains with a [110] growth direction and the subsequent Ostwald ripening, corresponding to the increasing lateral size and longitudinal size with prolonging the hydrothermal time. Equal amount of copper oxide totally highly distributed on the surface of CeO2(rod) supports with different abundance of oxygen vacancies facilitate to produce the strongly bound Cu-[Ox]-Ce species to different degrees (supported by XPS, H2-TPR and in situ DRIFTs results), which is encouraged by prolongation of hydrothermal time of CeO2(rod) supports. The essential role of interfacial Cu-Ce interaction in CuCe(rod) catalysts for CO-PROX was identified by the enhanced catalytic performance of CuCe(rod)-48h, on account of much stronger Cu-Ce interaction generated in it. Moreover, we proposed a potential structural model of strongly bound Cu-[Ox]-Ce to interpret the synergetic effect of copper and ceria species in CuO/CeO2 catalysts and generalized the possible reaction mechanism for CO-PROX over the CuCe(rod) catalyst.

  13. 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.

  14. 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.

  15. 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.

  16. 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

  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. 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.

  19. 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

  20. Photocatalytic reduction of CO2 based on a CeO2 photocatalyst loaded with imidazole fabricated N-doped graphene and Cu(ii) as cocatalysts.

    PubMed

    Zhou, Shan-Shan; Liu, Shou-Qing

    2017-09-08

    Cocatalysts are vital for improving photocatalytic activity. Incorporating nitrogen atoms on a graphene frame using an imidazole cycle resulted in a new N-doped graphene (denoted as ING). Cerium(iv) oxide (CeO2) nanoparticles were dispersed on ING sheets, producing an ING/CeO2 hybrid material. The ING/CeO2 hybrid material was characterized using X-ray diffraction, transmission electron microscopy, Raman spectroscopy, ultraviolet-visible diffuse reflectance spectroscopy and surface photovoltage spectroscopy. Copper(ii) ions [Cu(ii)] were adsorbed on the ING/CeO2 hybrid material to directly form Cu(ii)/ING/CeO2, which could capture the photogenerated electrons to reduce carbon dioxide (CO2) to methanol (CH3OH) under incident light irradiation. The results showed that the yield from reducing CO2 to CH3OH during the photocatalytic process using Cu(ii)/ING/CeO2 as the photocatalyst approached 385.8 μmol g(-1) cat. h(-1), whereas the yield was only 3.57 μmol g(-1) cat. h(-1) using ING/CeO2 as the photocatalyst. This shows that the Cu(ii) ions play a vital role during photocatalytic reduction of CO2 by forming copper(i) ions [Cu(i)]. The percentage of ING in the ING/CeO2 hybrid material was investigated, and the results indicated that 3.6% of ING achieved an optimal yield of CH3OH during the photo-reduction process. The simultaneous roles of Cu(ii) ions and ING sheets demonstrate a synergistic strategy for improving the photocatalytic CO2 reduction.

  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. Enhancement of the Power Conversion Efficiency in the Inverted Organic Solar Cells Fabricated Utilizing a CeO2 Interlayer Between the Poly(3-hexylthiophene) (P3HT):[6,6]-Phenyl C6 Butyric Acid Methyl Ester and the Cathode.

    PubMed

    Arul, N Sabari; Lee, Yong Hun; Lee, Dea Uk; Kim, Tae Whan

    2015-01-01

    CeO2 nanoparticles were synthesized by using a precipitation method. High-resolution transmission electron microscopy images, X-ray diffraction patterns, energy dispersive X-ray spectroscopy spectra, and UV-Visible absorption spectroscopy spectra showed that the formed samples were CeO2 polycrystalline nanoparticles. Inverted organic solar cells with a structure of indium-tin-oxide/CeO2/poly(3-hexylthiophene) (P3HT):[6,6]-phenyl C61 butyric acid methyl ester (PCBM)/MoO3/Ag were fabricated. Current density-voltage results showed that the power conversion efficiency of the device of the fabricated inverted OPV cells with a CeO2 interlayer between the P3HT:PCBM and the cathode was 0.39% larger than that without a CeO2 interlayer.

  4. 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.

  5. 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. © The Author(s) 2016.

  6. 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.

  7. 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. Copyright © 2016 Elsevier Ltd. All rights reserved.

  8. 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).

  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

    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

  11. 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.

  12. Investigation of formaldehyde oxidation over Co3O4-Ce2 and Au/Co3O4-CeO2 catalysts at room temperature: effective removal and determination of reaction mechanism.

    PubMed

    Ma, Chunyan; Wang, Donghui; Xue, Wenjuan; Dou, Baojuan; Wang, Hailin; Hao, Zhengping

    2011-04-15

    Formaldehyde is regarded as the major indoor pollutant emitted from widely used building and decorative materials in airtight buildings, which should be eliminated under indoor environmental conditions. We report here catalytic oxidation process of formaldehyde over mesoporous Co(3)O(4), Co(3)O(4)-CeO(2), Au/Co(3)O(4), and Au/Co(3)O(4)-CeO(2) catalysts and their excellent catalytic performances at room temperature. These catalysts were prepared by a "nanocasting" method with the mesostructure generated from SBA-15 silica with 2D structure. The adsorbed surface species in the formaldehyde oxidation process are analyzed, and some key steps in the oxidation pathway, active sites, and intermediate species are proposed. Among the detected species, some kinds of formate species formed on the catalysts were indentified as intermediates, which further transformed into bicarbonate or carbonate and which decomposed to carbon dioxide. The role of the mesoporous Co(3)O(4) and the gold nanoparticles in the mechanism are also revealed.

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

    NASA Astrophysics Data System (ADS)

    Cooper, M. W. D.; Kuganathan, N.; Burr, P. A.; Rushton, M. J. D.; Grimes, R. W.; Stanek, C. R.; Andersson, D. A.

    2016-10-01

    The development of embedded atom method (EAM) many-body potentials for actinide oxides and associated mixed oxide (MOX) systems has motivated the development of a complementary parameter set for gas-actinide and gas-oxygen interactions. A comprehensive set of density functional theory (DFT) calculations were used to study Xe and Kr incorporation at a number of sites in CeO2, ThO2, UO2 and PuO2. These structures were used to fit a potential, which was used to generate molecular dynamics (MD) configurations incorporating Xe and Kr at 300 K, 1500 K, 3000 K and 5000 K. Subsequent matching to the forces predicted by DFT for these MD configurations was used to refine the potential set. This fitting approach ensured weighted fitting to configurations that are thermodynamically significant over a broad temperature range, while avoiding computationally expensive DFT-MD calculations. The resultant gas potentials were validated against DFT trapping energies and are suitable for simulating combinations of Xe and Kr in solid solutions of CeO2, ThO2, UO2 and PuO2, providing a powerful tool for the atomistic simulation of conventional nuclear reactor fuel UO2 as well as advanced MOX fuels.

  14. 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.

  15. CeO2-based Pd(Pt) nanoparticles grafted onto Fe3O4/graphene: a general self-assembly approach to fabricate highly efficient catalysts with magnetic recyclable capability.

    PubMed

    Wang, Xiao; Liu, Dapeng; Song, Shuyan; Zhang, Hongjie

    2013-04-15

    New Pd(Pt) catalysts have been fabricated by assembling multicomponents of Fe3O4 and CeO2/Pd(Pt) on the surface of reduced graphene oxide (RGO) nanosheets in layers. The as-obtained Pd(Pt) catalysts exhibit extremely high catalytic activity in the selective hydrogenation reaction of nitrobenzene. Owing to the presence of Fe3O4, the catalysts can be easily recycled from the catalytic system through magnetic separation. Their high activity, stability, and magnetic recyclability make the as-obtained hybrids very promising as catalysts in catalytic applications. Compared to other traditional multishell magnetic catalysts that were prepared by means of layer-by-layer technology, our process is much more facile and more easily controlled. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. 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).

  17. 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.

  18. 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.

  19. 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.

  20. 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.