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Sample records for doped ceria oxide

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

    PubMed Central

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

    2016-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

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

  3. Is Steam an Oxidant or a Reductant for Nickel/Doped-Ceria Cermets?

    PubMed

    Papaefthimiou, Vasiliki; Niakolas, Dimitris K; Paloukis, Fotios; Dintzer, Thierry; Zafeiratos, Spyridon

    2017-01-04

    Nickel/doped-ceria composites are promising electrocatalysts for solid-oxide fuel and electrolysis cells. Very often steam is present in the feedstock of the cells, frequently mixed with other gases, such as hydrogen or CO2 . An increase in the steam concentration in the feed mixture is considered accountable for the electrode oxidation and the deactivation of the device. However, direct experimental evidence of the steam interaction with nickel/doped-ceria composites, with adequate surface specificity, are lacking. Herein we explore in situ the surface state of nickel/gadolinium-doped ceria (NiGDC) under O2 , H2 , and H2 O environments by using near-ambient-pressure X-ray photoelectron and absorption spectroscopies. Changes in the surface oxidation state and composition of NiGDC in response to the ambient gas are observed. It is revealed that, in the mbar pressure regime and at intermediate temperature conditions (500-700 °C), steam acts as an oxidant for nickel but has a dual oxidant/reductant function for doped ceria.

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

    PubMed Central

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

    2016-01-01

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

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

    PubMed

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

    2016-01-01

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

  6. Energetics of Intermediate Temperature Solid Oxide Fuel Cell Electrolytes: Singly and Doubly doped Ceria Systems

    NASA Astrophysics Data System (ADS)

    Buyukkilic, Salih

    Solid oxide fuel cells (SOFCs) have potential to convert chemical energy directly to electrical energy with high efficiency, with only water vapor as a by-product. However, the requirement of extremely high operating temperatures (~1000 °C) limits the use of SOFCs to only in large scale stationary applications. In order to make SOFCs a viable energy solution, enormous effort has been focused on lowering the operating temperatures below 700 °C. A low temperature operation would reduce manufacturing costs by slowing component degradation, lessening thermal mismatch problems, and sharply reducing costs of operation. In order to optimize SOFC applications, it is critical to understand the thermodynamic stabilities of electrolytes since they directly influence device stability, sustainability and performance. Rare-earth doped ceria electrolytes have emerged as promising materials for SOFC applications due to their high ionic conductivity at the intermediate temperatures (500--700 °C). However there is a fundamental lack of understanding regarding their structure, thermodynamic stability and properties. Therefore, the enthalpies of formation from constituent oxides and ionic conductivities were determined to investigate a relationship between the stability, composition, structural defects and ionic conductivity in rare earth doped ceria systems. For singly doped ceria electrolytes, we investigated the solid solution phase of bulk Ce1-xLnxO2-0.5x where Ln = Sm and Nd (0 ≤ x ≤ 0.30) and analyzed their enthalpies of formation, mixing and association, and bulk ionic conductivities while considering cation size mismatch and defect associations. It was shown that for ambient temperatures in the dilute dopant region, the positive heat of formation reaches a maximum as the system becomes increasingly less stable due to size mismatch. In concentrated region, stabilization to a certain solubility limit was observed probably due to the defect association of trivalent cations

  7. Enhancing oxide ion incorporation kinetics by nanoscale Yttria-doped ceria interlayers.

    PubMed

    Fan, Zeng; Prinz, Fritz B

    2011-06-08

    Interlayering 17.5 nm of Yttria-doped ceria (YDC) thin films between bulk yttria-stabilized-zirconia electrolyte and a porous Pt cathode enhanced the performance of low-temperature solid oxide fuel cells. The added YDC interlayer (14.11% doped Y(2)O(3)) was fabricated by atomic layer deposition and reduced the cathode/electrolyte interfacial resistances while increasing the exchange current density j(0) by a factor of 4 at operating temperatures between 300-500 °C. Tafel plots and the fitted impedance data suggest that the charge transfer coefficient α of interlayered SOFCs was 1.25 times higher, and the electrode/interfacial activation energy was reduced from 0.85 to 0.76 eV.

  8. Calcium-doped ceria materials for anode of solid oxide fuel cells running on methane fuel

    NASA Astrophysics Data System (ADS)

    Zhao, Kai; Du, Yanhai

    2017-04-01

    A calcium-doped ceria with nominal compositions of Ce1-xCaxO2-δ (0.00 ≤ x ≤ 0.30) has been developed as an anode component for solid oxide fuel cells running on methane fuel. Crystal phases of Ce1-xCaxO2-δ are investigated with respect to the amount of calcium dopant. The Ce1-xCaxO2-δ shows single fluorite phase when the calcium is within 15 mol.%, and higher calcium doping levels lead to the appearance of a secondary phase (CaO). Conductivities of Ce1-xCaxO2-δ ceramics are studied by a four-probe method in air and the composition of Ce0.9Ca0.1O2-δ (x = 0.10) is found exhibiting the highest conductivity among the samples investigated in this work. Electrocatalytic properties of Ce0.9Ca0.1O2-δ are evaluated based on Ni-Ce1-xCaxO2-δ anode supported single cell running on methane fuel. At 800 °C, the single cell with Ni-Ce0.9Ca0.1O2-δ (x = 0.10) anode exhibits an optimum maximum powder density (618 mW cm-2) and good performance stability during 30 h operation in methane fuel. The promising findings substantiate the good performance of Ni-Ce0.9Ca0.1O2-δ anode for electrochemical oxidation of methane fuel.

  9. Incubational domain characterization in lightly doped ceria

    SciTech Connect

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

    2012-08-15

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

  10. Detonation nanodiamond introduced into samarium doped ceria electrolyte improving performance of solid oxide fuel cell

    NASA Astrophysics Data System (ADS)

    Pei, Kai; Li, Hongdong; Zou, Guangtian; Yu, Richeng; Zhao, Haofei; Shen, Xi; Wang, Liying; Song, Yanpeng; Qiu, Dongchao

    2017-02-01

    A novel electrolyte materials of introducing detonation nanodiamond (DNDs) into samarium doped ceria (SDC) is reported here. 1%wt. DNDs doping SDC (named SDC/ND) can enlarge the electrotyle grain size and change the valence of partial ceria. DNDs provide the widen channel to accelerate the mobility of oxygen ions in electrolyte. Larger grain size means that oxygen ions move easier in electrolyte, it can also reduce the alternating current (AC) impedance spectra of internal grains. The lower valence of partial Ce provides more oxygen vacancies to enhance mobility rate of oxygen ions. Hence all of them enhance the transportation of oxygen ions in SDC/ND electrolyte and the OCV. Ultimately the power density of SOFC can reach 762 mw cm-2 at 800 °C (twice higher than pure SDC, which is 319 mw cm-2 at 800 °C), and it remains high power density in the intermediate temperature (600-800 °C). It is relatively high for the electrolyte supported (300 μm) cells.

  11. Structural/surface characterization and catalytic evaluation of rare-earth (Y, Sm and La) doped ceria composite oxides for CH3SH catalytic decomposition

    NASA Astrophysics Data System (ADS)

    He, Dedong; Chen, Dingkai; Hao, Husheng; Yu, Jie; Liu, Jiangping; Lu, Jichang; Liu, Feng; Wan, Gengping; He, Sufang; Luo, Yongming

    2016-12-01

    A series of rare earth (Y, Sm and La) doped ceria composite oxides and pure CeO2 were synthesized and evaluated by conducting CH3SH catalytic decomposition test. Several characterization studies, including XRD, BET, Raman, H2-TPR, XPS, FT-IR, CO2-TPD and CH3SH-TPD, were undertaken to correlate structural and surface properties of the obtained ceria-based catalysts with their catalytic performance for CH3SH decomposition. More oxygen vacancies and increased basic sites exhibited in the rare earth doped ceria catalysts. Y doped ceria sample (Ce0.75Y0.25O2-δ), with a moderate increase in basic sites, contained more oxygen vacancies. More structural defects and active sites could be provided, and a relatively small amount of sulfur would accumulate, which resulted in better catalytic performance. The developed catalyst presented good catalytic behavior with stability very similar to that of typical zeolite-based catalysts reported previously. However, La doped ceria catalyst (Ce0.75La0.25O2-δ) with the highest alkalinity was not the most active one. More sulfur species would be adsorbed and a large amount of cerium sulfide species (Ce2S3) would accumulate, which caused deactivation of the catalysts. The combined effect of increased oxygen vacancies and alkalinity led to the catalytic stability of Ce0.75Sm0.25O2-δ sample was comparable to that of pure CeO2 catalyst.

  12. Optimization of ionic conductivity in doped ceria

    PubMed Central

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

    2006-01-01

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

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

    PubMed

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

    2016-05-25

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

  14. Solid oxide fuel cell bi-layer anode with gadolinia-doped ceria for utilization of solid carbon fuel

    NASA Astrophysics Data System (ADS)

    Kellogg, Isaiah D.; Koylu, Umit O.; Dogan, Fatih

    Pyrolytic carbon was used as fuel in a solid oxide fuel cell (SOFC) with a yttria-stabilized zirconia (YSZ) electrolyte and a bi-layer anode composed of nickel oxide gadolinia-doped ceria (NiO-GDC) and NiO-YSZ. The common problems of bulk shrinkage and emergent porosity in the YSZ layer adjacent to the GDC/YSZ interface were avoided by using an interlayer of porous NiO-YSZ as a buffer anode layer between the electrolyte and the NiO-GDC primary anode. Cells were fabricated from commercially available component powders so that unconventional production methods suggested in the literature were avoided, that is, the necessity of glycine-nitrate combustion synthesis, specialty multicomponent oxide powders, sputtering, or chemical vapor deposition. The easily-fabricated cell was successfully utilized with hydrogen and propane fuels as well as carbon deposited on the anode during the cyclic operation with the propane. A cell of similar construction could be used in the exhaust stream of a diesel engine to capture and utilize soot for secondary power generation and decreased particulate pollution without the need for filter regeneration.

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

    SciTech Connect

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

    2013-02-15

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

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

    SciTech Connect

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

    2011-12-11

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

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

    SciTech Connect

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

    2005-07-12

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

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

    PubMed

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

    2011-05-28

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

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

    PubMed

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

    2014-08-01

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

  20. Gadolinia-doped ceria mixed with alkali carbonates for solid oxide fuel cell applications: I. A thermal, structural and morphological insight

    NASA Astrophysics Data System (ADS)

    Benamira, M.; Ringuedé, A.; Albin, V.; Vannier, R.-N.; Hildebrandt, L.; Lagergren, C.; Cassir, M.

    Ceria-based composites are developed and considered as potential electrolytes for intermediate solid oxide fuel cell applications (ITSOFC). After giving a survey of the most relevant results in the literature, the structural, thermal and morphological properties of composite materials based on gadolinia-doped ceria (GDC) and alkali carbonates (Li 2CO 3-K 2CO 3 or Li 2CO 3-Na 2CO 3) are carefully examined. Thermal analyses demonstrate the stability of the composite with very low weight losses of both water and CO 2 during thermal cycling and after 168 h ageing. High-temperature and room-temperature X-ray diffraction allowed determining the precise structure of the composite and its regular and reversible evolution with the temperature. The microstructure and morphology of electrolyte pellets, as observed by scanning electron microscopy (SEM), show two-well separated phases: nanocrystals of GDC and a well-distributed carbonate phase. Finally, electrical conductivity determined by impedance spectroscopy is presented as a function of time to highlight the stability of such composites over 1500 h.

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

    NASA Astrophysics Data System (ADS)

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

    2008-05-01

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

  2. Oxygen vacancy migration in ceria and Pr-doped ceria: a DFT+U study.

    PubMed

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

    2010-03-07

    Oxygen vacancy formation and migration in ceria (CeO(2)) is central to its performance as an ionic conductor. It has been observed that ceria doped with suitable aliovalent cationic dopants improves its ionic conductivity. To investigate this phenomenon, we present total energy calculations within the framework of density functional theory to study oxygen vacancy migration in ceria and Pr-doped ceria (PDC). We report activation energies for oxygen vacancy formation and migration in undoped ceria and for different migration pathways in PDC. The activation energy value for oxygen vacancy migration in undoped ceria was found to be in reasonable agreement with the available experimental and theoretical results. Conductivity values for reduced undoped ceria calculated using theoretical activation energy and attempt frequency were found in reasonably good agreement with the experimental data. For PDC, oxygen vacancy formation and migration were investigated at first, second, and third nearest neighbor positions to a Pr ion. The second nearest neighbor site is found to be the most favorable vacancy formation site. Vacancy migration between first, second, and third nearest neighbors was calculated (nine possible jumps), with activation energies ranging from 0.41 to 0.78 eV for first-nearest-neighbor jumps. Overall, the presence of Pr significantly affects vacancy formation and migration, in a complex manner requiring the investigation of many different migration events. We propose a relationship illuminating the role of additional dopants toward lowering the activation energy for vacancy migration in PDC.

  3. Defect equilibria and chemical expansion in undoped and doped ceria and strontium doped lanthanum cobalt iron oxide oxygen conducting materials and their applications in solid-state electrochemical cells

    NASA Astrophysics Data System (ADS)

    Bishop, Sean R.

    Ceramic oxygen conducting materials are used in many energy-related applications from fuel reforming to electricity generation. In a typical ceramic oxygen conductor, oxygen ions are transmitted through a dense membrane via defects in the material. Hence, defects control the performance of these materials. In low oxygen partial pressure, ceria based materials become non-stoichiometric and can form defect complexes that hinder ionic conductivity. In addition, oxygen non-stoichiometry induces strain (chemical expansion) that can result in stresses for composite or constrained applications. In this dissertation the non-stoichiometry and chemical expansion behavior is reported as a function of PO2 for undoped ceria, gadolinium doped ceria (GDC) and strontium doped lanthanum cobalt iron oxide (LSCF). Undoped ceria was measured at 800°C and GDC and LSCF at 600--900°C in a wide PO2 range. It was found that defect interactions could effectively be modeled in ceria based materials using defect complex formation in a mass action formalism and the results were used to model nonlinear chemical expansion behavior. In LSCF, non-stoichiometry and chemical expansion were modeled using using metallic and semi-conductor models. A semi-conductor model with B-site small polarons best represented the measured behavior. The resulting models and parameters can be used to predict mechanical and electrical behavior of SOFC components. Surface oxygen non-stoichiometry has also been measured by comparing low surface area to high surface area samples. It was found that surface defect concentration previously ignored in the literature can result in erroneous non-stoichiometry measurements. In the latter half of this dissertation these materials are applied in SOFC and ceramic oxygen generator (COG) technology. A strategy is presented here for advanced life support systems employs a catalytic layer combined with a COG cell so that CO2 is reduced all the way to solid carbon and oxygen without

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

    PubMed Central

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

    2016-01-01

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

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

    PubMed

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

    2016-02-29

    An 8 nm-thick gadolinium-doped ceria (GDC) layer was inserted as a cathodic interlayer between the nanoscale proton-conducting yttrium-doped barium zirconate (BZY) electrolyte and the porous platinum cathode of a micro-solid oxide fuel cell (μ-SOFC), which has effectively improved the cathode reaction kinetics and rendered high cell power density. The addition of the GDC interlayer significantly reduced the cathodic activation loss and increased the peak power density of the μ-SOFC by 33% at 400 °C. The peak power density reached 445 mW/cm(2) at 425 °C, which is the highest among the reported μ-SOFCs using proton-conducting electrolytes. The impressive performance was attributed to the mixed protonic and oxygen ionic conducting properties of the nano-granular GDC, and also to the high densities of grain boundaries and lattice defects in GDC interlayer that favored the oxygen incorporation and transportation during the oxygen reduction reaction (ORR) and the water evolution reaction at cathode.

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

    NASA Astrophysics Data System (ADS)

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

    2016-02-01

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

  7. Pyrolysis result of polyethylene waste as fuel for solid oxide fuel cell with samarium doped-ceria (SDC)-carbonate as electrolyte

    NASA Astrophysics Data System (ADS)

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

    2017-02-01

    In this research, the result of pyrolysis on polyethylene was used as fuel for a solid oxide fuel cell (SOFC). The pyrolysis result is a liquid which consists of hydrocarbon chains. According to GC-MS analysis, the hydrocarbons mainly consist of C7 to C20 hydrocarbon chain. Then, the liquid was applied to a single cell of NSDC-L | NSDC | NSDC-L. NSDC is a composite SDC (samarium doped-ceria) with sodium carbonate. Meanwhile, NSDC-L is a composite of NSDC with LiNiCuO (LNC). NSDC and LNC were analyzed by X-ray diffraction to understand their crystal structure. The result shows that presence of carbonate did not change the crystal structure of SDC. SEM EDX analysis for fuel cell before and after being loaded with polyethylene oil to get information of element diffusion to the electrolyte. Meanwhile, the conductivity properties were investigated through impedance measurement. The presence of carbonate even increases the electrical conductivity. The single cell test with the pyrolysis result of polyethylene at 300 – 600 °C, found that the highest power density is at 600 °C with the maximum power density of 0.14 mW/cm2 and open circuit voltage of 0.4 Volt. Elemental analysis at three point spots of single cell NDSC-L |NSDC|NSDC-L found that a migration of ions was occurred during fuel operation at 300 – 600 °C.

  8. Evaluation of the Effect of Sulfur on the Performance of Nickel/Gadolinium‐Doped Ceria Based Solid Oxide Fuel Cell Anodes

    PubMed Central

    Yurkiv, Vitaliy; Costa, Rémi; Schiller, Günter; Friedrich, K. Andreas

    2016-01-01

    Abstract The focus of this study is the measurement and understanding of the sulfur poisoning phenomena of Ni/gadolinium‐doped ceria (CGO) based solid oxide fuel cells (SOFC). Cells with Ni/CGO10 and NiCu5/CGO40 anodes were characterized by using impedance spectroscopy at different temperatures and H2/H2O fuel ratios. The short‐term sulfur poisoning behavior was investigated systematically at temperatures of 800–950 °C, current densities of 0–0.75 A cm−2, and H2S concentrations of 1–20 ppm. A sulfur poisoning mitigation effect was observed at high current loads and temperatures. The poisoning behavior was reversible for short exposure times. It was observed that the sulfur‐affected processes exhibited significantly different relaxation times that depend on the Gd content in the CGO phase. Moreover, it was demonstrated that the capacitance of Ni/CGO10 anodes is strongly dependent on the temperature and gas‐phase composition, which reflects a changing Ce3+/Ce4+ ratio. PMID:27863123

  9. Samarium doped ceria-(Li/Na) 2CO 3 composite electrolyte and its electrochemical properties in low temperature solid oxide fuel cell

    NASA Astrophysics Data System (ADS)

    Di, Jing; Chen, Mingming; Wang, Chengyang; Zheng, Jiaming; Fan, Liangdong; Zhu, Bin

    A composite of samarium doped ceria (SDC) and a binary carbonate eutectic (52 mol% Li 2CO 3/48 mol% Na 2CO 3) is investigated with respect to its morphology, conductivity and fuel cell performances. The morphology study shows the composition could prevent SDC particles from agglomeration. The conductivity is measured under air, argon and hydrogen, respectively. A sharp increase in conductivity occurs under all the atmospheres, which relates to the superionic phase transition in the interface phases between SDC and carbonates. Single cells with the composite electrolyte are fabricated by a uniaxial die-press method using NiO/electrolyte as anode and lithiated NiO/electrolyte as cathode. The cell shows a maximum power density of 590 mW cm -2 at 600 °C, using hydrogen as the fuel and air as the oxidant. Unlike that of cells based on pure oxygen ionic conductor or pure protonic conductor, the open circuit voltage of the SDC-carbonate based fuel cell decreases with an increase in water content of either anodic or cathodic inlet gas, indicating the electrolyte is a co-ionic (H +/O 2-) conductor. The results also exhibit that oxygen ionic conductivity contributes to the major part of the whole conductivity under fuel cell circumstances.

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

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

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

  11. Multi-scale analysis of the diffusion barrier layer of gadolinia-doped ceria in a solid oxide fuel cell operated in a stack for 3000 h

    NASA Astrophysics Data System (ADS)

    Morales, M.; Miguel-Pérez, V.; Tarancón, A.; Slodczyk, A.; Torrell, M.; Ballesteros, B.; Ouweltjes, J. P.; Bassat, J. M.; Montinaro, D.; Morata, A.

    2017-03-01

    The state-of-the-art materials for SOFCs are yttria-stabilized zirconia as electrolyte and lanthanum strontium cobalt ferrite as cathode. However, the formation of insulating phases between them requires the use of diffusion barriers, typically made of gadolinia doped ceria. The study of the stability of this layer during the fabrication and in operando is currently one of the major goals of the SOFC industry. In this work, the cation inter-diffusion at the cathode/barrier layer/electrolyte region is analysed for an anode-supported cell industrially fabricated by conventional techniques, assembled in a short-stack and tested under real operation conditions for 3000 h. A comprehensive study of this cell, and an equivalent non-operated one, is performed in order to understand the inter-diffusion mechanisms with possible effects on the final performance. The analyses evidence that the cation diffusion is occurring during the fabrication process. Despite the significant diffusion of Ce,Gd, Zr, Y and Sr cations, the formation of typically reported CGO-YSZ solid solution is not observed while the presence of isolated grains of SrZrO3 is proved. All in all, this study presents new insights into the stability of the typically employed diffusion barriers for solid oxide cells that will guide future strategies to improve their performance and durability.

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

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

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

  13. Local structural study of doped-ceria by EXAFS spectroscopy

    NASA Astrophysics Data System (ADS)

    Shirbhate, S. C.; Yadav, A. K.; Acharya, S. A.; Sagdeo, A. P.; Jha, S. N.

    2016-05-01

    In the present work, Structural and Local structural study of Sm, Gd doped and Sm-Gd co-doped ceria system has been studied by Extended X-ray Absorption Fine Structure Spectroscopy (EXAFS). These ceria based systems are synthesized by hydrothermal synthesis route. Fluorite structure is confirmed by X-ray diffraction (XRD) and data is well fitted using Rietveld refinement by Full-Prof suite. Local structural changes in terms of coordination with surrounding, inter atomic distances and Debye Waller factor of nearest neighbor and next nearest neighbor has been discussed.

  14. Influence of samaria doping on the resistance of ceria thin films and its implications to the planar oxygen sensing devices

    SciTech Connect

    Gupta, Shilpi; Kuchibhatla, Satyanarayana V N T; Engelhard, Mark H.; Shutthanandan, V.; Nachimuthu, Ponnusamy; Jiang, Weilin; Saraf, Laxmikant V.; Thevuthasan, Suntharampillai; Prasad, Shalini

    2009-05-27

    In order to evaluate and analyze the effect of samarium (Sm) doping on the resistance of cerium oxide, we have grown highly oriented samaria doped ceria (SDC) thin films on sapphire, Al2O3 (0001) substrates by using oxygen plasma-assisted molecular beam epitaxy (OPA-MBE). The film growth was monitored using reflection high-energy electron diffraction (RHEED) which shows two-dimensional growth throughout the deposition. Following growth, the thin films were characterized by X-ray photoelectron spectroscopy (XPS), high-resolution X-ray diffraction (HRXRD), and Rutherford backscattering spectrometry (RBS). XPS depth-profile shows Sm atoms are uniformly distributed in ceria lattice throughout the bulk of the film. The valence states of Ce and Sm in doped thin films are found to be Ce4+ and Sm3+, respectively. HRXRD shows the samaria doped ceria films on Al2O3(0001) exhibit (111) preferred orientation. Ion-channeling in RBS measurements confirms high quality of the thin films. The resistance of the samaria doped ceria films, obtained by two probe measurement capability under various oxygen pressure (1mTorr-100Torr) and temperatures (623K to 973K), is significantly lower than that of pure ceria under same conditions. The 6Sm% doped ceria film is the optimum composition for highest conductivity. This is attributed to the increased oxygen vacant sites in fluorite crystal structure of the epitaxial thin films which facilitate faster oxygen diffusion through hopping process.

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  16. Ceria and copper/ceria functional coatings for electrochemical applications: Materials preparation and characterization

    NASA Astrophysics Data System (ADS)

    Melnik, J.; Fu, X. Z.; Luo, J. L.; Sanger, A. R.; Chuang, K. T.; Yang, Q. M.

    Following preliminary investigations, two electrodeposition techniques (electrophoretic and electrolytic) were selected and adapted for deposition of doped ceria ceramic and copper/doped ceria composite coatings on Ni substrates (foil and foam). The copper/doped ceria composites have potential value as protective functional coatings for current collectors in electrochemical cells including solid oxide fuel sells (SOFC). The doped ceria ceramic coating has potential application as a porous matrix for anodes of SOFCs operating on syngas, sour gas, or hydrocarbons.

  17. Nanodomain formation and distribution in Gd-doped ceria

    SciTech Connect

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

    2012-03-15

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

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

    PubMed

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

    2015-03-28

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

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

    PubMed

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

    2016-12-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

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

  1. Study of fluorescence quenching in aluminum-doped ceria nanoparticles: potential molecular probe for dissolved oxygen.

    PubMed

    Shehata, N; Meehan, K; Leber, D

    2013-05-01

    This work investigates a novel usage of aluminum-doped ceria nanoparticles (ADC-NPs), as the molecular probe in optical fluorescence quenching for sensing the dissolved oxygen (DO). Cerium oxide (ceria) nanoparticles can be considered one of the most unique nanomaterials that are being studied today due to the diffusion and reactivity of oxygen vacancies in ceria, which contributes to its high oxygen storage capability. Aluminum can be considered a promising dopant to increase the oxygen ionic conductivity in ceria nanoparticles which can improve the sensitivity of ceria nanoparticles to DO. The fluorescence intensity of ADC-NPs, synthesized via chemical precipitation, is found to have a strong inverse relationship with the DO concentration in aqueous solutions. Stern-Volmer constant of ADC-NPs at room temperature is determined to be 454.6 M(-1), which indicates that ADC-NPs have a promising sensitivity to dissolved oxygen, compared to many presently used fluorophores. In addition, Stern-Volmer constant is found to have a relatively small dependence on temperature between 25 °C to 50 °C, which shows excellent thermal stability of ADC-NPs sensitivity. Our work suggests that ADC-NPs, at 6 nm, are the smallest diameter DO molecular probes between the currently used optical DO sensors composed of different nanostructures. This investigation can improve the performance of fluorescence-quenching DO sensors for industrial and environmental applications.

  2. Structural and catalytic properties of lanthanide (La, Eu, Gd) doped ceria

    SciTech Connect

    Hernandez, W.Y.; Laguna, O.H.; Centeno, M.A.; Odriozola, J.A.

    2011-11-15

    Ce{sub 0.9}M{sub 0.1}O{sub 2-{delta}} mixed oxides (M=La, Eu and Gd) were synthesized by coprecipitation. Independent of the dopant cation, the obtained solids maintain the F-type crystalline structure, characteristic of CeO{sub 2} (fluorite structure) without phase segregation. The ceria lattice expands depending on the ionic radii of the dopant cation, as indicated by X-ray diffraction studies. This effect also agrees with the observed shift of the F{sub 2g} Raman vibrational mode. The presence of the dopant cations in the ceria lattice increases the concentration of structural oxygen vacancies and the reducibility of the redox pair Ce{sup 4+}/Ce{sup 3+}. All synthesized materials show higher catalytic activity for the CO oxidation reaction than that of bare CeO{sub 2}, being Eu-doped solid the one with the best catalytic performances despite of its lower surface area. - Graphical abstract: In this work, Ce{sub 0.9}M{sub 0.1}O{sub 2-{delta}} mixed oxides (M=La, Eu and Gd) were synthesized by coprecipitation. Independent of the dopant cation, the obtained solids maintain the F-type crystalline structure, characteristic of CeO{sub 2} (fluorite structure) without phase segregation. The ceria lattice expands depending on the ionic radii of the dopant cation, as indicated by X-ray diffraction studies. This effect also agrees with the observed shift of the F{sub 2g} Raman vibrational mode. The presence of the dopant cations in the ceria lattice increases the concentration of structural oxygen vacancies and the reducibility of the redox pair Ce{sup 4+}/Ce{sup 3+}. All synthesized materials show higher catalytic activity for the CO oxidation reaction than that of bare CeO{sub 2}, being Eu-doped solid the one with the best catalytic performances despite of its lower surface area. Highlights: > Lanthanide doped ceria as catalytic supports for CO oxidation reaction. > A higher concentration of oxygen vacancies promotes a higher catalytic activity. > Eu-doped ceria shows

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

    SciTech Connect

    Datta, Pradyot Majewski, Peter; Aldinger, Fritz

    2009-02-15

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

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

    NASA Astrophysics Data System (ADS)

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

    2017-03-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-09-01

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

  6. Gadolinia-Doped Ceria Cathodes for Electrolysis of CO2

    NASA Technical Reports Server (NTRS)

    Adler, Stuart B.

    2009-01-01

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

  7. Carbon deposition behaviour in metal-infiltrated gadolinia doped ceria electrodes for simulated biogas upgrading in solid oxide electrolysis cells

    NASA Astrophysics Data System (ADS)

    Duboviks, V.; Lomberg, M.; Maher, R. C.; Cohen, L. F.; Brandon, N. P.; Offer, G. J.

    2015-10-01

    One of the attractive applications for reversible Solid Oxide Cells (SOCs) is to convert CO2 into CO via high temperature electrolysis, which is particularly important for biogas upgrading. To improve biogas utility, the CO2 component can be converted into fuel via electrolysis. A significant issue for SOC operation on biogas is carbon-induced catalyst deactivation. Nickel is widely used in SOC electrodes for reasons of cost and performance, but it has a low tolerance to carbon deposition. Two different modes of carbon formation on Ni-based electrodes are proposed in the present work based on ex-situ Raman measurements which are in agreement with previous studies. While copper is known to be resistant towards carbon formation, two significant issues have prevented its application in SOC electrodes - namely its relatively low melting temperature, inhibiting high temperature sintering, and low catalytic activity for hydrogen oxidation. In this study, the electrodes were prepared through a low temperature metal infiltration technique. Since the metal infiltration technique avoids high sintering temperatures, Cu-Ce0.9Gd0.1O2-δ (Cu-CGO) electrodes were fabricated and tested as an alternative to Ni-CGO electrodes. We demonstrate that the performance of Cu-CGO electrodes is equivalent to Ni-CGO electrodes, whilst carbon formation is fully suppressed when operated on biogas mixture.

  8. Is Steam an Oxidant or a Reductant for Nickel/Doped‐Ceria Cermets?

    PubMed Central

    Papaefthimiou, Vasiliki; Niakolas, Dimitris K.; Paloukis, Fotios; Dintzer, Thierry

    2016-01-01

    Abstract Nickel/doped‐ceria composites are promising electrocatalysts for solid‐oxide fuel and electrolysis cells. Very often steam is present in the feedstock of the cells, frequently mixed with other gases, such as hydrogen or CO2. An increase in the steam concentration in the feed mixture is considered accountable for the electrode oxidation and the deactivation of the device. However, direct experimental evidence of the steam interaction with nickel/doped‐ceria composites, with adequate surface specificity, are lacking. Herein we explore in situ the surface state of nickel/gadolinium‐doped ceria (NiGDC) under O2, H2, and H2O environments by using near‐ambient‐pressure X‐ray photoelectron and absorption spectroscopies. Changes in the surface oxidation state and composition of NiGDC in response to the ambient gas are observed. It is revealed that, in the mbar pressure regime and at intermediate temperature conditions (500–700 °C), steam acts as an oxidant for nickel but has a dual oxidant/reductant function for doped ceria. PMID:27792266

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

    NASA Astrophysics Data System (ADS)

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

    2013-11-01

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

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

    PubMed Central

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

    2016-01-01

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

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

    PubMed

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

    2016-01-01

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

  12. Mechanical characterization of hydroxyapatite, thermoelectric materials and doped ceria

    NASA Astrophysics Data System (ADS)

    Fan, Xiaofeng

    For a variety of applications of brittle ceramic materials, porosity plays a critical role structurally and/or functionally, such as in engineered bone scaffolds, thermoelectric materials and in solid oxide fuel cells. The presence of porosity will affect the mechanical properties, which are essential to the design and application of porous brittle materials. In this study, the mechanical property versus microstructure relations for bioceramics, thermoelectric (TE) materials and solid oxide fuel cells were investigated. For the bioceramic material hydroxyapatite (HA), the Young's modulus was measured using resonant ultrasound spectroscopy (RUS) as a function of (i) porosity and (ii) microcracking damage state. The fracture strength was measured as a function of porosity using biaxial flexure testing, and the distribution of the fracture strength was studied by Weibull analysis. For the natural mineral tetrahedrite based solid solution thermoelectric material (Cu10Zn2As4S13 - Cu 12Sb4S13), the elastic moduli, hardness and fracture toughness were studied as a function of (i) composition and (ii) ball milling time. For ZiNiSn, a thermoelectric half-Heusler compound, the elastic modulus---porosity and hardness---porosity relations were examined. For the solid oxide fuel cell material, gadolina doped ceria (GDC), the elastic moduli including Young's modulus, shear modulus, bulk modulus and Poisson's ratio were measured by RUS as a function of porosity. The hardness was evaluated by Vickers indentation technique as a function of porosity. The results of the mechanical property versus microstructure relations obtained in this study are of great importance for the design and fabrication of reliable components with service life and a safety factor. The Weibull modulus, which is a measure of the scatter in fracture strength, is the gauge of the mechanical reliability. The elastic moduli and Poisson's ratio are needed in analytical or numerical models of the thermal and

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

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

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

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

    SciTech Connect

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

    2010-07-15

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

  15. A correlation between the ionic conductivities and the formation enthalpies of trivalent-doped ceria at relatively low temperatures.

    PubMed

    Avila-Paredes, Hugo J; Shvareva, Tatiana; Chen, Weiqun; Navrotsky, Alexandra; Kim, Sangtae

    2009-10-14

    We report a correlation between oxygen ionic conductivity and the enthalpy of formation of trivalent-doped ceria from the component binary oxides observed at relatively low temperatures (150-275 degrees C). The bulk conductivities of La-doped ceria samples identical to those previously examined by thermochemical studies were measured as a function of La content for a direct comparison. The conductivity showed a maximum at a La concentration of 5 mol%, implying that the number of freely mobile oxygen vacancies reaches a maximum near that doping level in the temperature range of interest. The formation enthalpies previously reported by Chen and Navrotsky also show a maximum, indicating destabilization near that composition. Additional measurements show that this maximum is very pronounced and sharply peaked near that composition. These enthalpies suggest that the energetically favorable long-range interactions between the charged defects that trap the oxygen vacancies become dominant above 5 mol% doping in the CeO2-LaO1.5 solid solution. In addition, the conductivities measured from independently prepared Gd-doped ceria samples show a maximum at around 10 mol% doping below 450 degrees C as anticipated from a pronounced maximum in the formation enthalpies of the CeO2-GdO1.5 solid solution. These empirical findings confirm that the ionic conductivity of trivalent-doped ceria is strongly enough correlated with its formation enthalpy at relatively low temperatures so that information about the critical dopant concentration associated with the conductivity maximum may be gained from the formation enthalpies of the solid solutions, and vice versa. We have no direct information about this correlation at higher temperatures; both thermodynamics and conductivity maximum might change if the defect clusters dissociate to any significant extent.

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

    SciTech Connect

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

    2014-03-17

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

  17. The interaction of biomass gasification syngas components with tar in a solid oxide fuel cell and operational conditions to mitigate carbon deposition on nickel-gadolinium doped ceria anodes

    NASA Astrophysics Data System (ADS)

    Mermelstein, J.; Millan, M.; Brandon, N. P.

    The combination of biomass gasification with solid oxide fuel cells (SOFCs) is gaining increasing interest as an efficient and environmentally benign method of producing electricity and heat. However, tars in the gas stream arising from the gasification of biomass material can deposit carbon on the SOFC anode, having detrimental effects to the life cycle and operational characteristics of the fuel cell. This work examines the impact of biomass gasification syngas components combined with benzene as a model tar, on carbon formation on Ni/CGO (gadolinium-doped ceria) SOFC anodes. Thermodynamic calculations suggest that SOFCs operating at temperatures > 750 °C are not susceptible to carbon deposition from a typical biomass gasification syngas containing 15 g m -3 benzene. However, intermediate temperature SOFCs operating at temperatures < 650 °C require threshold current densities well above what is technologically achievable to inhibit the effects of carbon deposition. SOFC anodes have been shown to withstand tar levels of 2-15 g m -3 benzene at 765 °C for 3 h at a current density of 300 mA cm -2, with negligible impact on the electrochemical performance of the anode. Furthermore, no carbon could be detected on the anode at this current density when benzene levels were <5 g m -3.

  18. Improved performance of a symmetrical solid oxide fuel cell by swapping the roles of doped ceria and La0.6Sr1.4MnO4+δ in the electrode

    NASA Astrophysics Data System (ADS)

    Shen, Jian; Yang, Guangming; Zhang, Zhenbao; Tadé, Moses O.; Zhou, Wei; Shao, Zongping

    2017-02-01

    Symmetrical solid oxide fuel cells (SSOFCs) show many advantageous features as compared with conventional cells with nickel cermet anode and oxide cathode. A K2NiF4-type layer-structured oxide, La0.6Sr1.4MnO4+δ (LSMO4), was reported to be a potential electrode for SSOFCs, and the modification of LSMO4 surface with samaria-doped ceria (SDC) and NiO was found to be the key in improving performance. In this study, the swapping of roles for SDC and LSMO4 in electrodes of SSOFCs is exploited, i.e., SDC is applied as the scaffold and LSMO4 as the surface modifier. Different from pristine LSMO4, the impregnated LSMO4 demonstrates amorphous phase. Compared to NiO-SDC impregnated LSMO4, NiO-LSMO4/SDC electrodes show a superior cathodic performance with an area specific resistance of 0.1 Ω cm2 at 700 °C. Under optimized conditions, maximum power densities of 714 and 108 mW cm-2 at 800 °C are achieved for an electrolyte-supported symmetrical single cell with a NiO-LSMO4/SDC electrode operating with hydrogen and methane, respectively. The difference in performance of the electrodes built by swapping the role and function of the SDC and LSMO4 phases is discussed, and a possible mechanism responsible for such different behaviours in cell power outputs via the impregnation of LSMO4 (NiO)+SDC electrodes is proposed.

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

    PubMed

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

    2015-08-12

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-02-01

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

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

    SciTech Connect

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

    2014-11-17

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

  2. Stable high conductivity ceria/bismuth oxide bilayered electrolytes

    SciTech Connect

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

    1997-01-01

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

  3. Structure and segregation of dopant-defect complexes at grain boundaries in nanocrystalline doped ceria.

    PubMed

    Dholabhai, Pratik P; Aguiar, Jeffery A; Wu, Longjia; Holesinger, Terry G; Aoki, Toshihiro; Castro, Ricardo H R; Uberuaga, Blas P

    2015-06-21

    Grain boundaries (GBs) dictate vital properties of nanocrystalline doped ceria. Thus, to understand and predict its properties, knowledge of the interaction between dopant-defect complexes and GBs is crucial. Here, we report atomistic simulations, corroborated with first principles calculations, elucidating the fundamental dopant-defect interactions at model GBs in gadolinium-doped and manganese-doped ceria. Gadolinium and manganese are aliovalent dopants, accommodated in ceria via a dopant-defect complex. While the behavior of isolated dopants and vacancies is expected to depend on the local atomic structure at GBs, the added structural complexity associated with dopant-defect complexes is found to have key implications on GB segregation. Compared to the grain interior, energies of different dopant-defect arrangements vary significantly at the GBs. As opposed to bulk, the stability of oxygen vacancy is found to be sensitive to the dopant arrangement at GBs. Manganese exhibits a stronger propensity for segregation to GBs than gadolinium, revealing that accommodation of dopant-defect clusters depends on the nature of dopants. Segregation strength is found to depend on the GB character, a result qualitatively supported by our experimental observations based on scanning transmission electron microscopy. The present results indicate that segregation energies, availability of favorable sites, and overall stronger binding of dopant-defect complexes would influence ionic conductivity across GBs in nanocrystalline doped ceria. Our comprehensive investigation emphasizes the critical role of dopant-defect interactions at GBs in governing functional properties in fluorite-structured ionic conductors.

  4. Peculiar surface-interface properties of nanocrystalline ceria-cobalt oxides with enhanced oxygen storage capacity.

    PubMed

    Qiu, Nan; Zhang, Jing; Wu, Ziyu

    2014-11-07

    Peculiar surface-interface properties of nanocrystalline ceria-cobalt oxides were evidenced by X-ray diffraction, transmission electron microscopy and X-ray absorption spectroscopy. It was found that cobalt foreign cations modify the surface oxygen vacancies of ceria at the atomic level, inducing the exposure of well-defined reactive faces between the ceria-host and the cobalt oxide interface. These modifications of the surface-interface structure promoted a remarkable increase in the oxygen storage capacity of ceria nanocrystals.

  5. H2 and CO oxidation process at the three-phase boundary of Cu-ceria cermet anode for solid oxide fuel cell

    NASA Astrophysics Data System (ADS)

    Zheng, Minghao; Wang, Shuang; Li, Mei; Xia, Changrong

    2017-03-01

    Cu-ceria cermets have been widely investigated as the anode materials for solid oxide fuel cells (SOFCs) that operated with hydrocarbon fuels. However, the anode reaction processes are not clear yet, especially those at the ceria-Cu-gas three phase boundary (3 PB). This work investigates samaria-doped ceria (SDC)-Cu-gas 3 PB reaction kinetics for the oxidation of H2 and CO, the products from hydrocarbons via external and internal reforming. Electrochemical conductivity relaxation measurement demonstrates that Cu is a synergistic catalyst that can significantly increase the reaction rate. The reaction at 3 PB contributes 81.3/66.8% of H2/CO oxidation when 5.4% SDC surface is covered with Cu particles. Combining with AC impedance analysis, elementary steps are proposed for the reaction at 3 PB. Water vapor combining to oxygen vacancy and carbon monoxide transforming to carbonate are the rate-determining steps for the oxidation of H2 and CO, respectively. Cu-SDC has shown much higher catalytic activity, i.e. about fivefold reaction rate, for the oxidation of CO than H2. In addition, Cu-SDC electrodes exhibit lower interfacial polarization resistance and lower activation energy for the electrochemical oxidation of CO than H2. Consequently, CO is easier to be oxidized than H2 when the Cu-ceria anode is fueled with syngas, the reforming product from hydrocarbons.

  6. Tailoring gadolinium-doped ceria-based solid oxide fuel cells to achieve 2 W cm(-2) at 550 °C.

    PubMed

    Lee, Jin Goo; Park, Jeong Ho; Shul, Yong Gun

    2014-06-04

    Low-temperature operation is necessary for next-generation solid oxide fuel cells due to the wide variety of their applications. However, significant increases in the fuel cell losses appear in the low-temperature solid oxide fuel cells, which reduce the cell performance. To overcome this problem, here we report Gd0.1Ce0.9O1.95-based low-temperature solid oxide fuel cells with nanocomposite anode functional layers, thin electrolytes and core/shell fibre-structured Ba0.5Sr0.5Co0.8Fe0.2O3-δ-Gd0.1Ce0.9O1.95 cathodes. In particular, the report describes the use of the advanced electrospinning and Pechini process in the preparation of the core/shell-fibre-structured cathodes. The fuel cells show a very high performance of 2 W cm(-2) at 550 °C in hydrogen, and are stable for 300 h even under the high current density of 1 A cm(-2). Hence, the results suggest that stable and high-performance solid oxide fuel cells at low temperatures can be achieved by modifying the microstructures of solid oxide fuel cell components.

  7. Effect of 1 MeV electrons on ceria-doped solar cell cover glass

    NASA Technical Reports Server (NTRS)

    Haynes, G. A.

    1973-01-01

    The effect of 1 MeV electrons on the transmission properties of 1.5-percent ceria-doped solar cell cover glass was studied. Samples of doped and undoped cover glass and synthetic fused silica were irradiated with a total integrated flux of 10 to the 15th power e/sq cm. Wideband transmission and spectral transmission measurements were made before and after irradiation. The results indicate that 1.5-percent ceria-doped cover glass is much less sensitive to radiation induced discoloration than undoped cover glass. Consequently, the glass is comparable to synthetic fused silica when used as a radiation resistant solar cell cover for many space missions.

  8. High electrochemical activity of the oxide phase in model ceria-Pt and ceria-Ni composite anodes.

    PubMed

    Chueh, William C; Hao, Yong; Jung, WooChul; Haile, Sossina M

    2011-12-04

    Fuel cells, and in particular solid-oxide fuel cells (SOFCs), enable high-efficiency conversion of chemical fuels into useful electrical energy and, as such, are expected to play a major role in a sustainable-energy future. A key step in the fuel-cell energy-conversion process is the electro-oxidation of the fuel at the anode. There has been increasing evidence in recent years that the presence of CeO(2)-based oxides (ceria) in the anodes of SOFCs with oxygen-ion-conducting electrolytes significantly lowers the activation overpotential for hydrogen oxidation. Most of these studies, however, employ porous, composite electrode structures with ill-defined geometry and uncontrolled interfacial properties. Accordingly, the means by which electrocatalysis is enhanced has remained unclear. Here we demonstrate unambiguously, through the use of ceria-metal structures with well-defined geometries and interfaces, that the near-equilibrium H(2) oxidation reaction pathway is dominated by electrocatalysis at the oxide/gas interface with minimal contributions from the oxide/metal/gas triple-phase boundaries, even for structures with reaction-site densities approaching those of commercial SOFCs. This insight points towards ceria nanostructuring as a route to enhanced activity, rather than the traditional paradigm of metal-catalyst nanostructuring.

  9. Structure of vanadium oxide supported on ceria by multi-wavelength Raman spectroscopy

    SciTech Connect

    Wu, Zili; Rondinone, Adam Justin; Overbury, Steven {Steve} H

    2011-01-01

    ABSTRACT The structure of vanadium oxide species supported on ceria (VOx/CeO2) was investigated under various conditions by in situ multi-wavelength Raman spectroscopy, IR spectroscopy, isotopic labeling and temperature programmed reduction (TPR). For the first time, the detailed structure of dehydrated VOx species was revealed on the polycrystalline ceria support. VOx species can co-exist on ceria surface in the structure of monomer, dimer, trimer, polymer, crystalline V2O5 and CeVO4 as a function of VOx loading. These species interact strongly with both the defect sites and labile surface oxygen of ceria, passivating the redox property of ceria. Under ambient condition, the dispersed VOx species are hydrated into polyvanadate species which can be reversibly dehydrated back to the original structure forms. The ceria support with defect sites facilitates the interaction between water (H218O) and V16Ox species, leading to very facile isotopic oxygen exchange between the two even at room temperature. During H2 reduction, both the VOx species and the ceria support can be reduced with ceria surface being more reducible. The reducibility of various dispersed VOx species scales with their polymerization degree, i.e., polymer > trimer > dimer > monomer. The reoxidation of reduced VOx species is found to proceed via ceria lattice oxygen instead of the gas phase oxygen where ceria acts as an oxygen buffer. The revealed structure evolution of surface VOx species on ceria under hydrated, dehydrated, reduced, and regenerated conditions provides a basis for understanding the vanadia-ceria catalysis.

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

    SciTech Connect

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

    2010-12-01

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

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

    SciTech Connect

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

    2011-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-11-01

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

  13. Low-temperature ceria-electrolyte solid oxide fuel cells for efficient methanol oxidation

    NASA Astrophysics Data System (ADS)

    Meng, Xie; Zhan, Zhongliang; Liu, Xuejiao; Wu, Hao; Wang, Shaorong; Wen, Tinglian

    Low temperature anode-supported solid oxide fuel cells with thin films of samarium-doped ceria (SDC) as electrolytes, graded porous Ni-SDC anodes and composite La 0.6Sr 0.4Co 0.2Fe 0.8O 3 (LSCF)-SDC cathodes are fabricated and tested with both hydrogen and methanol fuels. Power densities achieved with hydrogen are between 0.56 W cm -2 at 500 °C and 1.09 W cm -2 at 600 °C, and with methanol between 0.26 W cm -2 at 500 °C and 0.82 W cm -2 at 600 °C. The difference in the cell performance can be attributed to variation in the interfacial polarization resistance due to different fuel oxidation kinetics, e.g., 0.21 Ω cm 2 for methanol versus 0.10 Ω cm 2 for hydrogen at 600 °C. Further analysis suggests that the leakage current densities as high as 0.80 A cm -2 at 600 °C and 0.11 A cm -2 at 500 °C, resulting from the mixed electronic and ionic conductivity in the SDC electrolyte and thus reducing the fuel efficiency, can nonetheless help remove any carbon deposit and thereby ensure stable and coking-free operation of low temperature SOFCs in methanol fuels.

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

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

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

  15. Highly CO2-Tolerant Cathode for Intermediate-Temperature Solid Oxide Fuel Cells: Samarium-Doped Ceria-Protected SrCo0.85Ta0.15O3-δ Hybrid.

    PubMed

    Li, Mengran; Zhou, Wei; Zhu, Zhonghua

    2017-01-25

    Susceptibility to CO2 is one of the major challenges for the long-term stability of the alkaline-earth-containing cathodes for intermediate-temperature solid oxide fuel cells. To alleviate the adverse effects from CO2, we incorporated samarium-stabilized ceria (SDC) into a SrCo0.85Ta0.15O3-δ (SCT15) cathode by either mechanical mixing or a wet impregnation method and evaluated their cathode performance stability in the presence of a gas mixture of 10% CO2, 21% O2, and 69% N2. We observed that the CO2 tolerance of the hybrid cathode outperforms the pure SCT15 cathode by over 5 times at 550 °C. This significant enhancement is likely attributable to the low CO2 adsorption and reactivity of the SDC protective layer, which are demonstrated through thermogravimetric analysis, energy-dispersive spectroscopy, and electrical conductivity study.

  16. Characterization of Cu, Ag and Pt added La 0.6Sr 0.4Co 0.2Fe 0.8O 3- δ and gadolinia-doped ceria as solid oxide fuel cell electrodes by temperature-programmed techniques

    NASA Astrophysics Data System (ADS)

    Huang, Ta-Jen; Shen, Xian-De; Chou, Chien-Liang

    Cu, Ag and Pt added La 0.6Sr 0.4Co 0.2Fe 0.8O 3- δ (LSCF) and gadolinia-doped ceria (GDC) were analyzed by the temperature-programmed techniques for their characteristics as either the cathode or the anode of the solid oxide fuel cells (SOFCs). Temperature-programmed oxidation using CO 2 was used to characterize the cathode materials while temperature-programmed reduction (TPR) using H 2 and TPR using CO were used to characterize the anode materials. These techniques can offer an easy screening of the materials as the SOFC electrodes. The effects of adding Cu, Ag and Pt to LSCF for the cathodic reduction activity and the anodic oxidation activity are different-Cu > Ag > Pt for reduction and Pt > Cu > Ag for oxidation. The CO oxidation activities are higher than the H 2 oxidation activities. Adding GDC to LSCF can increase both reduction and oxidation activities. The LSCF-GDC composite has a maximum activity for either reduction or oxidation when LSCF/GDC is 2 in weight.

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

    SciTech Connect

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

    2012-01-01

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

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

    PubMed

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

    2016-06-28

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

  19. UV and visible Raman studies of oxygen vacancies in rare-earth-doped ceria.

    PubMed

    Guo, Ming; Lu, Jiqing; Wu, Yanni; Wang, Yuejuan; Luo, Mengfei

    2011-04-05

    Surface properties of rare-earth (RE) doped ceria (RE = Sm, Gd, Pr, and Tb) were investigated by UV (325 nm) and visible (514, 633, and 785 nm) Raman spectroscopy, combined with UV-vis diffuse reflectance spectroscopy, high-resolution transmission electron microscopy, and X-ray photoelectron spectra techniques. It was found that the optical absorption property of samples, the wavelength of detecting laser line, and the inhomogeneous distribution of the dopants significantly affected the obtained surface information, namely, the peak intensity and shape at ca. 460 and 570 cm(-1), as well as the observed oxygen vacancy concentration (A(570)/A(460)). The UV laser line detected the surface information of RE-doped ceria and disclosed the presence of many oxygen vacancies in the samples. The visible laser lines penetrated into the inner layer of the Sm- or Gd-doped CeO(2) and reflected the whole information of samples because of their weak absorptions of the visible laser. However, the Pr- or Tb-doped CeO(2) absorbed visible light strongly; thus, the laser can only determine the outer surface information of the sample.

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

    SciTech Connect

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

    2008-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-08-01

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

  2. Methane Oxidation on Pd-Ceria. A DFT Study of the Combustion Mechanism over Pd, PdO and Pd-ceria Sites

    SciTech Connect

    Mayernick, Adam D.; Janik, Michael J.

    2010-12-24

    Palladium/ceria exhibits unique catalytic activity for hydrocarbon oxidation; however, the chemical and structural properties of active sites on the palladium–ceria surface are difficult to characterize. Strong interactions between palladium and the ceria support stabilize oxidized Pdδ+ species, which may contribute to the significant activity of Pd/ceria for methane oxidation. We present a density functional theory (DFT + U) investigation into methane oxidation over Pd/ceria and quantify the activity of the PdxCe1-xO2(1 1 1) mixed oxide surface in comparison with the PdO(1 0 0) and Pd(1 1 1) surfaces. The methane activation barrier is lowest over the PdxCe1-xO2(1 1 1) surface, even lower than over the Pd(1 1 1) surface or low coordinated stepped or kinked Pd sites. Subsequent reaction steps in complete oxidation, including product desorption and vacancy refilling, are considered to substantiate that methane activation remains the rate-limiting step despite the low barrier over PdxCe1-xO2(1 1 1). The low barrier over the PdxCe1-xO2(1 1 1) surface demonstrates that mixed ceria-noble metal oxides offer the potential for improved hydrocarbon oxidation performance with respect to dispersed noble metal particles on ceria.

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

    PubMed Central

    Kim, Sang Woo; Ahn, Jae-Pyoung

    2013-01-01

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

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

    SciTech Connect

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

    2007-04-12

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

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

    DOE PAGES

    Yang, Nan; Shi, Yanuo; Schweiger, Sebastian; ...

    2016-05-18

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

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

    SciTech Connect

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

    2016-05-18

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

  7. Role of Associated Defects in Oxygen Ion Conduction and Surface Exchange Reaction for Epitaxial Samaria-Doped Ceria Thin Films as Catalytic Coatings.

    PubMed

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

    2016-06-15

    Samaria-doped ceria (SDC) thin films are particularly important for energy and electronic applications such as microsolid oxide fuel cells, electrolyzers, sensors, and memristors. In this paper, we report a comparative study investigating ionic conductivity and surface reactions for well-grown epitaxial SDC films varying the samaria doping concentration. With increasing doping above 20 mol % of samaria, an enhancement in the defect association is observed by Raman spectroscopy. The role of such associated defects on the films̀ oxygen ion transport and exchange is investigated by electrochemical impedance spectroscopy and electrochemical strain microscopy (ESM). The measurements reveal that the ionic transport has a sharp maximum in ionic conductivity and drops in its activation energy down to 0.6 eV for 20 mol % doping. Increasing the doping concentration further up to 40 mol %, it raises the activation energy substantially by a factor of 2. We ascribe the sluggish transport kinetics to the "bulk" ionic-near ordering in case of the heavily doped epitaxial films. Analysis of the ESM first-order reversal curve measurements indicates that these associated defects may have a beneficial role by lowering the activation of the oxygen exchange "surface" reaction for heavily doped 40 mol % of samaria. In a model experiment, through a solid solution series of samaria doped ceria epitaxial films, we reveal that the occurrence of associated defects in the bulk affects the surface charging state of the SDC films to increase the exchange rates. The implication of these findings is the design of coatings with tuned oxygen surface exchange by controlling the bulk associated clusters for future electrocatalytic applications.

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

    NASA Astrophysics Data System (ADS)

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

    2016-12-01

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

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

    PubMed Central

    Takacs, M.; Steinfeld, A.

    2015-01-01

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

  10. The origin of grain boundary capacitance in highly doped ceria.

    PubMed

    Souza, Eduardo Caetano C; Goodenough, John B

    2016-02-17

    The origin of a grain-boundary capacitance in mixed oxide-ion/electronic conductors has been investigated for the case of Ce0.8Sm0.2O1.9-δ using a.c. impedance spectroscopy under low pO2 from 250 to 400 °C. The observed capacitance is interpreted in terms of Ce(III):4f(1) electrons first introduced into the grains and not into the grain boundaries.

  11. Rat brain pro-oxidant effects of peripherally administered 5 nm ceria 30 days after exposure.

    PubMed

    Hardas, Sarita S; Sultana, Rukhsana; Warrier, Govind; Dan, Mo; Florence, Rebecca L; Wu, Peng; Grulke, Eric A; Tseng, Michael T; Unrine, Jason M; Graham, Uschi M; Yokel, Robert A; Butterfield, D Allan

    2012-10-01

    The objective of this study was to determine the residual pro-or anti-oxidant effects in rat brain 30 days after systemic administration of a 5 nm citrate-stabilized ceria dispersion. A ∼4% aqueous ceria dispersion was iv-infused (0 or 85 mg/kg) into rats which were terminated 30 days later. Ceria concentration, localization, and chemical speciation in the brain was assessed by inductively coupled plasma mass spectrometry (ICP-MS), light and electron microscopy (EM), and electron energy loss spectroscopy (EELS), respectively. Pro- or anti-oxidant effects were evaluated by measuring levels of protein carbonyls (PC), 3-nitrotyrosine (3NT), and protein-bound-4-hydroxy-2-trans-nonenal (HNE) in the hippocampus, cortex, and cerebellum. Glutathione reductase (GR), glutathione peroxidase (GPx), superoxide dismutase (SOD), and catalase levels and activity were measured in addition to levels of inducible nitric oxide (iNOS), and heat shock protein-70 (Hsp70). The blood brain barrier (BBB) was visibly intact and no ceria was seen in the brain cells. Ceria elevated PC and Hsp70 levels in hippocampus and cerebellum, while 3NT and iNOS levels were elevated in the cortex. Whereas glutathione peroxidase and catalase activity were decreased in the hippocampus, GR levels were decreased in the cortex, and GPx and catalase levels were decreased in the cerebellum. The GSH:GSSG ratio, an index of cellular redox status, was decreased in the hippocampus and cerebellum. The results are in accordance with the observation that this nanoscale material remains in this mammal model up to 30 days after its administration and the hypothesis that it exerts pro-oxidant effects on the brain without crossing the BBB. These results have important implications on the potential use of ceria ENM as therapeutic agents.

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

    SciTech Connect

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

    2015-01-01

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

  13. In Vivo Processing of Ceria Nanoparticles inside Liver: Impact on Free-Radical Scavenging Activity and Oxidative Stress.

    PubMed

    Graham, Uschi M; Tseng, Michael T; Jasinski, Jacek B; Yokel, Robert A; Unrine, Jason M; Davis, Burtron H; Dozier, Alan K; Hardas, Sarita S; Sultana, Rukhsana; Grulke, Eric A; Allan Butterfield, D

    2014-08-01

    The cytotoxicity of ceria ultimately lies in its electronic structure, which is defined by the crystal structure, composition, and size. Despite previous studies focused on ceria uptake, distribution, biopersistance, and cellular effects, little is known about its chemical and structural stability and solubility once sequestered inside the liver. Mechanisms will be presented that elucidate the in vivo transformation in the liver. In vivo processed ceria reveals a particle-size effect towards the formation of ultrafines, which represent a second generation of ceria. A measurable change in the valence reduction of the second-generation ceria can be linked to an increased free-radical scavenging potential. The in vivo processing of the ceria nanoparticles in the liver occurs in temporal relation to the brain cellular and protein clearance responses that stem from the ceria uptake. This information is critical to establish a possible link between cellular processes and the observed in vivo transformation of ceria. The temporal linkage between the reversal of the pro-oxidant effect (brain) and ceria transformation (liver) suggests a cause-effect relationship.

  14. Investigations of oxidative stress effects and their mechanisms in rat brain after systemic administration of ceria engineered nanomaterials

    NASA Astrophysics Data System (ADS)

    Hardas, Sarita S.

    Advancing applications of engineered nanomaterials (ENM) in various fields create the opportunity for intended (e.g. drug and gene delivery) or unintended (e.g. occupational and environmental) exposure to ENM. However, the knowledge of ENM-toxicity is lagging behind their application development. Understanding the ENM hazard can help us to avoid potential human health problems associated with ENM applications as well as to increase their public acceptance. Ceria (cerium [Ce] oxide) ENM have many current and potential commercial applications. Beyond the traditional use of ceria as an abrasive, the scope of ceria ENM applications now extends into fuel cell manufacturing, diesel fuel additives and for therapeutic intervention as a putative antioxidant. However, the biological effects of ceria ENM exposure have yet to be fully defined. Both pro-and anti-oxidative effects of ceria ENM exposure are repeatedly reported in literature. EPA, NIEHS and OECD organizations have nominated ceria for its toxicological evaluation. All these together gave us the impetus to examine the oxidative stress effects of ceria ENM after systemic administration. Induction of oxidative stress is one of the primary mechanisms of ENM toxicity. Oxidative stress plays an important role in maintaining the redox homeostasis in the biological system. Increased oxidative stress, due to depletion of antioxidant enzymes or molecules and / or due to increased production of reactive oxygen (ROS) or nitrogen (RNS) species may lead to protein oxidation, lipid peroxidation and/or DNA damage. Increased protein oxidation or lipid peroxidation together with antioxidant protein levels and activity can serve as markers of oxidative stress. To investigate the oxidative stress effects and the mechanisms of ceria-ENM toxicity, fully characterized ceria ENM of different sizes (˜ 5nm, 15nm, 30nm, 55nm and nanorods) were systematically injected into rats intravenously in separate experiments. Three brain regions

  15. 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).

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

    PubMed

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

    2015-03-03

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

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

    SciTech Connect

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

    2011-04-15

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

  18. Doped zinc oxide microspheres

    DOEpatents

    Arnold, Jr., Wesley D.; Bond, Walter D.; Lauf, Robert J.

    1993-01-01

    A new composition and method of making same for a doped zinc oxide microsphere and articles made therefrom for use in an electrical surge arrestor which has increased solid content, uniform grain size and is in the form of a gel.

  19. Doped zinc oxide microspheres

    DOEpatents

    Arnold, W.D. Jr.; Bond, W.D.; Lauf, R.J.

    1993-12-14

    A new composition and method of making same for a doped zinc oxide microsphere and articles made therefrom for use in an electrical surge arrestor which has increased solid content, uniform grain size and is in the form of a gel. 4 figures.

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

    NASA Astrophysics Data System (ADS)

    Mirfakhraei, Behzad

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

  1. Electrical, Electrochemical, and Optical Characterization of Ceria Films

    NASA Astrophysics Data System (ADS)

    Oh, Tae-Sik

    Acceptor-doped ceria has been recognized as a promising intermediate temperature solid oxide fuel cell electrode/electrolyte material. For practical implementation of ceria as a fuel cell electrolyte and for designing model experiments for electrochemical activity, it is necessary to fabricate thin films of ceria. Here, metal-organic chemical vapor deposition was carried out in a homemade reactor to grow ceria films for further electrical, electrochemical, and optical characterization. Doped/undoped ceria films are grown on single crystalline oxide wafers with/without Pt line pattern or Pt solid layer. Deposition conditions were varied to see the effect on the resultant film property. Recently, proton conduction in nanograined polycrystalline pellets of ceria drew much interest. Thickness-mode (through-plane, z-direction) electrical measurements were made to confirm the existence of proton conductivity and investigate the nature of the conduction pathway: exposed grain surfaces and parallel grain boundaries. Columnar structure presumably favors proton conduction, and we have found measurable proton conductivity enhancement. Electrochemical property of gas-columnar ceria interface on the hydrogen electrooxidation is studied by AC impedance spectroscopy. Isothermal gas composition dependence of the electrode resistance was studied to elucidate Sm doping level effect and microstructure effect. Significantly, preferred orientation is shown to affect the gas dependence and performance of the fuel cell anode. A hypothesis is proposed to explain the origin of this behavior. Lastly, an optical transmittance based methodology was developed to obtain reference refractive index and microstructural parameters (thickness, roughness, porosity) of ceria films via subsequent fitting procedure.

  2. Arsenic doped zinc oxide

    SciTech Connect

    Volbers, N.; Lautenschlaeger, S.; Leichtweiss, T.; Laufer, A.; Graubner, S.; Meyer, B. K.; Potzger, K.; Zhou Shengqiang

    2008-06-15

    As-doping of zinc oxide has been approached by ion implantation and chemical vapor deposition. The effect of thermal annealing on the implanted samples has been investigated by using secondary ion mass spectrometry and Rutherford backscattering/channeling geometry. The crystal damage, the distribution of the arsenic, the diffusion of impurities, and the formation of secondary phases is discussed. For the thin films grown by vapor deposition, the composition has been determined with regard to the growth parameters. The bonding state of arsenic was investigated for both series of samples using x-ray photoelectron spectroscopy.

  3. Synthesis and characterization of ZrO2-CuO co-doped ceria nanoparticles via chemical precipitation method.

    PubMed

    Viruthagiri, G; Gopinathan, E; Shanmugam, N; Gobi, R

    2014-10-15

    In the present study, the fluorite cubic phase of bare and ZrO2-CuO co-doped ceria (CeO2) nanoparticles have been synthesized through a simple chemical precipitation method. X-ray diffraction results revealed that average grain sizes of the samples are within 5-6nm range. The functional groups present in the samples were identified by Fourier Transform Infrared Spectroscopy (FTIR) study. Surface area measurement was carried out for the ceria nanoparticles to characterize the surface properties of the synthesized samples. The direct optical cutoff wavelength from DRS analysis was blue-shifted evidently with respect to the bulk material and indicated quantum-size confinement effect in the nanocrystallites. PL spectra revealed the strong and sharp UV emission at 401nm. The surface morphology and the element constitution of the pure and doped nanoparticles were studied by scanning electron microscope fitted with energy dispersive X-ray spectrometer arrangement. The thermal decomposition course was followed using thermo gravimetric and differential thermal analyses (TG-DTA).

  4. Shape-Dependent Activity of Ceria for Hydrogen Electro-Oxidation in Reduced-Temperature Solid Oxide Fuel Cells.

    PubMed

    Tong, Xiaofeng; Luo, Ting; Meng, Xie; Wu, Hao; Li, Junliang; Liu, Xuejiao; Ji, Xiaona; Wang, Jianqiang; Chen, Chusheng; Zhan, Zhongliang

    2015-11-04

    Single crystalline ceria nanooctahedra, nanocubes, and nanorods are hydrothermally synthesized, colloidally impregnated into the porous La0.9Sr0.1Ga0.8Mg0.2O3-δ (LSGM) scaffolds, and electrochemically evaluated as the anode catalysts for reduced temperature solid oxide fuel cells (SOFCs). Well-defined surface terminations are confirmed by the high-resolution transmission electron microscopy--(111) for nanooctahedra, (100) for nanocubes, and both (110) and (100) for nanorods. Temperature-programmed reduction in H2 shows the highest reducibility for nanorods, followed sequentially by nanocubes and nanooctahedra. Measurements of the anode polarization resistances and the fuel cell power densities reveal different orders of activity of ceria nanocrystals at high and low temperatures for hydrogen electro-oxidation, i.e., nanorods > nanocubes > nanooctahedra at T ≤ 450 °C and nanooctahedra > nanorods > nanocubes at T ≥ 500 °C. Such shape-dependent activities of these ceria nanocrystals have been correlated to their difference in the local structure distortions and thus in the reducibility. These findings will open up a new strategy for design of advanced catalysts for reduced-temperature SOFCs by elaborately engineering the shape of nanocrystals and thus selectively exposing the crystal facets.

  5. Catalytic combustion of soot over ceria-zinc mixed oxides catalysts supported onto cordierite.

    PubMed

    Nascimento, Leandro Fontanetti; Martins, Renata Figueredo; Silva, Rodrigo Ferreira; Serra, Osvaldo Antonio

    2014-03-01

    Modified substrates as outer heterogeneous catalysts was employed to reduce the soot generated from incomplete combustion of diesel or diesel/biodiesel blends, a process that harms the environment and public health. The unique storage properties of ceria (CeO2) makes it one of the most efficient catalysts available to date. Here, we proposed that ceria-based catalysts can lower the temperature at which soot combustion occurs; more specifically, from 610°C to values included in the diesel exhausts operation range (300-450°C). The sol-gel method was used to synthesize mixed oxide-based catalysts (CeO2:ZnO); the resulting catalysts were deposited onto cordierite substrates. In addition, the morphological and structural properties of the material were evaluated by XRD, BET, TPR-H2, and SEM. Thermogravimetric (TG/DTA) analysis revealed that the presence of the catalyst decreased the soot combustion temperature by 200°C on average, indicating that the oxygen species arise at low temperatures in this situation, promoting highly reactive oxidation reactions. Comparative analysis of soot emission by diffuse reflectance spectroscopy (DRS) showed that catalyst-impregnated cordierite samples efficiently oxidized soot in a diesel/biodiesel stationary motor: soot emission decreased by more than 70%.

  6. Ultrasmooth reaction-sintered silicon carbide surface resulting from combination of thermal oxidation and ceria slurry polishing.

    PubMed

    Shen, Xinmin; Dai, Yifan; Deng, Hui; Guan, Chaoliang; Yamamura, Kazuya

    2013-06-17

    An ultrasmooth reaction-sintered silicon carbide surface with an rms roughness of 0.424 nm is obtained after thermal oxidation for 30 min followed by ceria slurry polishing for 30 min. By SEM-EDX analysis, we investigated the thermal oxidation behavior of RS-SiC, in which the main components are Si and SiC. As the oxidation rate is higher in the area with defects, there are no scratches or cracks on the surface after oxidation. However, a bumpy structure is formed after oxidation because the oxidation rates of Si and SiC differ. Through a theoretical analysis of thermal oxidation using the Deal-Grove model and the removal of the oxide layer by ceria slurry polishing in accordance with the Preston equation, a model for obtaining an ultrasmooth surface is proposed and the optimal processing conditions are presented.

  7. Surface and redox properties of cobalt-ceria binary oxides: On the effect of Co content and pretreatment conditions

    NASA Astrophysics Data System (ADS)

    Konsolakis, Michalis; Sgourakis, Michalis; Carabineiro, Sónia A. C.

    2015-06-01

    Ceria-based transition metal catalysts have recently received considerable attention both in heterogeneous catalysis and electro-catalysis fields, due to their unique physicochemical characteristics. Their catalytic performance is greatly affected by the surface local chemistry and oxygen vacancies. The present study aims at investigating the impact of Co/Ce ratio and pretreatment conditions on the surface and redox properties of cobalt-ceria binary oxides. Co-ceria mixed oxides with different Co content (0, 20, 30, 60, 100 wt.%) were prepared by impregnation method and characterized by means of N2 adsorption at -196 °C, X-ray diffraction (XRD), H2 temperature-programmed reduction (H2-TPR) and X-ray photoelectron spectroscopy (XPS). The results shown the improved reducibility of Co/CeO2 mixed oxides compared to single oxides, due to a synergistic interaction between cobalt and cerium. Oxidation pretreatment results in a preferential localization of cerium species on the outer surface. In contrast, a uniform distribution of cobalt and cerium species over the entire catalyst surface is obtained by the reduction process, which facilitates the formation of oxygen vacancies though Co3+/Co2+ and Ce3+/Ce4+ redox cycles. Fundamental insights toward tuning the surface chemistry of cobalt-ceria binary oxides are provided, paving the way for real-life industrial applications.

  8. Ceria-based model catalysts: fundamental studies on the importance of the metal-ceria interface in CO oxidation, the water-gas shift, CO2 hydrogenation, and methane and alcohol reforming.

    PubMed

    Rodriguez, José A; Grinter, David C; Liu, Zongyuan; Palomino, Robert M; Senanayake, Sanjaya D

    2017-04-03

    Model metal/ceria and ceria/metal catalysts have been shown to be excellent systems for studying fundamental phenomena linked to the operation of technical catalysts. In the last fifteen years, many combinations of well-defined systems involving different kinds of metals and ceria have been prepared and characterized using the modern techniques of surface science. So far most of the catalytic studies have been centered on a few reactions: CO oxidation, the hydrogenation of CO2, and the production of hydrogen through the water-gas shift reaction and the reforming of methane or alcohols. Using model catalysts it has been possible to examine in detail correlations between the structural, electronic and catalytic properties of ceria-metal interfaces. In situ techniques (X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, infrared spectroscopy, scanning tunneling microscopy) have been combined to study the morphological changes under reaction conditions and investigate the evolution of active phases involved in the cleavage of C-O, C-H and C-C bonds. Several studies with model ceria catalysts have shown the importance of strong metal-support interactions. In general, a substantial body of knowledge has been acquired and concepts have been developed for a more rational approach to the design of novel technical catalysts containing ceria.

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

    SciTech Connect

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

    2015-01-26

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

  10. Reduced erbium-doped ceria nanoparticles: one nano-host applicable for simultaneous optical down- and up-conversions.

    PubMed

    Shehata, Nader; Meehan, Kathleen; Hassounah, Ibrahim; Hudait, Mantu; Jain, Nikhil; Clavel, Michael; Elhelw, Sarah; Madi, Nabil

    2014-01-01

    This paper introduces a new synthesis procedure to form erbium-doped ceria nanoparticles (EDC NPs) that can act as an optical medium for both up-conversion and down-conversion in the same time. This synthesis process results qualitatively in a high concentration of Ce(3+) ions required to obtain high fluorescence efficiency in the down-conversion process. Simultaneously, the synthesized nanoparticles contain the molecular energy levels of erbium that are required for up-conversion. Therefore, the synthesized EDC NPs can emit visible light when excited with either UV or IR photons. This opens new opportunities for applications where emission of light via both up- and down-conversions from a single nanomaterial is desired such as solar cells and bio-imaging.

  11. Altering properties of cerium oxide thin films by Rh doping

    SciTech Connect

    Ševčíková, Klára; Nehasil, Václav; Vorokhta, Mykhailo; Haviar, Stanislav; Matolín, Vladimír; and others

    2015-07-15

    Highlights: • Thin films of ceria doped by rhodium deposited by RF magnetron sputtering. • Concentration of rhodium has great impact on properties of Rh–CeO{sub x} thin films. • Intensive oxygen migration in films with low concentration of rhodium. • Oxygen migration suppressed in films with high amount of Rh dopants. - Abstract: Ceria containing highly dispersed ions of rhodium is a promising material for catalytic applications. The Rh–CeO{sub x} thin films with different concentrations of rhodium were deposited by RF magnetron sputtering and were studied by soft and hard X-ray photoelectron spectroscopies, Temperature programmed reaction and X-ray powder diffraction techniques. The sputtered films consist of rhodium–cerium mixed oxide where cerium exhibits a mixed valency of Ce{sup 4+} and Ce{sup 3+} and rhodium occurs in two oxidation states, Rh{sup 3+} and Rh{sup n+}. We show that the concentration of rhodium has a great influence on the chemical composition, structure and reducibility of the Rh–CeO{sub x} thin films. The films with low concentrations of rhodium are polycrystalline, while the films with higher amount of Rh dopants are amorphous. The morphology of the films strongly influences the mobility of oxygen in the material. Therefore, varying the concentration of rhodium in Rh–CeO{sub x} thin films leads to preparing materials with different properties.

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

    PubMed

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

    2016-08-24

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

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

    PubMed

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

    2014-10-06

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

  14. Active Gold-Ceria and Gold-Ceria/titania Catalysts for CO Oxidation. From Single-Crystal Model Catalysts to Powder Catalysts

    SciTech Connect

    Rodriguez, Jose A.; Si, Rui; Evans, Jaime; Xu, Wenqian; Hanson, Jonathan C.; Tao, Jing; Zhu, Yimei

    2014-07-23

    We studied CO oxidation on model and powder catalysts of Au-CeO2 and Au-CeOx/TiO2. Phenomena observed in Au-CeO2(1 1 1) and Au-CeO2/TiO2(1 1 0) provided useful concepts for designing and preparing highly active and stable Au-CeOx/TiO2 powder catalysts for CO oxidation. Small particles of Au dispersed on CeO2(1 1 1) displayed high catalytic activity, making Au-CeO2(1 1 1) a better CO oxidation catalyst than Au-TiO2(1 1 0) or Au-MgO(1 0 0). An excellent support for gold was found after depositing nanoparticles of ceria on TiO2(1 1 0). The CeOx nanoparticles act as nucleation centers for gold, improving dispersion of the supported metal and helping in the creation of reaction sites efficient for the adsorption of CO and the dissociation of the O2 molecule. High-surface area catalysts were prepared by depositing gold on ceria nanorods and CeOx/TiO2 powders. The samples were tested for the low-temperature (10–70 °C) oxygen-rich (1%CO/4%O2/He) CO oxidation reaction after pre-oxidation (20%O2/He, 300 °C) and pre-reduction (5%H2/He, 300 °C) treatments. Moreover, synchrotron-based operando X-ray diffraction (XRD) and X-ray absorption (XAS) spectroscopy were used to study the Au-CeO2 and Au-CeOx/TiO2 catalysts under reaction conditions. Our operando findings indicate that the most active phase of these catalysts for low-temperature CO oxidation consist of small particles of metallic Au dispersed on CeO2 or CeOx/TiO2.

  15. Ceria-Zirconia Particles Wrapped in a 2D Carbon Envelope: Improved Low-Temperature Oxygen Transfer and Oxidation Activity.

    PubMed

    Aneggi, Eleonora; Rico-Perez, Veronica; de Leitenburg, Carla; Maschio, Stefano; Soler, Lluís; Llorca, Jordi; Trovarelli, Alessandro

    2015-11-16

    Engineering the interface between different components of heterogeneous catalysts at nanometer level can radically alter their performances. This is particularly true for ceria-based catalysts where the interactions are critical for obtaining materials with enhanced properties. Here we show that mechanical contact achieved by high-energy milling of CeO2-ZrO2 powders and carbon soot results in the formation of a core of oxide particles wrapped in a thin carbon envelope. This 2D nanoscale carbon arrangement greatly increases the number and quality of contact points between the oxide and carbon. Consequently, the temperatures of activation and transfer of the oxygen in ceria are shifted to exceptionally low temperatures and the soot combustion rate is boosted. The study confirms the importance of the redox behavior of ceria-zirconia particles in the mechanism of soot oxidation and shows that the organization of contact points at the nanoscale can significantly modify the reactivity resulting in unexpected properties and functionalities.

  16. In situ formation of reduced graphene oxide structures in ceria by combined sol–gel and solvothermal processing

    PubMed Central

    Yang, Jingxia; Ofner, Johannes; Lendl, Bernhard

    2016-01-01

    Raman and IR investigations indicated the presence of reduced graphene oxide (rGO)-like residues on ceria nanoparticles after solvothermal treatment in ethanol. The appearance of such structures is closely related to cerium tert-butoxide as precursor and ethanol as solvothermal solvent. The rGO-like residues improve the catalytic CO oxidation activity. This was also confirmed by introduction of “external” graphene oxide during sol–gel processing, by which the rGO structures and the catalytic activity were enhanced. PMID:28144531

  17. Synthesis and characterization of nanocrystalline Gd and Tb co-doped ceria-based electrolyte materials for IT-SOFC.

    PubMed

    Choi, J W; Saradha, T; Heo, M H; Park, K

    2010-05-01

    Gd and Tb co-doped Ce0.8Gd0.2-xTb(x)O2-delta (0 < or = x < or = 0.09) nanopowders were synthesized by the combustion method using aspartic acid as fuel. The calcined powders formed a ceria-based single phase with a cubic fluorite structure. In addition, the powders were pure, homogeneous, and nanocrystalline nature, i.e., 20.1-23.4 nm in the calculated crystallite size. The partial incorporation of Tb for Gd caused a decrease in the average grain size of the sintered bodies. The high-quality nanosized Ce0.8Gd0.17Tb0.03O2-delta powders provided a high density, ultra-fine grain size, and high electrical conductivity even at the low sintering temperature of 1300 degrees C. The grain size and density of the Ce0.8Gd0.17Tb0.03O2-delta were approximately 146 nm and approximately 99% of the theoretical density, respectively, allowing enhanced electrical conductivity (0.106 Scm(-1) at 800 degrees C).

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

    SciTech Connect

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

    2010-11-09

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

  19. One-pot synthesis of a ceria-graphene oxide composite for the efficient removal of arsenic species.

    PubMed

    Sakthivel, Tamil S; Das, Soumen; Pratt, Cameron J; Seal, Sudipta

    2017-03-09

    Arsenic contamination has posed a health risk to millions of people around the world. In this study, we describe a simple and facile one-step hydrothermal synthesis of a ceria-graphene oxide (ceria-GO) composite for the efficient removal of arsenic species. The prepared ceria-GO composite materials exhibited almost complete (over 99.99%) and quick removal of both arsenic species within 0.1 mg L(-1) of the initial concentration. The calculated adsorption capacities were 185 mg g(-1) for As(iii) and 212 mg g(-1) for As(v). It was found that Ce(3+) is an active site and continuously adsorbs arsenic species; there is a concomitant change from Ce(4+) to Ce(3+) due to the solution redox environment. This increase in the Ce(3+) concentration further facilitates the complete removal of arsenic species in solution. Thus our approach offers a promising potential for the treatment of arsenic-contaminated drinking water.

  20. Hierarchically oriented macroporous anode-supported solid oxide fuel cell with thin ceria electrolyte film.

    PubMed

    Chen, Yu; Zhang, Yanxiang; Baker, Jeffrey; Majumdar, Prasun; Yang, Zhibin; Han, Minfang; Chen, Fanglin

    2014-04-09

    Application of anode-supported solid oxide fuel cell (SOFC) with ceria based electrolyte has often been limited by high cost of electrolyte film fabrication and high electrode polarization. In this study, dense Gd0.1Ce0.9O2 (GDC) thin film electrolytes have been fabricated on hierarchically oriented macroporous NiO-GDC anodes by a combination of freeze-drying tape-casting of the NiO-GDC anode, drop-coating GDC slurry on NiO-GDC anode, and co-firing the electrolyte/anode bilayers. Using 3D X-ray microscopy and subsequent analysis, it has been determined that the NiO-GDC anode substrates have a porosity of around 42% and channel size from around 10 μm at the electrolyte side to around 20 μm at the other side of the NiO-GDC (away from the electrolyte), indicating a hierarchically oriented macroporous NiO-GDC microstructure. Such NiO-GDC microstructure shows a tortuosity factor of ∼1.3 along the thickness direction, expecting to facilitate gas diffusion in the anode during fuel cell operation. SOFCs with such Ni-GDC anode, GDC film (30 μm) electrolyte, and La0.6Sr0.4Co0.2Fe0.8O3-GDC (LSCF-GDC) cathode show significantly enhanced cell power output of 1.021 W cm(-2) at 600 °C using H2 as fuel and ambient air as oxidant. Electrochemical Impedance Spectroscopy (EIS) analysis indicates a decrease in both activation and concentration polarizations. This study has demonstrated that freeze-drying tape-casting is a very promising approach to fabricate hierarchically oriented porous substrate for SOFC and other applications.

  1. CO oxidation on inverse CeO(x)/Cu(111) catalysts: high catalytic activity and ceria-promoted dissociation of O2.

    PubMed

    Yang, Fan; Graciani, Jesús; Evans, Jaime; Liu, Ping; Hrbek, Jan; Sanz, Javier Fdez; Rodriguez, José A

    2011-03-16

    A Cu(111) surface displays a low activity for the oxidation of carbon monoxide (2CO + O(2) → 2CO(2)). Depending on the temperature, background pressure of O(2), and the exposure time, one can get chemisorbed O on Cu(111) or a layer of Cu(2)O that may be deficient in oxygen. The addition of ceria nanoparticles (NPs) to Cu(111) substantially enhances interactions with the O(2) molecule and facilitates the oxidation of the copper substrate. In images of scanning tunneling microscopy, ceria NPs exhibit two overlapping honeycomb-type moiré structures, with the larger ones (H(1)) having a periodicity of 4.2 nm and the smaller ones (H(2)) having a periodicity of 1.20 nm. After annealing CeO(2)/Cu(111) in O(2) at elevated temperatures (600-700 K), a new phase of a Cu(2)O(1+x) surface oxide appears and propagates from the ceria NPs. The ceria is not only active for O(2) dissociation, but provides a much faster channel for oxidation than the step edges of Cu(111). Exposure to CO at 550-750 K led to a partial reduction of the ceria NPs and the removal of the copper oxide layer. The CeO(x)/Cu(111) systems have activities for the 2CO + O(2) → 2CO(2) reaction that are comparable or larger than those reported for surfaces of expensive noble metals such as Rh(111), Pd(110), and Pt(100). Density-functional calculations show that the supported ceria NPs are able to catalyze the oxidation of CO due to their special electronic and chemical properties. The configuration of the inverse oxide/metal catalyst opens new interesting routes for applications in catalysis.

  2. CO Oxidation on Inverse CeOx/Cu(111) Catalysts: High Catalytic Activity and Ceria-Promoted Dissociation of O2

    SciTech Connect

    F Yang; J Graciani; J Evans; P Liu; J Hrbek; J Fdez. Sanz; J Rodriguez

    2011-12-31

    A Cu(111) surface displays a low activity for the oxidation of carbon monoxide (2CO + O{sub 2} {yields} 2CO{sub 2}). Depending on the temperature, background pressure of O{sub 2}, and the exposure time, one can get chemisorbed O on Cu(111) or a layer of Cu{sub 2}O that may be deficient in oxygen. The addition of ceria nanoparticles (NPs) to Cu(111) substantially enhances interactions with the O{sub 2} molecule and facilitates the oxidation of the copper substrate. In images of scanning tunneling microscopy, ceria NPs exhibit two overlapping honeycomb-type moire structures, with the larger ones (H{sub 1}) having a periodicity of 4.2 nm and the smaller ones (H{sub 2}) having a periodicity of 1.20 nm. After annealing CeO{sub 2}/Cu(111) in O{sub 2} at elevated temperatures (600-700 K), a new phase of a Cu{sub 2}O{sub 1+x} surface oxide appears and propagates from the ceria NPs. The ceria is not only active for O{sub 2} dissociation, but provides a much faster channel for oxidation than the step edges of Cu(111). Exposure to CO at 550-750 K led to a partial reduction of the ceria NPs and the removal of the copper oxide layer. The CeO{sub x}/Cu(111) systems have activities for the 2CO + O{sub 2} {yields} 2CO{sub 2} reaction that are comparable or larger than those reported for surfaces of expensive noble metals such as Rh(111), Pd(110), and Pt(100). Density-functional calculations show that the supported ceria NPs are able to catalyze the oxidation of CO due to their special electronic and chemical properties. The configuration of the inverse oxide/metal catalyst opens new interesting routes for applications in catalysis.

  3. Dimethyl methylphosphonate Decomposition on fully Oxidized and Partially Reduced ceria Thin Films

    SciTech Connect

    Chen, D.; Ratliff, J; Hu, X; Gordon, W; Senanayake, S; Mullins, D

    2010-01-01

    The thermal decomposition of dimethyl methylphosphonate (DMMP) on crystalline ceria thin films grown on Ru(0 0 0 1) was studied by temperature programmed desorption (TPD), X-ray photoelectron spectroscopy (XPS) and infrared absorption reflection spectroscopy (IRAS). TPD experiments show that methanol and formaldehyde desorb as the two main products at 575 K, while water, formaldehyde and CO are produced above 800 K. IRAS studies demonstrate that DMMP adsorbs via the phosphoryl oxygen at 200 K, but the P{double_bond}O bond converts to a bridging O{single_bond}P{single_bond}O species at 300 K. DMMP decomposition initially occurs via P{_}OCH{sub 3} bond scission to form methyl methylphosphonate (MMP) and methyl phosphonate (MP) between 300 and 500 K; XPS and IRAS data are consistent with a methoxy intermediate on the surface at these temperatures. The more stable P{_}CH{sub 3} bonds remain intact up to 700 K, and the only surface intermediate at higher temperatures is believed to be PO{sub x}. Although the presence of PO{sub x} decreases activity for DMMP decomposition, some activity on the ceria surface remains even after 7 cycles of adsorption and reaction. The ceria films become reduced by multiple DMMP adsorption-reaction cycles, with the Ce{sup +4} content dropping to 30% after seven cycles. Investigations of DMMP reaction on reduced ceria surfaces show that CO and H{sub 2} are produced in addition to methanol and formaldehyde. Furthermore, DMMP decomposition activity on the reduced ceria films is almost completely inhibited after only 3 adsorption-reaction cycles. Similarities between DMMP and methanol chemistry on the ceria films suggest that methoxy is a key surface intermediate in both reactions.

  4. Shape-controlled ceria-reduced graphene oxide nanocomposites toward high-sensitive in situ detection of nitric oxide.

    PubMed

    Hu, Fang Xin; Xie, Jia Le; Bao, Shu Juan; Yu, Ling; Li, Chang Ming

    2015-08-15

    Nitric oxide (NO) is an important signal molecule released by most cancer cells under drug stimulation or/and disease development but it is extremely challenging to in situ while real-time sensitively detect NO due to its large diffusivity, low concentration and fast decay. Herein, shape-controlled reduced graphene oxide nanocomposing with ceria (rGO-CeO2) was synthesized via hydrothermal reaction to construct a highly sensitive real-time sensing platform for NO detection. The crystal shape of CeO2 nanoparticles in rGO-CeO2 composites significantly affects the sensing performance of rGO-CeO2, of which the regular hexagonal nanocrystal CeO2 achieves the highest sensitivity (1676.06 mA cm(-2) M(-1)), a wide dynamic range (18.0 nM to 5.6 µM) and a low detection limit (9.6 nM). This attributes to a synergical effect from high catalytic activity of the specifically shaped CeO2 nanocrystal and good conductivity/high surface area of rGO. This work demonstrates a way by rationally compose individual merit components while well control the nanostructure for a superior synergistic effect to build a smart sensing platform, while offering a great application potential to sensitively real-time detect NO released from living cells for diagnosis or/and studies of complicated biological processes.

  5. Composite solid oxide fuel cell anode based on ceria and strontium titanate

    DOEpatents

    Marina, Olga A.; Pederson, Larry R.

    2008-12-23

    An anode and method of making the same wherein the anode consists of two separate phases, one consisting of a doped strontium titanate phase and one consisting of a doped cerium oxide phase. The strontium titanate phase consists of Sr.sub.1-xM.sub.xTiO.sub.3-.delta., where M is either yttrium (Y), scandium (Sc), or lanthanum (La), where "x" may vary typically from about 0.01 to about 0.5, and where .delta. is indicative of some degree of oxygen non-stoichiometry. A small quantity of cerium may also substitute for titanium in the strontium titanate lattice. The cerium oxide consists of N.sub.yCe.sub.1-yO.sub.2-.delta., where N is either niobium (Nb), vanadium (V), antimony (Sb) or tantalum (Ta) and where "y" may vary typically from about 0.001 to about 0.1 and wherein the ratio of Ti in said first phase to the sum of Ce and N in the second phase is between about 0.2 to about 0.75. Small quantities of strontium, yttrium, and/or lanthanum may additionally substitute into the cerium oxide lattice. The combination of these two phases results in better performance than either phase used separately as an anode for solid oxide fuel cell or other electrochemical device.

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  7. The structure and stability of reduced and oxidized mononuclear platinum species on nanostructured ceria from density functional modeling.

    PubMed

    Aleksandrov, Hristiyan A; Neyman, Konstantin M; Vayssilov, Georgi N

    2015-06-14

    We report our results for the structure and relative stability of mononuclear platinum species on a ceria nanoparticle Ce21O42 depending on reduction or oxidation of the system. The most stable platinum species is Pt(2+) at small {100} facets, where the ion is coordinated in a square-planar complex with four oxygen anions as ligands. Partial reduction of the system does not affect the state of platinum in this position but causes reduction of cerium ions. Atomic platinum species in all other modeled positions on the surface of the ceria nanoparticle are found to be in the oxidation state 0. Based on the calculated thermodynamic quantities we analyzed the formation of a preferable type of platinum species depending on the temperature and O2 pressure. Our thermodynamic model shows that the most stable species under standard conditions is PtO, while at the partial pressure of O2 below 100 Pa the stoichiometric complex Pt-Ce21O42 is formed. In both structures there is Pt(2+) located in a square-planar complex. The characteristics of these two structures fit well the available EXAFS and XPS data. These structures are energetically stable with respect to sintering, while the agglomeration to platinum clusters is exothermic for the neutral mononuclear Pt species located at {111} facets.

  8. Engineering the defect state and reducibility of ceria based nanoparticles for improved anti-oxidation performance.

    PubMed

    Wang, Yan-Jie; Dong, Hao; Lyu, Guang-Ming; Zhang, Huai-Yuan; Ke, Jun; Kang, Li-Qun; Teng, Jia-Li; Sun, Ling-Dong; Si, Rui; Zhang, Jing; Liu, Yan-Jun; Zhang, Ya-Wen; Huang, Yun-Hui; Yan, Chun-Hua

    2015-09-07

    Due to their excellent anti-oxidation performance, CeO2 nanoparticles receive wide attention in pharmacological application. Deep understanding of the anti-oxidation mechanism of CeO2 nanoparticles is extremely important to develop potent CeO2 nanomaterials for anti-oxidation application. Here, we report a detailed study on the anti-oxidation process of CeO2 nanoparticles. The valence state and coordination structure of Ce are characterized before and after the addition of H2O2 to understand the anti-oxidation mechanism of CeO2 nanoparticles. Adsorbed peroxide species are detected during the anti-oxidation process, which are responsible for the red-shifted UV-vis absorption spectra of CeO2 nanoparticles. Furthermore, the coordination number of Ce in the first coordination shell slightly increased after the addition of H2O2. On the basis of these experimental results, the reactivity of coordination sites for peroxide species is considered to play a key role in the anti-oxidation performance of CeO2 nanoparticles. Furthermore, we present a robust method to engineer the anti-oxidation performance of CeO2 nanoparticles through the modification of the defect state and reducibility by doping with Gd(3+). Improved anti-oxidation performance is also observed in cell culture, where the biocompatible CeO2-based nanoparticles can protect INS-1 cells from oxidative stress induced by H2O2, suggesting the potential application of CeO2 nanoparticles in the treatment of diabetes.

  9. Hierarchically nanoporous ceria nanoparticles with a high-surface area: synthesis, characterization, and their catalytic activity.

    PubMed

    Ge, Jiechao; Zhong, Liangshu; Zhuo, Linhai; Tang, Bo; Song, Weiguo

    2011-01-01

    A redox route based on ethylene glycol mediated process was developed to synthesize hierarchically nanoporpous ceria nanoparticles (ceria HNPNPs). The synthesized ceria HNPNPs are composed of building blocks fabricated with cubic ceria nanocrystals of several nanometers in diameter. Scanning electron microscopy was performed to investigate the evolution process of ceria precursor, and a two-step growth process was suggested for the morphology evolution. The synthesized ceria HNPNPs exhibit high surface area, which lead to high catalytic activity for CO oxidation.

  10. Y-doped SrTiO 3 based sulfur tolerant anode for solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Kurokawa, Hideto; Yang, Liming; Jacobson, Craig P.; De Jonghe, Lutgard C.; Visco, Steven J.

    A solid oxide fuel cell (SOFC) anode with high sulfur tolerance was developed starting from a Y-doped SrTiO 3 (SYTO)-yttria stabilized zirconia (YSZ) porous electrode backbone, and infiltrated with nano-sized catalytic ceria and Ru. The size of the infiltrated particles on the SYTO-YSZ pore walls was 30-200 nm, and both infiltrated materials improved the performance of the SYTO-YSZ anode significantly. The infiltrated ceria covered most of the surface of the SYTO-YSZ pore walls, while Ru was dispersed as individual nano-particles. The performance and sulfur tolerance of a cathode supported cell with ceria- and Ru-infiltrated SYTO-YSZ anode was examined in humidified H 2 mixed with H 2S. The anode showed high sulfur tolerance in 10-40 ppm H 2S, and the cell exhibited a constant maximum power density 470 mW cm -2 at 10 ppm H 2S, at 1073 K. At an applied current density 0.5 A cm -2, the addition of 10 ppm H 2S to the H 2 fuel dropped the cell voltage slightly, from 0.79 to 0.78 V, but completely recovered quickly after the H 2S was stopped. The ceria- and Ru-infiltrated SYTO-YSZ anode showed much higher sulfur tolerance than conventional Ni-YSZ anodes.

  11. Nanocrystalline ceria coatings on solid oxide fuel cell anodes: the role of organic surfactant pretreatments on coating microstructures and sulfur tolerance

    PubMed Central

    Wu, Chieh-Chun; Tang, Ling

    2014-01-01

    Summary Treatments with organic surfactants, followed by the deposition of nanocrystalline ceria coatings from aqueous solution, were applied to anodes of solid oxide fuel cells. The cells were then operated in hydrogen/nitrogen fuel streams with H2S contents ranging from 0 to 500 ppm. Two surfactant treatments were studied: immersion in dodecanethiol, and a multi-step conversion of a siloxy-anchored alkyl bromide to a sulfonate functionality. The ceria coatings deposited after the thiol pretreatment, and on anodes with no pretreatment, were continuous and uniform, with thicknesses of 60–170 nm and 100–140 nm, respectively, and those cells exhibited better lifetime performance and sulfur tolerance compared to cells with untreated anodes and anodes with ceria coatings deposited after the sulfonate pretreatment. Possible explanations for the effects of the treatments on the structure of the coatings, and for the effects of the coatings on the performance of the cells, are discussed. PMID:25383282

  12. The role of CO2 as a soft oxidant for dehydrogenation of ethylbenzene to styrene over a high-surface-area ceria catalyst

    SciTech Connect

    Zhang, Li; Wu, Zili; Nelson, Nicholas; Sadow, Aaron D.; Slowing, Igor I.; Overbury, Steven H.

    2015-09-22

    Catalytic performance and the nature of surface adsorbates were investigated for high-surface-area ceria during ethylbenzene oxidative dehydrogenation (ODH) reaction using CO2 as a soft oxidant. A template assisted method was used to synthesize the high-surface-area ceria. The interactions between ethylbenzene, styrene and CO2 on the surface of ceria and the role of CO2 for the ethylbenzene ODH reaction have been investigated in detail by using activity test, in situ Diffuse Reflectance Infrared and Raman spectroscopy. Not only did CO2 as an oxidant favor the higher yield of styrene, but it also inhibited the deposition of coke during the ethylbenzene ODH reaction. Ethylbenzene ODH reaction over ceria followed a two-step pathway: Ethylbenzene is first dehydrogenated to styrene with H2 formed simultaneously, and then CO2 reacts with H2 via the reverse water gas shift. The styrene produced can easily polymerize to form polystyrene, a key intermediate for coke formation. In the absence of CO2, the polystyrene transforms into graphite-like coke at temperatures above 500 °C, which leads to catalyst deactivation. While in the presence of CO2, the coke deposition can be effectively removed via oxidation with CO2.

  13. The role of CO2 as a soft oxidant for dehydrogenation of ethylbenzene to styrene over a high-surface-area ceria catalyst

    DOE PAGES

    Zhang, Li; Wu, Zili; Nelson, Nicholas; ...

    2015-09-22

    Catalytic performance and the nature of surface adsorbates were investigated for high-surface-area ceria during ethylbenzene oxidative dehydrogenation (ODH) reaction using CO2 as a soft oxidant. A template assisted method was used to synthesize the high-surface-area ceria. The interactions between ethylbenzene, styrene and CO2 on the surface of ceria and the role of CO2 for the ethylbenzene ODH reaction have been investigated in detail by using activity test, in situ Diffuse Reflectance Infrared and Raman spectroscopy. Not only did CO2 as an oxidant favor the higher yield of styrene, but it also inhibited the deposition of coke during the ethylbenzene ODHmore » reaction. Ethylbenzene ODH reaction over ceria followed a two-step pathway: Ethylbenzene is first dehydrogenated to styrene with H2 formed simultaneously, and then CO2 reacts with H2 via the reverse water gas shift. The styrene produced can easily polymerize to form polystyrene, a key intermediate for coke formation. In the absence of CO2, the polystyrene transforms into graphite-like coke at temperatures above 500 °C, which leads to catalyst deactivation. While in the presence of CO2, the coke deposition can be effectively removed via oxidation with CO2.« less

  14. The effect of Pr co-dopant in samarium doped ceria

    NASA Astrophysics Data System (ADS)

    Venkatesh, V.; Kumar, V. Prashanth; Reddy, Y. S.; Reddy, C. Vishnuvardhan

    2013-02-01

    The compositions of Ce0.8-xSm0.2PrxO2-δ (x=0, 0.02, 0.04, 0.06) were prepared through the sol-gel route. The effect of Pr addition on the crystal structure, densification and thermal expansion of Ce0.8Sm0.2O2-δ was studied. The powder X-ray diffraction (XRD) analysis showed that all the samples exhibit a fluorite structure. The lattice parameters and volume of the unit cell increase with Pr doping. Density of all the samples is more than 90% of theoretical density. The thermal expansion was measured using dilatometric technique in the temperature range 30-1000°C and it was observed that the thermal expansion increased linearly with increasing temperature for all the samples.

  15. Nanofabrication of Doped, Complex Oxides

    SciTech Connect

    Stein, A.; Waller, G.H.; Abiade, J.T.

    2012-01-01

    Complex oxides have many promising attributes, including wide band gaps for high temperature semiconductors, ion conducting electrolytes in fuel cells, ferroelectricity and ferromagnetism. Bulk and thin film oxides can be readily manufactured and tested however these physically hard and chemically inert materials cannot be nanofabricated by direct application of conventional methods. In order to study these materials at the nanoscale there must first be a simple and effective means to achieve the desired structures. Here we discuss the use of pulsed laser deposition at room temperature onto electron beam lithography defined templates of poly methyl methacrylate photoresist. Following a resist liftoff in organic solvents, a heat treatment was used to crystallize the nanostructures. The morphology of these structures was studied using scanning electron microscopy and atomic force microscopy. Crystallinity and composition as determined by x ray diffraction and photo-electron spectroscopy respectively is reported for thin film analogues of the nanostructured oxide. The oxide studied in this report is Nb doped SrTiO{sub 3}, which has been investigated for use as a high temperature thermoelectric material; however the approach used is not materials-dependent.

  16. Effect of Er, Gd, and Nd Co-Dopants on the Properties of Sm-Doped Ceria Electrolyte for IT-SOFC

    NASA Astrophysics Data System (ADS)

    Arabacı, Aliye

    2017-02-01

    Doped ceria electrolytes of Ce0.8Sm0.20O1.90 (SDC), Ce0.8Er0.08Sm0.12O1.90 (ESDC), Ce0.8Gd0.08Sm0.12O1.90 (GSDC), and Ce0.8Nd0.08Sm0.12O1.90 (NSDC) were prepared by a citric-nitrate combustion process. The thermal decomposition of the precursor was investigated by simultaneous thermogravimetric analysis and differential thermal analysis experiments. The phase structure of the calcined and sintered powders was characterized by X-ray diffraction analysis. All of the samples were fluorite-type ceria-based solid solutions. The calcined and sintered powders were also characterized by Fourier transform infrared spectroscopy. Scanning electron microscopy was used to characterize the samples after calcination and sintering. A relative density over 95 percent of the theoretical density was achieved after the sintering process. Electrical conductivities of the sintered samples were measured using the impedance spectra method. The highest ionic conductivity value was found to be 5.28 × 10-2 S cm-1 at 1023 K (750 °C) for GSDC sintered at 1673 K (1400 °C) for 6 hours.

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

    NASA Astrophysics Data System (ADS)

    Wang, Ruigang

    2007-12-01

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

  18. X-ray diffraction study of the t-to-m phase transformation in 12-mol%-ceria-doped zirconia at low temperatures

    SciTech Connect

    Zhu, H.Y. . Dept. of Materials Science and Engineering)

    1994-09-01

    The t-to-m phase transformation in a 12-mol%-ceria-doped zirconia to subzero temperatures was studied in situ by XRD with a cryogenic sample stage. It was found that the t-to-m transformation continuously proceeded to 30 vol% as the temperature decreased to 125 K, when a burstlike transformation suddenly occurred with a transformation to 75 vol%. A preferred orientation of the ([bar 1]11)[sub m] plane parallel to the surface during the preburst transformation and XRD line broadening of both m and t phases after the burst were observed. The preburst transformation, which has not been revealed by previous dilatometry studies, is explained as surface martensitic transformation. This surface transformation occurs at higher temperature than the burstlike transformation due to less matrix constraint and the higher probability of nucleation.

  19. Kinetics of CO2 Reduction over Nonstoichiometric Ceria

    PubMed Central

    2015-01-01

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

  20. Characterization of ceria-based SOFCs

    SciTech Connect

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

    1996-12-31

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

  1. Energetics of Rare Earth Doped Uranium Oxide Solid Solutions

    NASA Astrophysics Data System (ADS)

    Zhang, Lei

    J/mol. Since all the other doped fluorite oxides based on zirconia, hafnia, ceria, and thoria are in the oxygen deficit (oxygen vacancy formation) regime, a systematic study of these rare earth doped fluorite oxides (LnxA 1-xO2-0.5x) was made comparing experimental and computational results. A consistent trend suggested by both calorimetry and computation, was found for all oxygen vacancy containing systems (actinide and non-actinide oxide systems). Larger size mismatch between the smaller host cation (A 4+) and the larger rare earth dopant cation (Ln3+) generally produces more stable solid solutions. The energetics of these systems is the result of competition between strain energy arising from size mismatch (endothermic) and defect association (exothermic). The formation enthalpies of LnxU1-xO2-0.5x obtained from calculation are slightly positive.

  2. The evolution mechanism of the dislocation loops in irradiated lanthanum doped cerium oxide

    NASA Astrophysics Data System (ADS)

    Miao, Yinbin; Aidhy, Dilpuneet; Chen, Wei-Ying; Mo, Kun; Oaks, Aaron; Wolf, Dieter; Stubbins, James F.

    2014-02-01

    Cerium dioxide, a non-radioactive surrogate of uranium dioxide, is useful for simulating the radiation responses of uranium dioxide and mixed oxide fuel (MOX). Controlled additions of lanthanum can also be used to form various levels of lattice oxide or anion vacancies. In previous transmission electron microscopy (TEM) experimental studies, the growth rate of dislocation loops in irradiated lanthanum doped ceria was reported to vary with lanthanum concentration. This work reports findings of the evolution mechanisms of the dislocation loops in cerium oxide with and without lanthanum dopants based on a combination of molecular statics and molecular dynamics simulations. These dislocation loops are found to be b = 1 / 3 < 1 1 1 > interstitial type Frank loops. Calculations of the defect energy profiles of the dislocation loops with different structural configurations and radii reveal the basis for preference of nucleation as well as the driving force of growth. Frenkel pair evolution simulations and displacement cascade overlaps simulations were conducted for a variety of lanthanum doping conditions. The nucleation and growth processes of the Frank loop were found to be controlled by the mobility of cation interstitials, which is significantly influenced by the lanthanum doping concentration. Competition mechanisms coupled with the mobility of cation point defects were discovered, and can be used to explain the lanthanum effects observed in experiments.

  3. IR-doped ruthenium oxide catalyst for oxygen evolution

    NASA Technical Reports Server (NTRS)

    Valdez, Thomas I. (Inventor); Narayanan, Sekharipuram R. (Inventor)

    2012-01-01

    A method for preparing a metal-doped ruthenium oxide material by heating a mixture of a doping metal and a source of ruthenium under an inert atmosphere. In some embodiments, the doping metal is in the form of iridium black or lead powder, and the source of ruthenium is a powdered ruthenium oxide. An iridium-doped or lead-doped ruthenium oxide material can perform as an oxygen evolution catalyst and can be fabricated into electrodes for electrolysis cells.

  4. Effect of relative humidity in high temperature oxidation of ceria nanoparticles coating on 316L austenitic stainless steel

    NASA Astrophysics Data System (ADS)

    Giraldez Pizarro, Luis Miguel

    A solution of 20 wt. % colloidal dispersion of Cerium Oxide (CeO2) in 2.5% of acetic acid, was used for depositing a coating film on an austenitic stainless steel 316L. Cerium compounds have been distinguished as potential corrosion inhibitors in coatings over several alloys. The oxidation behavior of the cerium oxide coating on 316L austenitic stainless steel alloy was evaluated in dry and humid environments, the weight changes (W/A) was monitored as a function of time using a custom built Thermogravimetrical Analysis (TGA) instrument at temperatures of 750°C, 800°C and 850°C, and different relative humidity levels (0%, 10% and 20%) respectively. The parabolic oxidation rate and activation energy is calculated experimentally for each relative humidity level. A measurement of the effective diameter size of the ceria nanoparticles was performed using a Light Scattering technique. A characterization of the film morphology and thickness before the oxidation was executed using Atomic Force Microscopy (AFM). Microstructure and chemical composition of the oxidized coated substrates were analyzed using Scanning Electronic Microscopy (SEM) with energy dispersive spectroscopy (EDS). X-Ray Diffractometer (XRD) was used to characterize oxides formed in the surface upon isothermal treatment. A comparison of activation energy values obtained to identify the influence of relative humidity in the oxidation process at high temperature was conducted. Cerium oxides coating may prevent crevice corrosion and increase pitting resistance of 316L relative to the uncoated substrate at high temperatures and different levels of relative humidity acting as a protective oxidation barrier. The calculated parabolic rate constants, kp, at the experimental temperatures tend to increase as a function of humidity levels. The activation energy tends to increase proportionally to higher level of humidity exposures. At 0% relative humidity a value of 319.29 KJ/mol of activation energy is being

  5. Lattice Strain Defects in a Ceria Nanolayer

    PubMed Central

    2016-01-01

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

  6. Lattice Strain Defects in a Ceria Nanolayer.

    PubMed

    Ma, Liying; Doudin, Nassar; Surnev, Svetlozar; Barcaro, Giovanni; Sementa, Luca; Fortunelli, Alessandro; Netzer, Falko P

    2016-04-07

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

  7. Structural analysis of nickel doped cerium oxide catalysts for fuel reforming in solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Cavendish, Rio

    As world energy demands increase, research into more efficient energy production methods has become imperative. Heterogeneous catalysis and nanoscience are used to promote chemical transformations important for energy production. These concepts are important in solid oxide fuel cells (SOFCs) which have attracted attention because of their potential to provide an efficient and environmentally favorable power generation system. The SOFC is also fuel-flexible with the ability to run directly on many fuels other than hydrogen. Internal fuel reforming directly in the anode of the SOFC would greatly reduce the cost and complexity of the device. Methane is the simplest hydrocarbon and a main component in natural gas, making it useful when testing catalysts on the laboratory scale. Nickel (Ni) and gadolinium (Gd) doped ceria (CeO 2) catalysts for potential use in the SOFC anode were synthesized with a spray drying method and tested for catalytic performance using partial oxidation of methane and steam reforming. The relationships between catalytic performance and structure were then investigated using X-ray diffraction, transmission electron microscopy, and environmental transmission electron microscopy. The possibility of solid solutions, segregated phases, and surface layers of Ni were explored. Results for a 10 at.% Ni in CeO2 catalyst reveal a poor catalytic behavior while a 20 at.% Ni in CeO2 catalyst is shown to have superior activity. The inclusion of both 10 at.% Gd and 10 at.% Ni in CeO2 enhances the catalytic performance. Analysis of the presence of Ni in all 3 samples reveals Ni heterogeneity and little evidence for extensive solid solution doping. Ni is found in small domains throughout CeO2 particles. In the 20 at.% Ni sample a segregated, catalytically active NiO phase is observed. Overall, it is found that significant interaction between Ni and CeO2 occurs that could affect the synthesis and functionality of the SOFC anode.

  8. Sprayed lanthanum doped zinc oxide thin films

    NASA Astrophysics Data System (ADS)

    Bouznit, Y.; Beggah, Y.; Ynineb, F.

    2012-01-01

    Lanthanum doped zinc oxide thin films were deposited on soda-lime glass substrates using a pneumatic spray pyrolysis technique. The films were prepared using different lanthanum concentrations at optimum deposition parameters. We studied the variations in structural, morphological and optical properties of the samples due to the change of doping concentration in precursor solutions. X-ray diffraction (XRD) patterns show that pure and La-doped ZnO thin films are highly textured along c-axis perpendicular to the surface of the substrate. Scanning electron micrographs show that surface morphology of ZnO films undergoes a significant change according to lanthanum doping. All films exhibit a transmittance higher than 80% in the visible region.

  9. Tuning the Thickness of Ba-Containing "Functional" Layer toward High-Performance Ceria-Based Solid Oxide Fuel Cells.

    PubMed

    Gong, Zheng; Sun, Wenping; Shan, Duo; Wu, Yusen; Liu, Wei

    2016-05-04

    Developing highly efficient ceria-based solid oxide fuel cells with high power density is still a big concern for commercial applications. In this work, a novel structured Ce0.8Sm0.2O2-δ (SDC)-based fuel cell with a bilayered anode consisting of Ni-SDC and Ni-BaZr0.1Ce0.7Y0.2O3-δ (Ni-BZCY) was designed. In addition to the catalysis function, the Ni-BZCY anode "functional" layer also provides Ba source for generating an electron-blocking layer in situ at the anode/electrolyte interface during sintering. The Ni-BZCY thickness significantly influences the quality of the electron-blocking layer and electrochemical performances of the cell. The cell with a 50 μm thick Ni-BZCY layer exhibits the best performance in terms of open circuit voltage (OCV) and peak power density (1068 mW cm(-2) at 650 °C). The results demonstrate that this cell with an optimal structure has a distinct advantage of delivering high power performance with a high efficiency at reduced temperatures.

  10. Optimizing structural and compositional properties of electrodeposited ceria coatings for enhanced oxidation resistance of a nickel-based superalloy

    NASA Astrophysics Data System (ADS)

    Bouchaud, B.; Balmain, J.; Bonnet, G.; Pedraza, F.

    2013-03-01

    Cathodic electrodeposition was used to generate ceria coatings onto a Ni-based superalloy substrate. The electrochemical parameters were optimized so as to obtain relatively thick but adherent films with tailored composition and microstructural features (multi-cracked network) designed for high temperature applications. Whereas the applied current density was shown to mainly influence the appearance and size of the cracks as well as the amount of oxygen vacancies, the linear trend between the deposited mass and the deposition time allowed a good control of the deposited thickness. A crystallization/diffusion thermal treatment was then applied to promote the dehydration of the deposit, thus resulting in a network of refined cracks, and in the complete crystallization of nanometric CeO2-x exhibiting either a needle-like or a quasi "foam-like" microstructure depending on the applied temperature. This also provided the establishment of an inwardly grown α-Al2O3 scale at the substrate/coating interface expected to further increase the high temperature oxidation resistance of the coated superalloy.

  11. Doped palladium containing oxidation catalysts

    SciTech Connect

    Mohajeri, Nahid

    2014-02-18

    A supported oxidation catalyst includes a support having a metal oxide or metal salt, and mixed metal particles thereon. The mixed metal particles include first particles including a palladium compound, and second particles including a precious metal group (PMG) metal or PMG metal compound, wherein the PMG metal is not palladium. The oxidation catalyst may also be used as a gas sensor.

  12. Aluminum doped zinc oxide for organic photovoltaics

    SciTech Connect

    Murdoch, G. B.; Hinds, S.; Sargent, E. H.; Tsang, S. W.; Mordoukhovski, L.; Lu, Z. H.

    2009-05-25

    Aluminum doped zinc oxide (AZO) was grown via magnetron sputtering as a low-cost alternative to indium tin oxide (ITO) for organic photovoltaics (OPVs). Postdeposition ozone treatment resulted in devices with lower series resistance, increased open-circuit voltage, and power conversion efficiency double that of devices fabricated on untreated AZO. Furthermore, cells fabricated using ozone treated AZO and standard ITO displayed comparable performance.

  13. Impact of dynamic specimen shape evolution on the atom probe tomography results of doped epitaxial oxide multilayers: Comparison of experiment and simulation

    SciTech Connect

    Madaan, Nitesh; Nandasiri, Manjula; Devaraj, Arun; Bao, Jie; Xu, Zhijie; Thevuthasan, Suntharampillai

    2015-08-31

    The experimental atom probe tomography (APT) results from two different specimen orientations (top-down and sideways) of a high oxygen ion conducting Samaria-doped-ceria/Scandia-stabilized-zirconia multilayer thin film solid oxide fuel cell electrolyte was compared with level-set method based field evaporation simulations for the same specimen orientations. This experiment-simulation comparison explains the dynamic specimen shape evolution and ion trajectory aberrations that can induce density artifacts in final reconstruction, leading to inaccurate estimation of interfacial intermixing. This study highlights the importance of comparing experimental results with field evaporation simulations when using APT to study oxide heterostructure interfaces.

  14. Impact of Dynamic Specimen Shape Evolution on the Atom Probe Tomography Results of Doped Epitaxial Oxide Multilayers: Comparison of Experiment and Simulation

    SciTech Connect

    Madaan, Nitesh; Bao, Jie; Nandasiri, Manjula I.; Xu, Zhijie; Thevuthasan, Suntharampillai; Devaraj, Arun

    2015-08-31

    The experimental atom probe tomography results from two different specimen orientations (top-down and side-ways) of a high oxygen ion conducting Samaria-doped-ceria/Scandia-stabilized-zirconia multilayer thin film solid oxide fuel cell electrolyte was correlated with level-set method based field evaporation simulations for the same specimen orientations. This experiment-theory correlation explains the dynamic specimen shape evolution and ion trajectory aberrations that can induce density artifacts in final reconstruction leading to inaccurate estimation of interfacial intermixing. This study highlights the need and importance of correlating experimental results with field evaporation simulations when using atom probe tomography for studying oxide heterostructure interfaces.

  15. The importance of polarizability in the modeling of ionic diffusion in ceria

    NASA Astrophysics Data System (ADS)

    Lucid, A. K.; Watson, G. W.

    2017-02-01

    Classical molecular dynamics can be used to investigate ionic diffusion and its limitations in trivalently doped ceria and at the surfaces and interfaces of these materials. Here we compare the performance of two interatomic potentials derived for samarium doped ceria from the same set of ab-initio data, a dipole polarizable ion model (DIPPIM) and a rigid ion model (RIM). The DIPPIM allows for polarization effects resulting from induced dipoles whereas the RIM does not. In this study we aim to elucidate whether or not this system can be modelled successfully using a RIM or if a DIPPIM is necessary due to the large polarization effects caused by the presence of oxide (O2‑) ions.

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

    NASA Astrophysics Data System (ADS)

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

    2013-07-01

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

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

    NASA Astrophysics Data System (ADS)

    Dikmen, Sibel; Ozsakarya, Rabia; Dikmen, Erdal

    2014-03-01

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

  18. Template engaged synthesis of hollow ceria-based composites

    NASA Astrophysics Data System (ADS)

    Chen, Guozhu; Rosei, Federico; Ma, Dongling

    2015-03-01

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

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

    PubMed

    Chen, Guozhu; Rosei, Federico; Ma, Dongling

    2015-03-19

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

  20. Continuum Modeling of Mixed Conductors: a Study of Ceria

    NASA Astrophysics Data System (ADS)

    Ciucci, Francesco

    In this thesis we have derived a new way to analyze the impedance response of mixed conducting materials for use in solid oxide fuel cells (SOFCs), with the main focus on anodic materials, in particular cerium oxides. First we have analyzed the impact of mixed conductivity coupled to electrocatalytic behavior in the linear time-independent domain for a thick ceria sample. We have derived that, for a promising fuel cell material, Samarium Doped Ceria, chemical reactions are the determining component of the polarization resistance. As a second step we have extended the previous model to the time-dependent case, where we focused on single harmonic excitation, the impedance spectroscopy conditions. We extended the model to the case where some input diffusivities are spatially nonuniform. For instance we considered the case where diffusivities change significantly in the vicinity of the electrocatalytic region. As a third and final step we use to model to capture the two dimensional behavior of mixed conducting thin films, where the electronic motion from one side of the sample to the other is impeded. Such conditions are similar to those encountered in fuel cells where an electrolyte conducting exclusively oxygen ions is placed between the anode and the cathode. The framework developed was also extended to study a popular cathodic material, Lanthanum Manganite. The model is used to give unprecedented insight in SOFC polarization resistance analysis of mixed conductors. It helps elucidate rigorously rate determining steps and to address the interplay of diffusion with diffusion losses. Electrochemical surface losses dominate for most experimental conditions of Samarium Doped Ceria and they are shown to be strongly dependent on geometry.

  1. The growth and structure of thin oxide films on nickel superficially modified with ceria and cerium

    NASA Astrophysics Data System (ADS)

    Czerwinski, Franciszek

    A small addition of elements with a high affinity to oxygen can have a profound effect on the high temperature oxidation behaviour of many metals and alloys. In order to explain the improvement in oxidation resistance, the research was conducted using Ni-NiO as a model system of cation-diffusing oxides, and Ce as a typical reactive element. Three essential techniques were employed to modify the surface of Ni with Ce and CeO2: ion implantation, sol-gel technology, and reactive sputtering. The improvement of Ni oxidation resistance was assessed by oxygen uptake measurements mainly during the early stages but also for long-term exposures at temperatures between 873 and 1073 K in pure oxygen, both at low and atmospheric pressures. The variety of oxides produced were examined in detail by several advanced techniques including Rutherford backscattering spectrometry, Auger electron spectroscopy, secondary ion-mass spectrometry, transmission- and scanning-transmission electron microscopy equipped with electron and x-ray analyzers, atomic force microscopy, infrared spectroscopy, and x-ray diffraction techniques. In order to provide direct evidence regarding the mechanism of oxide growth, a sequential oxidation using oxygen isotopes 16O2/18O2 was conducted. After conversion to the form of ceramic coating, superficially applied CeO2 sol-gel significantly reduced the Ni oxidation rate as well as changing the NiO morphology and internal microstructure. The extent of the effect depended on coating thickness, size of CeO2 particles, substrate surface finishing and preoxidation before coating. Under optimum conditions, the reduction in the Ni oxidation rate achieved by sol-gel, reactive sputtering, and ion implantation, was similar. It was found that Ni oxidation resistance is controlled by a well-defined NiO sublayer that is composed of randomly-oriented NiO grains and CeO2 particles. Moreover, in this sublayer, the Ce4+ ions segregate to the NiO grain boundaries. At high

  2. Aerobic oxidation of cyclic amines to lactams catalyzed by ceria-supported nanogold

    DOE PAGES

    Dairo, Taiwo O.; Nelson, Nicholas C.; Slowing, Igor I.; ...

    2016-09-23

    Here, the oxidative transformation of cyclic amines to lactams, which are important chemical feedstocks, is efficiently catalyzed by CeO2-supported gold nanoparticles (Au/CeO2) and Aerosil 200 in the presence of an atmosphere of O2. The complete conversion of pyrrolidine was achieved in 6.5 h at 160 °C, affording a 97 % yield of the lactam product 2-pyrrolidone (γ-butyrolactam), while 2-piperidone (δ-valerolactam) was synthesized from piperidine (83 % yield) in 2.5 h. Caprolactam, the precursor to the commercially important nylon-6, was obtained from hexamethyleneimine in 37 % yield in 3 h. During the oxidation of pyrrolidine, two transient species, 5-(pyrrolidin-1-yl)-3,4-dihydro-2H-pyrrole (amidine-5) andmore » 4-amino-1-(pyrrolidin-1-yl)butan-1-one, were observed. Both of these compounds were oxidized to 2-pyrrolidone under catalytic conditions, indicating their role as intermediates in the reaction pathway. In addition to the reactions of cyclic secondary amines, Au/CeO2 also efficiently catalyzes the oxidation of N-methyl cyclic tertiary amines to the corresponding lactams at 80 and 100 °C.« less

  3. Aerobic oxidation of cyclic amines to lactams catalyzed by ceria-supported nanogold

    SciTech Connect

    Dairo, Taiwo O.; Nelson, Nicholas C.; Slowing, Igor I.; Angelici, Robert J.; Woo, L. Keith

    2016-09-23

    Here, the oxidative transformation of cyclic amines to lactams, which are important chemical feedstocks, is efficiently catalyzed by CeO2-supported gold nanoparticles (Au/CeO2) and Aerosil 200 in the presence of an atmosphere of O2. The complete conversion of pyrrolidine was achieved in 6.5 h at 160 °C, affording a 97 % yield of the lactam product 2-pyrrolidone (γ-butyrolactam), while 2-piperidone (δ-valerolactam) was synthesized from piperidine (83 % yield) in 2.5 h. Caprolactam, the precursor to the commercially important nylon-6, was obtained from hexamethyleneimine in 37 % yield in 3 h. During the oxidation of pyrrolidine, two transient species, 5-(pyrrolidin-1-yl)-3,4-dihydro-2H-pyrrole (amidine-5) and 4-amino-1-(pyrrolidin-1-yl)butan-1-one, were observed. Both of these compounds were oxidized to 2-pyrrolidone under catalytic conditions, indicating their role as intermediates in the reaction pathway. In addition to the reactions of cyclic secondary amines, Au/CeO2 also efficiently catalyzes the oxidation of N-methyl cyclic tertiary amines to the corresponding lactams at 80 and 100 °C.

  4. Real-Time Observation of Platinum Redispersion on Ceria-Based Oxide by In-situ Turbo-XAS in Fluorescence Mode

    SciTech Connect

    Nagai, Yasutaka; Dohmae, Kazuhiko; Tanabe, Toshitaka; Shinjoh, Hirofumi; Takagi, Nobuyuki; Ikeda, Yasuo; Guilera, Gemma; Pascarelli, Sakura; Newton, Mark; Matsumoto, Shin'ichi

    2007-02-02

    A real-time observation of the redispersion behavior of sintered Pt on ceria-based oxide was made possible by in-situ time-resolved Turbo-XAS in fluorescence mode. 2 wt% Pt/Ce-Zr-Y mixed oxide samples were prepared, and then treated under an aging condition. The average Pt particle size measured by CO absorption method after aging was 7 nm. Redispersion treatments of the previously aged catalyst were carried out at 600 deg. C within an in-situ XAS cell in a cyclical flow of reducing/oxidizing gases. Pt L3-edge XANES spectra were collected every 1.1 second under in-situ conditions. From a change in the XANES spectra, we observed that the Pt particle size of the aged catalyst decreased from 7 to 5 nm after 60 seconds and then to 3 nm after 1000 seconds.

  5. Effect of Gd dopant concentration on the defect engineering in ceria nanostructures

    SciTech Connect

    Sakar, M.; Rajkumar, Rubini; Tripathy, S.; Balakumar, S.

    2012-12-15

    Graphical abstract: Display Omitted Highlights: ► Investigates the ionic conductivity of defect engineered Gd doped nano scale ceria. ► Reveals that there exists an optimum concentration of dopant to engineer ceria with large O{sub 2} vacancies. ► For the first time the Nanosponge morphology observed in the Gd doped nanoceria. ► It is observed that 5% of Gd in ceria is optimum to induce appropriate amount of defects. ► Thereby an enhanced ionic conductivity is achieved in 5% Gd doped ceria. -- Abstract: In this study, the fabrication and characterization of pure and gadolinium (Gd) doped ceria nanostructures (Ce{sub 1−x}Gd{sub x}O{sub 2−δ} where x = 0.05, 0.1 and 0.2) are investigated. The origin of defect formation has been systematically investigated by XRD and UV-Visible Raman. All the fabricated ceria are found to be “Nanosponge” morphology which is observed by using FESEM technique. The charge transfer of O{sup 2−} ions and Ce{sup 3+}/Ce{sup 4+} in the ceria host due to these defect structures are studied by UV–DRS. Impedance analysis is showed an enhanced ionic conductivity for 5% Gd doped ceria compared to other concentration of Gd, revealing that the dopant concentration is a critical parameter in engineering a large number of vacancy defects in ceria nanostructures.

  6. Ferroelectricity in yttrium-doped hafnium oxide

    NASA Astrophysics Data System (ADS)

    Müller, J.; Schröder, U.; Böscke, T. S.; Müller, I.; Böttger, U.; Wilde, L.; Sundqvist, J.; Lemberger, M.; Kücher, P.; Mikolajick, T.; Frey, L.

    2011-12-01

    Structural and electrical evidence for a ferroelectric phase in yttrium doped hafnium oxide thin films is presented. A doping series ranging from 2.3 to 12.3 mol% YO1.5 in HfO2 was deposited by a thermal atomic layer deposition process. Grazing incidence X-ray diffraction of the 10 nm thick films revealed an orthorhombic phase close to the stability region of the cubic phase. The potential ferroelectricity of this orthorhombic phase was confirmed by polarization hysteresis measurements on titanium nitride based metal-insulator-metal capacitors. For 5.2 mol% YO1.5 admixture the remanent polarization peaked at 24 μC/cm2 with a coercive field of about 1.2 MV/cm. Considering the availability of conformal deposition processes and CMOS-compatibility, ferroelectric Y:HfO2 implies high scaling potential for future, ferroelectric memories.

  7. Role of the oxidation state of cerium on the ceria surfaces for silicate adsorption

    NASA Astrophysics Data System (ADS)

    Seo, Jihoon; Moon, Jinok; Kim, Joo Hyun; Lee, Kangchun; Hwang, Junha; Yoon, Heesung; Yi, Dong Kee; Paik, Ungyu

    2016-12-01

    In this study, we have investigated the role of the Ce oxidation state (Ce3+/Ce4+) on the CeO2 surfaces for silicate adsorption. In aqueous medium, the Ce3+ sites lead to the formation of -OH groups at the CeO2 surface through H2O dissociation. Silicate ions can adsorb onto the CeO2 surface through interaction with the -OH groups (-Ce-OH- + -Si-O- ↔ -Ce-O-Si- + OH-). As the Ce3+ concentration increased from 19.3 to 27.6%, the surface density of -OH group increased from 0.34 to 0.72 OH/nm2. To evaluate the adsorption behaviors of silicate ions onto CeO2 NPs, we carried out an adsorption isothermal analysis, and the adsorption isotherm data followed the Freundlich model. The Freundlich constant for the relative adsorption capacity (KF) and adsorption intensity (1/n) indicated that CeO2 NPs with high Ce3+ concentration show higher adsorption affinity with silicate ions. As a result, we have demonstrated that the Ce oxidation state (Ce3+/Ce4+) on the CeO2 surface can have a significant influence on the silicate adsorption.

  8. Intermediate temperature single-chamber methane fed SOFC based on Gd doped ceria electrolyte and La 0.5Sr 0.5CoO 3- δ as cathode

    NASA Astrophysics Data System (ADS)

    Morales, M.; Piñol, S.; Segarra, M.

    Single-chamber fuel cells with electrodes supported on an electrolyte of gadolinium doped ceria Ce 1- xGd xO 2- y with x = 0.2 (CGO) 200 μm thickness has been successfully prepared and characterized. The cells were fed directly with a mixture of methane and air. Doped ceria electrolyte supports were prepared from powders obtained by the acetyl-acetonate sol-gel related method. Inks prepared from mixtures of precursor powders of NiO and CGO with different particle sizes and compositions were prepared, analysed and used to obtain optimal porous anodes thick films. Cathodes based on La 0.5Sr 0.5CoO 3 perovskites (LSCO) were also prepared and deposited on the other side of the electrolyte by inks prepared with a mixture of powders of LSCO, CGO and AgO obtained also by sol-gel related techniques. Both electrodes were deposited by dip coating at different thicknesses (20-30 μm) using a commercial resin where the electrode powders were dispersed. Finally, electrical properties were determined in a single-chamber reactor where methane, as fuel, was mixed with synthetic air below the direct combustion limit. Stable density currents were obtained in these experimental conditions. Temperature, composition and flux rate values of the carrier gas were determinants for the optimization of the electrical properties of the fuel cells.

  9. Transparent conducting oxides: A -doped superlattice approach

    SciTech Connect

    Cooper, Valentino R; Seo, Sung Seok A.; Lee, Suyoun; Kim, Jun Sung; Choi, Woo Seok; Okamoto, Satoshi; Lee, Ho Nyung

    2014-01-01

    Two-dimensional electron gases (2DEGs) at the interface of oxide heterostructures have been the subject of recent experiment and theory, due to the intriguing phenomena that occur in confined electronic states. However, while much has been done to understand the origin of 2DEGs and related phenomena, very little has been explored with regards to the control of conduction pathways and the distribution of charge carriers. Using first principles simulations and experimental thin film synthesis methods, we examine the effect of dimensionality on carrier transport in La delta-doped SrTiO3 (STO) superlattices, as a function of the thickness of the insulating STO spacer. Our computed Fermi surfaces and layer-resolved carrier density proles demonstrate that there is a critical thickness of the STO spacer, below which carrier transport is dominated by three-dimensional conduction of interface charges arising from appreciable overlap of the quantum mechanical wavefunctions between neighboring delta-doped layers. We observe that, experimentally, these superlattices remain highly transparent to visible light. Band structure calculations indicate that this is a result of the appropriately large gap between the O 2p and Ti d states. The tunability of the quantum mechanical wavefunctions and the optical transparency highlight the potential for using oxide heterostructures in novel opto-electronic devices; thus providing a route to the creation of novel transparent conducting oxides.

  10. Mitochondria-Targeting Ceria Nanoparticles as Antioxidants for Alzheimer's Disease.

    PubMed

    Kwon, Hyek Jin; Cha, Moon-Yong; Kim, Dokyoon; Kim, Dong Kyu; Soh, Min; Shin, Kwangsoo; Hyeon, Taeghwan; Mook-Jung, Inhee

    2016-02-23

    Mitochondrial oxidative stress is a key pathologic factor in neurodegenerative diseases, including Alzheimer's disease. Abnormal generation of reactive oxygen species (ROS), resulting from mitochondrial dysfunction, can lead to neuronal cell death. Ceria (CeO2) nanoparticles are known to function as strong and recyclable ROS scavengers by shuttling between Ce(3+) and Ce(4+) oxidation states. Consequently, targeting ceria nanoparticles selectively to mitochondria might be a promising therapeutic approach for neurodegenerative diseases. Here, we report the design and synthesis of triphenylphosphonium-conjugated ceria nanoparticles that localize to mitochondria and suppress neuronal death in a 5XFAD transgenic Alzheimer's disease mouse model. The triphenylphosphonium-conjugated ceria nanoparticles mitigate reactive gliosis and morphological mitochondria damage observed in these mice. Altogether, our data indicate that the triphenylphosphonium-conjugated ceria nanoparticles are a potential therapeutic candidate for mitochondrial oxidative stress in Alzheimer's disease.

  11. Template-assisted hydrothermally obtained titania-ceria composites and their application as catalysts in ethyl acetate oxidation and methanol decomposition with a potential for sustainable environment protection

    NASA Astrophysics Data System (ADS)

    Tsoncheva, Tanya; Mileva, Alexandra; Issa, Gloria; Dimitrov, Momtchil; Kovacheva, Daniela; Henych, Jiří; Scotti, Nicola; Kormunda, Martin; Atanasova, Genoveva; Štengl, Vaclav

    2017-02-01

    High surface area mesoporous ceria-titania binary materials with high Lewis acidity and improved reduction properties were synthesized using template assisted hydrothermal technique. The obtained materials were characterized by low temperature nitrogen physisorption, XRD, SEM, TEM, Raman, UV-vis, XPS, FTIR, FTIR of adsorbed pyridine and thermo-programmed reduction with hydrogen. Their catalytic activity was tested in total oxidation of ethyl acetate and methanol decomposition to CO and hydrogen with a potential application in VOCs elimination and alternative fuels, respectively. The structural changes in the binary materials, which could be tuned by the variation in the Ce/Ti ratio and the temperature of hydrothermal treatment, provoked significant changes in their textural, surface and redox properties, which is in close relation to the catalytic activity and selectivity in various catalytic processes. The intimate contact between the individual oxides results in the formation of different catalytic active sites and their role in the studied catalytic reactions was discussed in details.

  12. A novel Ni/ceria-based anode for metal-supported solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Rojek-Wöckner, Veronika A.; Opitz, Alexander K.; Brandner, Marco; Mathé, Jörg; Bram, Martin

    2016-10-01

    For optimization of ageing behavior, electrochemical performance, and sulfur tolerance of metal-supported solid oxide fuel cells a new anode concept is introduced, which is based on a Ni/GDC cermet replacing the established Ni/YSZ anodes. In the present work optimized processing parameters compatible with MSC substrates are specified by doing sintering studies on pressed bulk specimen and on real porous anode structures. The electrochemical performance of the Ni/GDC anodes was characterized by means of symmetrical electrolyte supported model-type cells. In this study, three main objectives are pursued. Firstly, the effective technical realization of the Ni/GDC concept is demonstrated. Secondly, the electrochemical behavior of Ni/GDC porous anodes is characterized by impedance spectroscopy and compared with the current standard Ni/YSZ anode. Further, a qualitative comparison of the sulfur poisoning behavior of both anode types is presented. Thirdly, preliminary results of a successful implementation of the Ni/GDC cermet into a metal-supported single cell are presented.

  13. One-Dimensional Ceria as Catalyst for the Low-Temperature Water-Gas Shift Reaction

    SciTech Connect

    Han, W.; Wen, W; Hanson, J; Teng, X; Marinkovic, N; Rodriguez, J

    2009-01-01

    Synchrotron-based in situ time-resolved X-ray diffraction and X-ray absorption spectroscopy were used to study pure ceria and Pd-loaded ceria nanotubes and nanorods (1D-ceria) as catalysts for the water-gas shift (WGS) reaction. While bulk ceria is very poor as WGS catalysts, pure 1D-ceria displayed catalytic activity at a temperature as low as 300 C. The reduction of the pure 1D-ceria in pure hydrogen started at 150 C, which is a much lower temperature than those previously reported for the reduction of 3D ceria nanoparticles. This low reduction temperature reflects the novel morphology of the oxide systems and may be responsible for the low-temperature WGS catalytic activity seen for the 1D-ceria. Pd-loaded 1D ceria displayed significant WGS activity starting at 200 C. During pretreatment in H{sub 2}, the ceria lattice parameter increased significantly around 60 C, which indicates that Pd-oxygen interactions may facilitate the reduction of Pd-loaded 1D-ceria. Pd and ceria both participate in the formation of the active sites for the catalytic reactions. The low-temperature hydrogen pretreatment results in higher WGS activity for Pd-loaded 1D-ceria.

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

    SciTech Connect

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

    2014-01-21

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

  15. Nanometer-sized ceria-coated silica-iron oxide for the reagentless microextraction/preconcentration of heavy metals in environmental and biological samples followed by slurry introduction to ICP-OES.

    PubMed

    Dados, A; Paparizou, E; Eleftheriou, P; Papastephanou, C; Stalikas, C D

    2014-04-01

    A slurry suspension sampling technique is developed and optimized for the rapid microextraction of heavy metals and analysis using nanometer-sized ceria-coated silica-iron oxide particles and inductively coupled plasma optical emission spectrometry (ICP-OES). Magnetic-silica material is synthesized by a co-precipitation and sol-gel method followed by ceria coating through a precipitation. The large particles are removed using a sedimentation-fractionation procedure and a magnetic homogeneous colloidal suspension of ceria-modified iron oxide-silica is produced for microextraction. The nanometer-sized particles are separated from the sample solution magnetically and analyzed with ICP-OES using a slurry suspension sampling approach. The ceria-modified iron oxide-silica does not contain any organic matter and this probably justifies the absence of matrix effect on plasma atomization capacity, when increased concentrations of slurries are aspirated. The As, Be, Mo, Cr, Cu, Pb, Hg, Sb, Se and V can be preconcentrated by the proposed method at pH 6.0 while Mn, Cd, Co and Ni require a pH ≥ 8.0. Satisfactory values are obtained for the relative standard deviations (2-6%), recoveries (88-102%), enrichment factors (14-19) and regression correlation coefficients as well as detectability, at sub-μg L(-1) levels. The applicability of magnetic ceria for the microextraction of metal ions in combination with the slurry introduction technique using ICP is substantiated by the analysis of environmental water and urine samples.

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

    PubMed

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

    2016-08-17

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

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

    PubMed Central

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

    2014-01-01

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

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

    PubMed

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

    2015-01-07

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

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

    SciTech Connect

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

    2012-01-12

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

  20. Cerium oxide for sunscreen cosmetics

    NASA Astrophysics Data System (ADS)

    Yabe, Shinryo; Sato, Tsugio

    2003-02-01

    Ultrafine particles of Mn+ -doped ceria ( Mn+ =Mg 2+, Ca 2+, Sr 2+, Ba 2+, Y 3+, La 3+, Nd 3+, Sm 3+, Eu 3+, Tb 3+) for UV filter were prepared via soft solution chemical routes at 40°C. X-ray diffraction revealed that the prepared doped particles had the cubic fluorite structures although peak positions changed depending on the kind and amount of doped metal ion. Doping with 20 mol% Ca 2+ and 20 mol% Zn 2+ resulted in extremely decreasing the particle size (2-4 nm) and the catalytic activity of ceria for oxidation of castor oil. Ca 2+-doped cerium dioxide showed excellent UV absorbing effect and transparency in the visible ray region compared with undoped cerium dioxide.

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

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

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

  2. Controlled synthesis of ceria nanoparticles for the design of nanohybrids.

    PubMed

    Nguyen, Thanh-Dinh; Dinh, Cao-Thang; Mrabet, Driss; Tran-Thi, Minh-Nguyet; Do, Trong-On

    2013-03-15

    Ceria nanoparticles were synthesized from reaction mixture of cerium nitrate/hexamethylenediamine/water-ethylene glycol. Lamellar, particle-aggregated array, platelet, rice, cube, quasi-sphere shapes of the ceria nanoparticles can be controlled by tuning reaction parameters (reagent concentration, reagent components, pH, and reaction conditions). Studies on shape-dependent catalysis of the bare ceria samples toward CO oxidation indicated that the cube-shaped ceria nanoparticles show better catalytic activity than the nanospheres and the commercial micropowders. As capped by hexamethylenediamine (HEA) molecules, amine-functionalized ceria nanoparticles act as platforms for depositing copper particles to produce efficient Cu/CeO(2) hybrid nanocatalysts for CO conversion. Coupling of the copper clusters with the HEA-capped ceria nanocubes was achieved with the Cu contents up to 15 wt.%. The Cu/CeO(2) nanohybrids show an enhanced catalytic efficiency of low temperature CO conversion. This could be due to high exposure of the reactive {100} facets in the ceria nanocubes and interfacial copper-ceria interactions.

  3. 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.

  4. Fluorine compounds for doping conductive oxide thin films

    DOEpatents

    Gessert, Tim; Li, Xiaonan; Barnes, Teresa M; Torres, Jr., Robert; Wyse, Carrie L

    2013-04-23

    Methods of forming a conductive fluorine-doped metal oxide layer on a substrate by chemical vapor deposition are described. The methods may include heating the substrate in a processing chamber, and introducing a metal-containing precursor and a fluorine-containing precursor to the processing chamber. The methods may also include adding an oxygen-containing precursor to the processing chamber. The precursors are reacted to deposit the fluorine-doped metal oxide layer on the substrate. Methods may also include forming the conductive fluorine-doped metal oxide layer by plasma-assisted chemical vapor deposition. These methods may include providing the substrate in a processing chamber, and introducing a metal-containing precursor, and a fluorine-containing precursor to the processing chamber. A plasma may be formed that includes species from the metal-containing precursor and the fluorine-containing precursor. The species may react to deposit the fluorine-doped metal oxide layer on the substrate.

  5. Surface Faceting and Reconstruction of Ceria Nanoparticles.

    PubMed

    Yang, Chengwu; Yu, Xiaojuan; Heißler, Stefan; Nefedov, Alexei; Colussi, Sara; Llorca, Jordi; Trovarelli, Alessandro; Wang, Yuemin; Wöll, Christof

    2017-01-02

    The surface atomic arrangement of metal oxides determines their physical and chemical properties, and the ability to control and optimize structural parameters is of crucial importance for many applications, in particular in heterogeneous catalysis and photocatalysis. Whereas the structures of macroscopic single crystals can be determined with established methods, for nanoparticles (NPs), this is a challenging task. Herein, we describe the use of CO as a probe molecule to determine the structure of the surfaces exposed by rod-shaped ceria NPs. After calibrating the CO stretching frequencies using results obtained for different ceria single-crystal surfaces, we found that the rod-shaped NPs actually restructure and expose {111} nanofacets. This finding has important consequences for understanding the controversial surface chemistry of these catalytically highly active ceria NPs and paves the way for the predictive, rational design of catalytic materials at the nanoscale.

  6. UV-shielding property, photocatalytic activity and photocytotoxicity of ceria colloid solutions.

    PubMed

    Zholobak, N M; Ivanov, V K; Shcherbakov, A B; Shaporev, A S; Polezhaeva, O S; Baranchikov, A Ye; Spivak, N Ya; Tretyakov, Yu D

    2011-01-10

    UV-shielding property, photocatalytic activity and cytotoxicity (including photocytotoxicity) of citrate-stabilized ceria colloid solutions were studied. It was established that UV-shielding property (namely, the sun protection factor, the critical absorption wavelength and the UVA/UVB-ratio) of ceria nanoparticles are as good as those of titanium dioxide and zinc oxide nanoparticles. It was further demonstrated that ceria nanoparticles possesses substantially lower photocatalytic activity, which additionally decreases upon decrease in ceria particle size. It was found that colloid ceria solutions are non-toxic to mouse fibroblasts (L929) and fibroblast-like cells of African Green monkey (VERO). Moreover, ceria nanoparticles are capable to protect these cells from UV-irradiation-induced damage. It was proposed that nanocrystalline ceria could be used not only as UV-blocking material, but also as prophylactic and even therapeutic compound for sunburns treatment.

  7. Highly ytterbium-doped bismuth-oxide-based fiber.

    PubMed

    Ohara, Seiki; Kuroiwa, Yutaka

    2009-08-03

    Thermally stable highly ytterbium-doped bismuth-oxide-based glasses have been investigated. The absorbance increased linearly with Yb(2)O(3) concentration, reaching 7800 dB/m with 3 mol-% of Yb(2)O(3). An ytterbium-doped bismuth-oxide-based fiber has also been fabricated with a fiber loss of 0.24 dB/m. A fiber laser is also demonstrated, and it shows a slope efficiency of 36%.

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

    PubMed

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

    2015-01-01

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

  9. Shape-controlled ceria-based nanostructures for catalysis applications.

    PubMed

    Qiao, Zhen-An; Wu, Zili; Dai, Sheng

    2013-10-01

    Among oxide catalysts, ceria is a technologically important material because of its wide applications as a promoter in three-way catalysts for the elimination of toxic exhaust gases, low-temperature water-gas-shift reaction, oxygen sensors, oxygen permeation membrane systems, and fuel cells. The catalytic activities of cerium oxide are highly dependent on interfacial structures and nanocrystal morphologies. This Minireview highlights the recent progress in the research of ceria nanoshapes as both catalysts and catalyst supports, including the synthesis, structure characterization, catalytic properties, surface chemistry, as well as reaction mechanisms. Insights from in situ spectroscopy study and theoretical modeling of nanostructured ceria-based materials have shed light on the origin of the ceria shape effect. It is suggested that the surface structure of ceria controls the catalytic activity and selectivity through structure-dependent surface-site geometry, surface vacancy formation energy, defect sites, and coordinatively unsaturated sites on ceria. The morphology-dependent catalysis in ceria has offered a new strategy to finely tune the catalytic activity and selectivity through shape control without altering the catalyst composition. A brief summary and an outlook on this research field will be presented at the end.

  10. Comparative pulmonary toxicity of two ceria nanoparticles with the same primary size.

    PubMed

    Peng, Lu; He, Xiao; Zhang, Peng; Zhang, Jing; Li, Yuanyuan; Zhang, Junzhe; Ma, Yuhui; Ding, Yayun; Wu, Zhenqiang; Chai, Zhifang; Zhang, Zhiyong

    2014-04-10

    Ceria nanoparticles (nano-ceria) have recently gained a wide range of applications, which might pose unwanted risks to both the environment and human health. The greatest potential for the environmental discharge of nano-ceria appears to be in their use as a diesel fuel additive. The present study was designed to explore the pulmonary toxicity of nano-ceria in mice after a single exposure via intratracheal instillation. Two types of nano-ceria with the same distribution of a primary size (3-5 nm), but different redox activity, were used: Ceria-p, synthesized by a precipitation route, and Ceria-h, synthesized by a hydrothermal route. Both Ceria-p and Ceria-h induced oxidative stress, inflammatory responses and cytotoxicity in mice, but their toxicological profiles were quite different. The mean size of Ceria-p agglomerates was much smaller compared to Ceria-h, thereby causing a more potent acute inflammation, due to their higher number concentration of agglomerates and higher deposition rate in the deep lung. Ceria-h had a higher reactivity to catalyzing the generation of reactive oxygen species (ROS), and caused two waves of lung injury: bronchoalveolar lavage (BAL) inflammation and cytotoxicity in the early stage and redox-activity-evoked lipid peroxidation and pro-inflammation in the latter stage. Therefore, the size distribution of ceria-containing agglomerates in the exhaust, as well as their surface chemistry are essential characteristics to assess the potential risks of using nano-ceria as a fuel additive.

  11. Influence of the activation conditions on the elimination of residual impurities on ceria-zirconia mixed oxides

    NASA Astrophysics Data System (ADS)

    Daturi, M.; Binet, C.; Lavalley, J. C.; Vidal, H.; Kaspar, J.; Graziani, M.; Blanchard, G.

    1998-10-01

    A series of samples belonging to the ceria-zirconia solid solution has been investigated from the point of view of surface impurities, via TPO/TPD and FTIR spectroscopy. Species likely due either to the precursors or to atmospheric contamination have been taken into account and their stability has been studied following two different thermal treatments. A complete cleaning treatment is proposed in order to obtain powders of satisfactory quality for catalytic purposes. Les impuretés superficielles contenues dans une série d'oxydes mixtes cérine- zircone ont été étudiées par TPO/TPD et spectroscopie infrarouge. Les impuretés provenant soit des précurseurs soit de la contamination atmosphérique (carbonates) ont été identifiées et leur stabilité thermique a été étudiée en fonction de différents traitements thermiques. Une méthode thermique de purification est proposée afin d'obtenir des poudres de qualité suffisante pour les applications catalytiques.

  12. Studies on Synthesis, Microstructure and Transport Properties of Doped Cerium Oxides

    NASA Astrophysics Data System (ADS)

    Handal, Hala Talaat Abd El-Samei

    Acceptor-doped ceria exhibits mixed ionic electronic conduction in reducing conditions and chemical stability against sulfur poisoning and coking. This thesis's primary goal is to explore new anode materials based on ceria--solid solutions for solid oxide fuel cells (SOFCs). The physicochemical and electrochemical performance of Ce0.9-xY 0.1MnxO2-delta ( x = 0 to 15 mol%) (CYMO) and Ce0.87Y0.1Mn 0.01N0.02O2-delta (N = Mg or Ca) were studied. Among the materials investigated in this study, Ce0.89Y 0.1Mn0.01Mg0.02O2-delta (Mg-CYMO) showed the highest total conductivity of 0.2 S cm-1 at 700°C in H2. An area specific polarization resistance of 0.23 O cm2 was observed for both Mg-CYMO and Ce0.8Y 0.1Mn0.1O2-delta (10CYMO) at 800°C, in wet H2. Chronoamperometric measurement for the symmetrical cell configuration based on 10CYMO electrodes showed stable performance upon exposure to 10 ppm H2S/H2. In a full cell configuration, 10CYMO (anode)/YSZ (electrolyte)/La0.8Sr0.2MnO3 (LSM)-YSZ cathode, polarization resistance of 1.4 O cm2 and power density of 75 mW/cm2 were obtained at 800°C in wet H2. The main challenge of employing proton-conducting electrolytes in SOFC is their poor chemical stability in the presence of steam and hydrocarbon fuels. Another goal of this thesis is to develop a chemically stable proton-conducting electrolyte for SOFCs. The effects of Fe and Co substitution on the electrical and physicochemical properties of BaCe0.9Sm0.1O 3-delta (BCS) were evaluated. Thermogravimetric analysis showed that incorporation of 5 to 10 mol% Fe or Co in BCS did not improve the chemical stability in CO2 at elevated temperatures. The BCSC10 sample sintering at 1400°C showed the highest electrical conductivity of 0.02 S cm -1 at 600°C in air, but it did not show any appreciable proton mobility under humidified atmosphere.

  13. Uptake and distribution of ceria nanoparticles in cucumber plants.

    PubMed

    Zhang, Zhiyong; He, Xiao; Zhang, Haifeng; Ma, Yuhui; Zhang, Peng; Ding, Yayun; Zhao, Yuliang

    2011-08-01

    The presence and release of nanoparticles (NPs) into the environment have important implications for human health and the environment. A critical aspect of the risk assessment of nanoparticles is to understand the interactions of manufactured nanoparticles with plants. In this study, the uptake and distribution characteristics of two types of ceria nanoparticles with sizes of ca. 7 nm and 25 nm in cucumber plants were investigated using a radiotracer method and other techniques. With increasing concentration of the nanoparticles, concentration dependent absorption by the plant roots was noticed, but the majority of the particles only loosely adhered to the root surface. The seedlings treated with 7 nm ceria particles showed significantly higher ceria contents in both roots and shoots than those exposed to 25 nm ceria particles at all test concentrations (2, 20, and 200 mg L(-1)). Only very limited amounts of ceria nanoparticles could be transferred from the roots to shoots because the entry of nanoparticles into the roots was difficult. However, the results of tissue distributions of ceria nanoparticles in the plants and two dimensional distributions of the particles in the leaves imply that once they have entered into the vascular cylinder, ceria nanoparticles could move smoothly to the end of the vascular bundle along with water flow. To the best of our knowledge, this is the first detailed study of uptake and distribution of metal oxide nanoparticles in plants.

  14. Defects and ferromagnetism in transition metal doped zinc oxide

    NASA Astrophysics Data System (ADS)

    Thapa, Sunil

    Transition metal doped zinc oxide has been studied recently due to its potential application in spintronic devices. The magnetic semiconductor, often called Diluted Magnetic Semiconductors (DMS), has the ability to incorporate both charge and spin into a single formalism. Despite a large number of studies on ferromagnetism in ZnO based DMS and the realization of its room temperature ferromagnetism, there is still a debate about the origin of the ferromagnetism. In this work, the synthesis and characterization of transition metal doped zinc oxide have been carried out. The sol-gel method was used to synthesize thin films, and they were subsequently annealed in air. Characterization of doped zinc oxide films was carried out using the UV-visible range spectrometer, scanning electron microscopy, superconducting quantum interference device (SQUID), x-ray diffraction(XRD) and positron annihilation spectroscopy. Hysteresis loops were obtained for copper and manganese doped zinc oxide, but a reversed hysteresis loop was observed for 2% Al 3% Co doped zinc oxide. The reversed hysteresis loop has been explained using a two-layer model.

  15. Synthesis and characterization of scandia ceria stabilized zirconia powders prepared by polymeric precursor method for integration into anode-supported solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Tu, Hengyong; Liu, Xin; Yu, Qingchun

    2011-03-01

    Scandia ceria stabilized zirconia (10Sc1CeSZ) powders are synthesized by polymeric precursor method for use as the electrolyte of anode-supported solid oxide fuel cell (SOFC). The synthesized powders are characterized in terms of crystalline structure, particle shape and size distribution by X-ray diffraction (XRD), transmission electron microscopy (TEM) and photon correlation spectroscopy (PCS). 10Sc1CeSZ electrolyte films are deposited on green anode substrate by screen-printing method. Effects of 10Sc1CeSZ powder characteristics on sintered films are investigated regarding the integration process for application as the electrolytes in anode-supported SOFCs. It is found that the 10Sc1CeSZ films made from nano-sized powders with average size of 655 nm are very porous with many open pores. In comparison, the 10Sc1CeSZ films made from micron-sized powders with average size of 2.5 μm, which are obtained by calcination of nano-sized powders at higher temperatures, are much denser with a few closed pinholes. The cell performances are 911 mW cm-2 at the current density of 1.25 A cm-2 and 800 °C by application of Ce0.8Gd0.2O2 (CGO) barrier layer and La0.6Sr0.4CoO3 (LSC) cathode.

  16. Monolayer Contact Doping from a Silicon Oxide Source Substrate.

    PubMed

    Ye, Liang; González-Campo, Arántzazu; Kudernac, Tibor; Núñez, Rosario; de Jong, Michel; van der Wiel, Wilfred G; Huskens, Jurriaan

    2017-04-03

    Monolayer contact doping (MLCD) is a modification of the monolayer doping (MLD) technique that involves monolayer formation of a dopant-containing adsorbate on a source substrate. This source substrate is subsequently brought into contact with the target substrate, upon which the dopant is driven into the target substrate by thermal annealing. Here, we report a modified MLCD process, in which we replace the commonly used Si source substrate by a thermally oxidized substrate with a 100 nm thick silicon oxide layer, functionalized with a monolayer of a dopant-containing silane. The thermal oxide potentially provides a better capping effect and effectively prevents the dopants from diffusing back into the source substrate. The use of easily accessible and processable silane monolayers provides access to a general and modifiable process for the introduction of dopants on the source substrate. As a proof of concept, a boron-rich carboranyl-alkoxysilane was used here to construct the monolayer that delivers the dopant, to boost the doping level in the target substrate. X-ray photoelectron spectroscopy (XPS) showed a successful grafting of the dopant adsorbate onto the SiO2 surface. The achieved doping levels after thermal annealing were similar to the doping levels acessible by MLD as demonstrated by secondary ion mass spectrometry measurements. The method shows good prospects, e.g. for use in the doping of Si nanostructures.

  17. Doping-Promoted Solar Water Oxidation on Hematite Photoanodes.

    PubMed

    Zhang, Yuchao; Ji, Hongwei; Ma, Wanhong; Chen, Chuncheng; Song, Wenjing; Zhao, Jincai

    2016-07-01

    As one of the most promising materials for solar water oxidation, hematite has attracted intense research interest for four decades. Despite their desirable optical band gap, stability and other attractive features, there are great challenges for the implementation of hematite-based photoelectrochemical cells. In particular, the extremely low electron mobility leads to severe energy loss by electron hole recombination. Elemental doping, i.e., replacing lattice iron with foreign atoms, has been shown to be a practical solution. Here we review the significant progresses in metal and non-metal element doping-promoted hematite solar water oxidation, focusing on the role of dopants in adjusting carrier density, charge collection efficiency and surface water oxidation kinetics. The advantages and salient features of the different doping categories are compared and discussed.

  18. Fluoride and Oxide Holmium Doped Lasers

    NASA Astrophysics Data System (ADS)

    Kalisky, Yehoshua

    1989-12-01

    Laser holmium belongs to a family of rare earth doped ions emitting in the near or mid-IR spectral range. Its 2.1 μm laser emission has potential applications in many fields as will be discussed below. In this review we will concentrate on the following topics: A. General characteristics of Ho3+ laser and hosts. B. Significant milestones in holmium laser development. C. Mechanism of basic processes. D. Engineering considerations E. Applications F. Trends and future. A. General Characteristics The main characteristics of holmium laser are as follows: 1-A. Its emission wavelength originates from the 517-->518 transition (≍2.1 μm) 2-A. The main laser hosts used are: oxide crystals such as YAG (Y3Al5O12), YAlO3 or fluorides such as YLF (YLiF4) or HoBaYb28. 3-A. Energy sensitizers such as Cr3+, Tm3+, Er3+ are used in order to increase the laser efficiency and to better utilize the lamp emission spectrum. 4-A. Holmium laser needs liquid nitrogen cooling for efficient operation. At ambient temperature it behaves as a quasi three-level system with high lasing threshold and low slope efficiency. 5-A. The laser can be operated both in CW or pulsed modes. 6-A. It has high gain cross section and a long lifetime of 5I7 level which results in an efficient Q-switched operation. 7-A. Applications: Medical Free space communication Eye-safe range finders or Target illuminators Remote sensing Tunable operational amplifier The most popular hosts for holmium laser are the aPHo:YAG (erbium-thulium-sensitized Ho:YAG) and aPHo:YLF. Tables 1 and 2 summarize the mechanical and optical properties of YLF, YAG and GSGG (gadolinium scandium galium garnet), respectively. The mechanical and thermal properties of YAG are better than those of GSGG and superior relative to YLF - see Table 1. From Table 2 it is inferred that YLF has a negative derivative of its refraction index with temperature, implying that YLF may show a lower thermal lensing effect than YAG in spite of its lower thermal

  19. CSA doped polypyrrole-zinc oxide thin film sensor

    NASA Astrophysics Data System (ADS)

    Chougule, M. A.; Jundale, D. M.; Raut, B. T.; Sen, Shashwati; Patil, V. B.

    2013-02-01

    The polypyrrole-zinc oxide (PPy-ZnO) hybrid sensor doped with different weight ratios of camphor sulphonic acid (CSA) were prepared by spin coating technique. These CSA doped PPy-ZnO hybrids were characterized by field emission scanning electron microscope (FESEM) and fourier transform infrared (FTIR) which proved the formation of polypyrrole, PPy-ZnO and the interaction between polypyrrole - ZnO (PPy-ZnO) hybrid with CSA doping. The gas sensing properties of the PPy-ZnO hybrid films doped with CSA have been studied for oxidizing (NO2) as well as reducing (H2S, NH3, CH4OH and CH3OH) gases at room temperature. We demonstrate that CSA doped PPy-ZnO hybrid films are highly selective to NO2 along with high-sensitivity at low concentration (80% to 100 ppm) and better stability, which suggested that the CSA doped PPy-ZnO hybrid films are potential candidate for NO2 detection at room temperature.

  20. On the wetting behavior of ceria thin films grown by pulsed laser deposition

    NASA Astrophysics Data System (ADS)

    Fu, Sin-Pui; Rossero, Jorge; Chen, Chen; Li, Daniel; Takoudis, Christos G.; Abiade, Jeremiah T.

    2017-02-01

    Polymers are most widely used in the production of water-repellant coatings. However, their use in applications requiring wear resistance or high-temperature stability is extremely limited. A recent report suggests that wear resistant, thermally stable rare earth oxide materials like cerium dioxide (ceria) are intrinsically water repellant. We have studied this intriguing finding for ceria thin films fabricated by pulsed laser deposition (PLD) at different oxygen pressures and different substrate temperatures. We used a custom apparatus for measuring water contact angles on ceria films deposited by PLD. X-ray photoelectron spectroscopy was used to determine the relationship between the ceria wetting behavior and ceria surface chemistry. Our results show that ceria thin films are intrinsically hydrophilic and that hydrophobicity arises due to adsorption of hydrocarbon species after ˜24 h.

  1. Non-Prestonian behavior of rectangular shaped ceria slurry in shallow trench isolation chemical mechanical planarization.

    PubMed

    Kim, Ye-Hwan; Jung, Yeon-Gil; Yoon, Gwang Seob; Moon, Jinok; Watanabe, Akira; Naito, Makio; Paik, Ungyu

    2012-03-01

    Rectangular ceria particles were synthesized using the flash creation method. The influence of the morphology of ceria particles and the surfactant concentration on the removal rate was systematically investigated. These ceria slurries with polymeric surfactant molecules as the passivation agents of Si3N4 film, shows an exceptional non-Prestonian behaviors. The non-Prestonian behavior can be attributed to the increase in the contact area of the ceria particles with the SiO2 film, which is dominated by the morphology of the ceria particles. Force measurements using an atomic force microscope (AFM) at different concentrations of polymeric surfactant molecules was used to identify the interactions between the polymeric molecules and the oxide film and analyze the non-Prestonian behavior of ceria slurry having rectangular abrasives.

  2. Dysprosium oxide and dysprosium-oxide-doped titanium oxide thin films grown by atomic layer deposition

    SciTech Connect

    Tamm, Aile Kozlova, Jekaterina; Aarik, Lauri; Aarik, Jaan; Kukli, Kaupo; Link, Joosep; Stern, Raivo

    2015-01-15

    Dysprosium oxide and dysprosium-oxide-doped titanium oxide thin films were grown by atomic layer deposition on silicon substrates. For depositing dysprosium and titanium oxides Dy(thd){sub 3}-O{sub 3} and TiCl{sub 4}-O{sub 3} were used as precursors combinations. Appropriate parameters for Dy(thd){sub 3}-O{sub 3} growth process were obtained by using a quartz crystal microbalance system. The Dy{sub 2}O{sub 3} films were deposited on planar substrates and on three-dimensional substrates with aspect ratio 1:20. The Dy/Ti ratio of Dy{sub 2}O{sub 3}-doped TiO{sub 2} films deposited on a planar silicon substrate ranged from 0.04 to 0.06. Magnetometry studies revealed that saturation of magnetization could not be observed in planar Dy{sub 2}O{sub 3} films, but it was observable in Dy{sub 2}O{sub 3} films on 3D substrates and in doped TiO{sub 2} films with a Dy/Ti atomic ratio of 0.06. The latter films exhibited saturation magnetization 10{sup −6} A cm{sup 2} and coercivity 11 kA/m at room temperature.

  3. Self-limited kinetics of electron doping in correlated oxides

    SciTech Connect

    Chen, Jikun Zhou, You; Jiang, Jun; Shi, Jian; Ramanathan, Shriram; Middey, Srimanta; Chakhalian, Jak; Chen, Nuofu; Chen, Lidong; Shi, Xun; Döbeli, Max

    2015-07-20

    Electron doping by hydrogenation can reversibly modify the electrical properties of complex oxides. We show that in order to realize large, fast, and reversible response to hydrogen, it is important to consider both the electron configuration on the transition metal 3d orbitals, as well as the thermodynamic stability in nickelates. Specifically, large doping-induced resistivity modulations ranging several orders of magnitude change are only observed for rare earth nickelates with small ionic radii on the A-site, in which case both electron correlation effects and the meta-stability of Ni{sup 3+} are important considerations. Charge doping via metastable incorporation of ionic dopants is of relevance to correlated oxide-based devices where advancing approaches to modify the ground state electronic properties is an important problem.

  4. Self-limited kinetics of electron doping in correlated oxides

    NASA Astrophysics Data System (ADS)

    Chen, Jikun; Zhou, You; Middey, Srimanta; Jiang, Jun; Chen, Nuofu; Chen, Lidong; Shi, Xun; Döbeli, Max; Shi, Jian; Chakhalian, Jak; Ramanathan, Shriram

    2015-07-01

    Electron doping by hydrogenation can reversibly modify the electrical properties of complex oxides. We show that in order to realize large, fast, and reversible response to hydrogen, it is important to consider both the electron configuration on the transition metal 3d orbitals, as well as the thermodynamic stability in nickelates. Specifically, large doping-induced resistivity modulations ranging several orders of magnitude change are only observed for rare earth nickelates with small ionic radii on the A-site, in which case both electron correlation effects and the meta-stability of Ni3+ are important considerations. Charge doping via metastable incorporation of ionic dopants is of relevance to correlated oxide-based devices where advancing approaches to modify the ground state electronic properties is an important problem.

  5. Molten carbonate fuel cell cathode with mixed oxide coating

    DOEpatents

    Hilmi, Abdelkader; Yuh, Chao-Yi

    2013-05-07

    A molten carbonate fuel cell cathode having a cathode body and a coating of a mixed oxygen ion conductor materials. The mixed oxygen ion conductor materials are formed from ceria or doped ceria, such as gadolinium doped ceria or yttrium doped ceria. The coating is deposited on the cathode body using a sol-gel process, which utilizes as precursors organometallic compounds, organic and inorganic salts, hydroxides or alkoxides and which uses as the solvent water, organic solvent or a mixture of same.

  6. Modification of solid oxide fuel cell anodes with cerium oxide coatings

    NASA Astrophysics Data System (ADS)

    Tang, Ling

    A priority for research in solid oxide fuel cells (SOFCs) is to develop cells that can maintain adequate performance in sulfur-containing fuel streams. There has been evidence that cerium oxide in the anode or electrolyte is associated with sulfur tolerance of the cell, but the mechanism underlying this effect is not well understood. The objective of the present research is to show that the porous cermet SOFC anodes can be coated with cerium oxide films, so that the cell performance can be evaluated as a function of the anode structure and the microstructure of the film. Three types of anodes---Ni/yttria-stabilized zirconia (YSZ), Ni/gadolinia-doped ceria (GDC), and Ni/GDC with GDC interlayer were infiltrated with an aqueous solution to deposit nanocrystalline ceria films. The cells were then tested in hydrogen/nitrogen fuel containing hydrogen sulfide at levels up to 500 ppm. Modification of the anodes with thiol-terminated and trichlorosilane-terminated surfactants was explored. Different ceria film morphology was achieved for each surface treatment. In the cells that underwent performance testing, the thiol treatment promoted ceria film deposition, while the sulfonate treatment suppressed ceria deposition. Uniform ceria films up to 100 nm thick could be deposited in 48 h. Results on cell testing conditions, e.g. current, time, and H2S exposure were related to different anode structures and ceria coating morphologies. In general, the Ni/GDC anodes showed better performance than the Ni/YSZ anode. The introduction of ceria films often resulted in higher cell current and longer testing time, including operation under H2S exposure. Post-testing characterization revealed that, for some anodes, microstructure changes such as coarsening of Ni in the anode, migration of Ni to the anode surface, and depletion of Ni occurred. These changes in microstructure were irreversible and might account for permanent loss of cell performance. The presence of ceria films delayed these

  7. Plasma sprayed ceria-containing interlayer

    DOEpatents

    Schmidt, Douglas S.; Folser, George R.

    2006-01-10

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

  8. Process for fabricating doped zinc oxide microsphere gel

    DOEpatents

    Arnold, W.D. Jr.; Bond, W.D.; Lauf, R.J.

    1991-11-05

    Disclosed are a new composition and method of making same for a doped zinc oxide microsphere and articles made therefrom for use in an electrical surge arrestor which has increased solid content, uniform grain size and is in the form of a gel. 4 figures.

  9. Process for fabricating doped zinc oxide microsphere gel

    DOEpatents

    Arnold, Jr., Wesley D.; Bond, Walter D.; Lauf, Robert J.

    1991-01-01

    A new composition and method of making same for a doped zinc oxide microsphere and articles made therefrom for use in an electrical surge arrestor which has increased solid content, uniform grain size and is in the form of a gel.

  10. Chemical vapor deposition of fluorine-doped zinc oxide

    DOEpatents

    Gordon, Roy G.; Kramer, Keith; Liang, Haifan

    2000-06-06

    Fims of fluorine-doped zinc oxide are deposited from vaporized precursor compounds comprising a chelate of a dialkylzinc, such as an amine chelate, an oxygen source, and a fluorine source. The coatings are highly electrically conductive, transparent to visible light, reflective to infrared radiation, absorbing to ultraviolet light, and free of carbon impurity.

  11. Metal oxide charge transport material doped with organic molecules

    DOEpatents

    Forrest, Stephen R.; Lassiter, Brian E.

    2016-08-30

    Doping metal oxide charge transport material with an organic molecule lowers electrical resistance while maintaining transparency and thus is optimal for use as charge transport materials in various organic optoelectronic devices such as organic photovoltaic devices and organic light emitting devices.

  12. Mutual diffusion occurring at the interface between La₀.₆Sr₀.₄Co₀.₈Fe₀.₂O₃ cathode and Gd-doped ceria electrolyte during IT-SOFC cell preparation.

    PubMed

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

    2011-07-01

    The microstructure and local chemistry of the interface between the screen-printed La(0.6)Sr(0.4)Co(0.8)Fe(0.2)O(3) (LSCF) thin film cathode and Gd-doped ceria (GDC) electrolyte substrate have been investigated. Elemental distribution analyses, by energy-dispersive X-ray spectroscopy operated in scanning transmission electron microscopy (STEM) mode, illustrate that all constituent elements in GDC and LSCF mutually diffuse across the LSCF/GDC interface, with equal diffusion length. This leads to the formation of mutual diffusion zones at the LSCF/GDC interfaces, with the resultant mixture of diffusing ions being associated with specific valence state changes, as verified by STEM electron energy loss spectroscopy analyses. Moreover, this mutual diffusion can result in microstructural changes, where superstructure formation is accompanied by enhancement of oxygen vacancy ordering at this region. Such mutual diffusion and associated microstructure evolution is considered to be detrimental to fuel cell efficiency and should be suppressed by lowering cell fabrication temperatures.

  13. Combustion Synthesis of Doped Thermoelectric Oxides

    SciTech Connect

    Selig, Jiri; Lin, Sidney; Lin, Hua-Tay; Johnson, D Ray

    2012-01-01

    Self-propagating high-temperature synthesis (SHS) was used to prepare silver doped calcium cobaltates (Ca1.24- xAgxCo1.62O3.86, x = 0.03 - 0.12) powders. SHS is a simple and economic process to synthesize ceramic materials with minimum energy requirements. The heat generated by the SHS reaction can sustain the propagation of the reaction front and convert reactants to desired products. The effect of doping level on thermoelectric properties was investigated in this study. Results show the substitution of calcium by silver decreases the thermal conductivity significantly. XRD and surface area measurements show synthesized powders are phase pure and have large specific surface areas.

  14. Extremely thin bilayer electrolyte for solid oxide fuel cells (SOFCs) fabricated by chemical solution deposition (CSD).

    PubMed

    Oh, Eun-Ok; Whang, Chin-Myung; Lee, Yu-Ri; Park, Sun-Young; Prasad, Dasari Hari; Yoon, Kyung Joong; Son, Ji-Won; Lee, Jong-Ho; Lee, Hae-Weon

    2012-07-03

    An extremely thin bilayer electrolyte consisting of yttria-stabilized zirconia (YSZ) and gadolinia-doped ceria (GDC) is successfully fabricated on a sintered NiO-YSZ substrate. Major processing flaws are effectively eliminated by applying local constraints to YSZ nanoparticles, and excellent open circuit voltage and cell performance are demonstrated in a solid oxide fuel cell (SOFC) at intermediate operating temperatures.

  15. Macro- and microscopic properties of strontium doped indium oxide

    NASA Astrophysics Data System (ADS)

    Nikolaenko, Y. M.; Kuzovlev, Y. E.; Medvedev, Y. V.; Mezin, N. I.; Fasel, C.; Gurlo, A.; Schlicker, L.; Bayer, T. J. M.; Genenko, Y. A.

    2014-07-01

    Solid state synthesis and physical mechanisms of electrical conductivity variation in polycrystalline, strontium doped indium oxide In2O3:(SrO)x were investigated for materials with different doping levels at different temperatures (T = 20-300 °C) and ambient atmosphere content including humidity and low pressure. Gas sensing ability of these compounds as well as the sample resistance appeared to increase by 4 and 8 orders of the magnitude, respectively, with the doping level increase from zero up to x = 10%. The conductance variation due to doping is explained by two mechanisms: acceptor-like electrical activity of Sr as a point defect and appearance of an additional phase of SrIn2O4. An unusual property of high level (x = 10%) doped samples is a possibility of extraordinarily large and fast oxygen exchange with ambient atmosphere at not very high temperatures (100-200 °C). This peculiarity is explained by friable structure of crystallite surface. Friable structure provides relatively fast transition of samples from high to low resistive state at the expense of high conductance of the near surface layer of the grains. Microscopic study of the electro-diffusion process at the surface of oxygen deficient samples allowed estimation of the diffusion coefficient of oxygen vacancies in the friable surface layer at room temperature as 3 × 10-13 cm2/s, which is by one order of the magnitude smaller than that known for amorphous indium oxide films.

  16. Effect of composition and calcination temperature of ceria-zirconia-alumina mixed oxides on catalytic performances of ethanol conversion

    NASA Astrophysics Data System (ADS)

    Chuklina, S. G.; Maslenkova, S. A.; Pylinina, A. I.; Podzorova, L. I.; Ilyicheva, A. A.

    2017-02-01

    In the present study, we investigated the effect of preparation method, phase composition and calcination temperature of the (Ce-TZP) – Al2O3 mixed oxides on their structural features and catalytic performance in ethanol conversion. Ceria–zirconia–alumina mixed oxides with different (Ce+Zr)/Al atomic ratios were prepared via sol–gel method. Catalytic activity and selectivity were investigated for ethanol conversion to acetaldehyde, ethylene and diethyl ether.

  17. Brain distribution and toxicological evaluation of a systemically delivered engineered nanoscale ceria.

    PubMed

    Hardas, Sarita S; Butterfield, David Allan; Sultana, Rukhsana; Tseng, Michael T; Dan, Mo; Florence, Rebecca L; Unrine, Jason M; Graham, Uschi M; Wu, Peng; Grulke, Eric A; Yokel, Robert A

    2010-08-01

    Engineered nanoscale ceria is used as a diesel fuel catalyst. Little is known about its mammalian central nervous system effects. The objective of this paper is to characterize the biodistribution of a 5-nm citrate-stabilized ceria dispersion from blood into brain and its pro- or antioxidant effects. An approximately 4% aqueous ceria dispersion was iv infused into rats (0, 100, and up to 250 mg/kg), which were terminated after 1 or 20 h. Ceria concentration, localization, and chemical speciation in the brain were assessed by inductively coupled plasma mass spectrometry, light and electron microscopy (EM), and electron energy loss spectroscopy (EELS). Pro- or antioxidative stress effects were assessed as protein carbonyls, 3-nitrotyrosine, and protein-bound 4-hydroxy-2-trans-nonenal in hippocampus, cortex, and cerebellum. Glutathione reductase, glutathione peroxidase, manganese superoxide dismutase, and catalase levels and activities were measured in hippocampus. Catalase levels and activities were also measured in cortex and cerebellum. Na fluorescein and horseradish peroxidase (HRP) were given iv as blood-brain barrier (BBB) integrity markers. Mortality was seen after administration of 175-250 mg ceria/kg. Twenty hours after infusion of 100 mg ceria/kg, brain HRP was marginally elevated. EM and EELS revealed mixed Ce(III) and Ce(IV) valence in the freshly synthesized ceria in vitro and in ceria agglomerates in the brain vascular compartment. Ceria was not seen in microvascular endothelial or brain cells. Ceria elevated catalase levels at 1 h and increased catalase activity at 20 h in hippocampus and decreased catalase activity at 1 h in cerebellum. Compared with a previously studied approximately 30-nm ceria, this ceria was more toxic, was not seen in the brain, and produced little oxidative stress effect to the hippocampus and cerebellum. The results are contrary to the hypothesis that a smaller engineered nanomaterial would more readily permeate the BBB.

  18. Surface structure of coherently strained ceria ultrathin films

    NASA Astrophysics Data System (ADS)

    Shi, Yezhou; Stone, Kevin H.; Guan, Zixuan; Monti, Matteo; Cao, Chuntian; El Gabaly, Farid; Chueh, William C.; Toney, Michael F.

    2016-11-01

    Cerium oxide, or ceria, is an important material for solid oxide fuel cells and water splitting devices. Although the ceria surface is active in catalytic and electrochemical reactions, how its catalytic properties are affected by the surface structure under operating conditions is far from understood. We investigate the structure of the coherently strained Ce O2 ultrathin films on yttria-stabilized zirconia (001) single crystals by specular synchrotron x-ray diffraction (XRD) under oxidizing conditions as a first step to study the surface structure in situ. An excellent agreement between the experiment data and the model is achieved by using a "stacks and islands" model that has a two-component roughness. One component is due to the tiny clusters of nanometer scale in lateral dimensions on each terrace, while the other component is due to slightly different Ce O2 thickness that span over hundreds of nanometers on neighboring terraces. We attribute the nonuniform thickness to step depairing during the thin film deposition that is supported by the surface morphology results on the microscopic level. Importantly, our model also shows that the polarity of the ceria surface is removed by a half monolayer surface coverage of oxygen. The successful resolution of the ceria surface structure using in situ specular synchrotron XRD paves the way to study the structural evolution of ceria as a fuel cell electrode under catalytically relevant temperatures and gas pressures.

  19. Selection Rule of Preferred Doping Site for n-Type Oxides

    SciTech Connect

    Li, C.; Li, J.; Li, S. S.; Xia, J. B.; Wei, S. H.

    2012-06-25

    Using first-principles calculations and analysis, we show that to create shallow n-type dopants in oxides, anion site doping is preferred for more covalent oxides such as SnO{sub 2} and cation site doping is preferred for more ionic oxides such as ZnO. This is because for more ionic oxides, the conduction band minimum (CBM) state actually contains a considerable amount of O 3s orbitals, thus anion site doping can cause large perturbation on the CBM and consequently produces deeper donor levels. We also show that whether it is cation site doping or anion site doping, the oxygen-poor condition should always be used.

  20. Nitrogen doped zinc oxide thin film

    SciTech Connect

    Li, Sonny Xiao-zhe

    2003-01-01

    To summarize, polycrystalline ZnO thin films were grown by reactive sputtering. Nitrogen was introduced into the films by reactive sputtering in an NO2 plasma or by N+ implantation. All ZnO films grown show n-type conductivity. In unintentionally doped ZnO films, the n-type conductivities are attributed to Zni, a native shallow donor. In NO2-grown ZnO films, the n-type conductivity is attributed to (N2)O, a shallow double donor. In NO2-grown ZnO films, 0.3 atomic % nitrogen was found to exist in the form of N2O and N2. Upon annealing, N2O decomposes into N2 and O2. In furnace-annealed samples N2 redistributes diffusively and forms gaseous N2 bubbles in the films. Unintentionally doped ZnO films were grown at different oxygen partial pressures. Zni was found to form even at oxygen-rich condition and led to n-type conductivity. N+ implantation into unintentionally doped ZnO film deteriorates the crystallinity and optical properties and leads to higher electron concentration. The free electrons in the implanted films are attributed to the defects introduced by implantation and formation of (N2)O and Zni. Although today there is still no reliable means to produce good quality, stable p-type ZnO material, ZnO remains an attractive material with potential for high performance short wavelength optoelectronic devices. One may argue that gallium nitride was in a similar situation a decade ago. Although we did not obtain any p-type conductivity, we hope our research will provide a valuable reference to the literature.

  1. Electronic Structure Investigation of Doping C60 with Metal Oxide

    NASA Astrophysics Data System (ADS)

    Wang, Chenggong; Gao, Yongli

    2014-03-01

    Fullerene (C60) has been used extensively as an acceptor material in organic photovoltaic (OPV) cells. Other applications including n-channel organic thin film transistors (OTFT) and C60 based organic superconductors have been reported more than a decade ago. We have investigated p-doping of C60 with molybdenum oxide (MoOx) with ultra-violet photoemission spectroscopy (UPS), inverse photoemission spectroscopy (IPES) and atomic force microscopy (AFM). Both surface doping and bulk doping by MoOx are studied. It was found that the thermally evaporated MoOx inter-layer substantially increased the surface workfunction. This increased surface workfunction strongly attract electrons towards the MoOx layer at the C60/MoOx interface, resulting in strong inversion of C60. Energy levels of C60 relax gradually as the thickness of C60 increases. An exceptionally long (greater than 400 Angstrom) band bending is observed during this relaxation in C60. Such a long band bending has not been observed for other organic/MoOx interface. For the bulk doping, MoOx doping ratios from 1% to over 100% were investigated. The saturation occurs at approximately 20 %, when the highest occupied molecular level (HOMO) of C60 starts to be pinned at the Fermi level. These studies demonstrate effective ways to manipulate the electronic structures of the fullerene. This work is supported by the National Science Foundation Grant No. DMR-1303742.

  2. Enhanced electrochromism in cerium doped molybdenum oxide thin films

    SciTech Connect

    Dhanasankar, M.; Purushothaman, K.K.; Muralidharan, G.

    2010-12-15

    Cerium (5-15% by weight) doped molybdenum oxide thin films have been prepared on FTO coated glass substrate at 250 {sup o}C using sol-gel dip coating method. The structural and morphological changes were observed with the help of XRD, SEM and EDS analysis. The amorphous structure of the Ce doped samples, favours easy intercalation and deintercalation processes. Mo oxide films with 10 wt.% of Ce exhibit maximum anodic diffusion coefficient of 24.99 x 10{sup -11} cm{sup 2}/s and the change in optical transmittance of ({Delta}T at 550 nm) of 79.28% between coloured and bleached state with the optical density of ({Delta}OD) 1.15.

  3. Nitrogen-doped reduced graphene oxide electrodes for electrochemical supercapacitors.

    PubMed

    Nolan, Hugo; Mendoza-Sanchez, Beatriz; Ashok Kumar, Nanjundan; McEvoy, Niall; O'Brien, Sean; Nicolosi, Valeria; Duesberg, Georg S

    2014-02-14

    Herein we use Nitrogen-doped reduced Graphene Oxide (N-rGO) as the active material in supercapacitor electrodes. Building on a previous work detailing the synthesis of this material, electrodes were fabricated via spray-deposition of aqueous dispersions and the electrochemical charge storage mechanism was investigated. Results indicate that the functionalised graphene displays improved performance compared to non-functionalised graphene. The simplicity of fabrication suggests ease of up-scaling of such electrodes for commercial applications.

  4. Measuring bandgap states in individual non-stoichiometric oxide nanoparticles using monochromated STEM EELS: The Praseodymium-ceria case.

    PubMed

    Bowman, W J; March, K; Hernandez, C A; Crozier, P A

    2016-08-01

    We describe a method to perform high spatial resolution measurement of the position and density of inter-band impurity states in non-stoichiometric oxides using ultra-high energy resolution electron energy-loss spectroscopy (EELS). This can be employed to study optical and electronic properties of atomic and nanoscale defects in electrically-conducting and optically-active oxides. We employ a monochromated scanning transmission electron microscope with subnanometer diameter electron probe, making this technique suitable for correlating spectroscopic information with high spatial resolution images from small objects such as nanoparticles, surfaces or interfaces. The specific experimental approach outlined here provides direct measurement of the Pr inter-band impurity states in Pr0.1Ce0.9O2-δ via valence-loss EELS, which is interpreted with valence-loss spectral simulation based on density of states data to determine the energy level and character of the inter-band state. Additionally, observation of optical color change upon chemically-induced oxygen non-stoichiometry indicates that the population of the inter-band state is accompanied by an energy level shift within the bandgap.

  5. Nanosecond Laser-Assisted Nitrogen Doping of Graphene Oxide Dispersions.

    PubMed

    Kepić, Dejan; Sandoval, Stefania; Pino, Ángel Pérez Del; György, Enikö; Cabana, Laura; Ballesteros, Belén; Tobias, Gerard

    2017-02-09

    N-doped reduced graphene oxide (RGO) has been prepared in bulk form by laser irradiation of graphene oxide (GO) dispersed in an aqueous solution of ammonia. A pulsed Nd:YAG laser with emission wavelengths in the infrared (IR) 1064 nm, visible (Vis) 532 nm, and ultraviolet (UV) 266 nm spectral regions was employed for the preparation of the N-doped RGO samples. Regardless of the laser energy employed, the resulting material presents a higher fraction of pyrrolic nitrogen compared to nitrogen atoms in pyridinic and graphitic coordination. Noticeably, whereas increasing the laser fluence of UV and Vis wavelengths results in an increase in the total amount of nitrogen, up to 4.9 at. % (UV wavelength at 60 mJ cm(-2) fluence), the opposite trend is observed when the GO is irradiated in ammonia solution through IR processing. The proposed laser-based methodology allows the bulk synthesis of N-doped reduced graphene oxide in a simple, fast, and cost efficient manner.

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

    NASA Astrophysics Data System (ADS)

    Menendez-Mora, Christian L.

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

  7. Macro- and microscopic properties of strontium doped indium oxide

    SciTech Connect

    Nikolaenko, Y. M.; Kuzovlev, Y. E.; Medvedev, Y. V.; Mezin, N. I.; Fasel, C.; Gurlo, A.; Schlicker, L.; Bayer, T. J. M.; Genenko, Y. A.

    2014-07-28

    Solid state synthesis and physical mechanisms of electrical conductivity variation in polycrystalline, strontium doped indium oxide In{sub 2}O{sub 3}:(SrO){sub x} were investigated for materials with different doping levels at different temperatures (T = 20–300 °C) and ambient atmosphere content including humidity and low pressure. Gas sensing ability of these compounds as well as the sample resistance appeared to increase by 4 and 8 orders of the magnitude, respectively, with the doping level increase from zero up to x = 10%. The conductance variation due to doping is explained by two mechanisms: acceptor-like electrical activity of Sr as a point defect and appearance of an additional phase of SrIn{sub 2}O{sub 4}. An unusual property of high level (x = 10%) doped samples is a possibility of extraordinarily large and fast oxygen exchange with ambient atmosphere at not very high temperatures (100–200 °C). This peculiarity is explained by friable structure of crystallite surface. Friable structure provides relatively fast transition of samples from high to low resistive state at the expense of high conductance of the near surface layer of the grains. Microscopic study of the electro-diffusion process at the surface of oxygen deficient samples allowed estimation of the diffusion coefficient of oxygen vacancies in the friable surface layer at room temperature as 3 × 10{sup −13} cm{sup 2}/s, which is by one order of the magnitude smaller than that known for amorphous indium oxide films.

  8. Enhanced thermal oxidation stability of reduced graphene oxide by nitrogen doping.

    PubMed

    Sandoval, Stefania; Kumar, Nitesh; Sundaresan, A; Rao, C N R; Fuertes, Amparo; Tobias, Gerard

    2014-09-15

    Nitrogen-doped reduced graphene oxide (N-doped RGO) samples with a high level of doping, up to 13 wt. %, have been prepared by annealing graphene oxide under a flow of pure ammonia. The presence of nitrogen within the structure of RGO induces a remarkable increase in the thermal stability against oxidation by air. The thermal stability is closely related with the temperature of synthesis and the nitrogen content. The combustion reaction of nitrogen in different coordination environments (pyridinic, pyrrolic, and graphitic) is analyzed against a graphene fragment (undoped) from a thermodynamic point of view. In agreement with the experimental observations, the combustion of undoped graphene turns out to be more spontaneous than when nitrogen atoms are present.

  9. Preparation and characterization of copper-doped cobalt oxide electrodes.

    PubMed

    Rosa-Toro, A La; Berenguer, R; Quijada, C; Montilla, F; Morallón, E; Vazquez, J L

    2006-11-30

    Cobalt oxide (Co3O4) and copper-doped cobalt oxide (CuxCo(3-x)O4) films have been prepared onto titanium support by the thermal decomposition method. The electrodes have been characterized by different techniques such as cyclic voltammetry, scanning electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy (XPS). The effect on the electrochemical and crystallographic properties and surface morphology of the amount of copper in the oxide layer has been analyzed. The XPS spectra correspond to a characteristic monophasic Cu-Co spinel oxides when x is below 1. However, when the copper content exceeds that for the stoichiometric CuCo2O4 spinel, a new CuO phase segregates at the surface. The analysis of the surface cation distribution indicates that Cu(II) has preference for octahedral sites.

  10. Shaped Ceria Nanocrystals Catalyze Efficient and Selective Para-Hydrogen-Enhanced Polarization.

    PubMed

    Zhao, Evan W; Zheng, Haibin; Zhou, Ronghui; Hagelin-Weaver, Helena E; Bowers, Clifford R

    2015-11-23

    Intense para-hydrogen-enhanced NMR signals are observed in the hydrogenation of propene and propyne over ceria nanocubes, nano-octahedra, and nanorods. The well-defined ceria shapes, synthesized by a hydrothermal method, expose different crystalline facets with various oxygen vacancy densities, which are known to play a role in hydrogenation and oxidation catalysis. While the catalytic activity of the hydrogenation of propene over ceria is strongly facet-dependent, the pairwise selectivity is low (2.4% at 375 °C), which is consistent with stepwise H atom transfer, and it is the same for all three nanocrystal shapes. Selective semi-hydrogenation of propyne over ceria nanocubes yields hyperpolarized propene with a similar pairwise selectivity of (2.7% at 300 °C), indicating product formation predominantly by a non-pairwise addition. Ceria is also shown to be an efficient pairwise replacement catalyst for propene.

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

    PubMed

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

    2011-05-15

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

  12. Synthesis of europium-doped zinc oxide micro- and nanowires

    NASA Astrophysics Data System (ADS)

    Al Rifai, S. A.; Ryabtsev, S. V.; Smirnov, M. S.; Domashevskaya, E. P.; Ivanov, O. N.

    2014-01-01

    Single crystalline Eu3+-doped wurtzite ZnO micro- and nanowires were synthesized by a chemical vapor deposition method (CVD). The nanostructures were grown by autocatalytic mechanism at walls of an alumina boat. The structure and properties of the doped ZnO is fully characterized by X-ray diffraction (XRD), energy-dispersive X-ray spectrometry (EDX), scanning and transmission electron microscopy (SEM and TEM), and photoluminescence (PL) methods. The synthesis was carried out for 10 min giving vertically aligned nanowires with mean diameter of 50-400 nm and with length of up to several microns. The nanowires were grown along ±[0001] direction. The concentration of Eu3+ dopant in the synthesized nanowires was varied from 0.7 to 0.9 at %. The crystal structure and microstructures of the doped nanomaterials were discussed and compared with undoped ZnO. The photoluminescence spectra show that emission of doped samples were shifted towards orange-red region (2.02 eV) relative to undoped zinc oxide nanostructures (2.37 eV) due to Eu3+ intraionic transitions from ZnO/Eu.

  13. Silica-Ceria Hybrid Nanostructures

    SciTech Connect

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

    2012-04-25

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

  14. Electrical properties of tin-doped zinc oxide nanostructures doped at different dopant concentrations

    NASA Astrophysics Data System (ADS)

    Nasir, M. F.; Zainol, M. N.; Hannas, M.; Mamat, M. H.; Rahman, S. A.; Rusop, Mohamad

    2016-07-01

    This project has been focused on the electrical and optical properties respectively on the effect of Tin doped zinc oxide (ZnO) thin films at different dopant concentrations. These thin films were doped with different Sn dopant concentrations at 1 at%, 2 at%, 3 at%, 4 at% and 5 at% was selected as the parameter to optimize the thin films quality while the annealing temperature is fixed 500 °C. Sn doped ZnO solutions were deposited onto the glass substrates using sol-gel spin coating method. This project was involved with three phases, which are thin films preparation, deposition and characterization. The thin films were characterized using Current Voltage (I-V) measurement and ultraviolet-visible-near-infrared (UV-vis-NIR) spectrophotometer (Perkin Elmer Lambda 750) for electrical properties and optical properties. The electrical properties show that the resistivity is the lowest at 4 at% Sn doping concentration with the value 3.08 × 103 Ωcm-1. The absorption coefficient spectrum obtained shows all films exhibit very low absorption in the visible (400-800nm) and near infrared (NIR) (>800nm) range but exhibit high absorption in the UV range.

  15. Fabrication and characterization of carbon doped molybdenum oxide nanostructures.

    PubMed

    Wisitsoraat, A; Tuantranont, A; Patthanasettakul, V; Lomas, T

    2009-02-01

    Molybdenum oxide (MoOx) nanostructure has gained considerable attention because of its low-cost fabrication by low-temperature evaporation/condensation technique and its promising properties for applications in the field of catalysts and chemical sensors. However, MoOx has some inferior properties including very high electrical resistivity and instability at elevated temperature. These properties may be improved by means of foreign atom addition into its nanostructure. In this work, we develop a simple mean for doping of MoOx nanostructures by introduction of gas source dopant during evaporation. Carbon doped MoOx nanostructures have been synthesized by MoOx powder evaporation in Argon/Acetylene mixture with varying process parameters. Depending on growth conditions, various nanostructures including, nanorod, nanoplate, nanodots, can be formed with different dimensions and doping concentrations. Structural characterization by scanning electron microscopy (SEM), energy dispersive X-ray spectrometry (EDX), and X-ray diffraction (XRD) indicate that the MoOx based nanostructures are highly crystalline and carbon dopant is successfully incorporated in the structure with controllable concentration. Electrical characterization shows that the electrical conductivity of molybdenum oxide nanostructures can be increased by several orders of magnitude with carbon incorporation.

  16. Rare earth doped zinc oxide varistors

    DOEpatents

    McMillan, A.D.; Modine, F.A.; Lauf, R.J.; Alim, M.A.; Mahan, G.D.; Bartkowiak, M.

    1998-12-29

    A varistor includes a Bi-free, essentially homogeneous sintered body of a ceramic composition including, expressed as nominal weight %, 0.2--4.0% oxide of at least one rare earth element, 0.5--4.0% Co{sub 3}O{sub 4}, 0.05--0.4% K{sub 2}O, 0.05--0.2% Cr{sub 2}O{sub 3}, 0--0.2% CaO, 0.00005--0.01% Al{sub 2}O{sub 3}, 0--2% MnO, 0--0.05% MgO, 0--0.5% TiO{sub 3}, 0--0.2% SnO{sub 2}, 0--0.02% B{sub 2}O{sub 3}, balance ZnO. 4 figs.

  17. Rare earth doped zinc oxide varistors

    DOEpatents

    McMillan, April D.; Modine, Frank A.; Lauf, Robert J.; Alim, Mohammad A.; Mahan, Gerald D.; Bartkowiak, Miroslaw

    1998-01-01

    A varistor includes a Bi-free, essentially homogeneous sintered body of a ceramic composition including, expressed as nominal weight %, 0.2-4.0% oxide of at least one rare earth element, 0.5-4.0% Co.sub.3 O.sub.4, 0.05-0.4% K.sub.2 O, 0.05-0.2% Cr.sub.2 O.sub.3, 0-0.2% CaO, 0.00005-0.01% Al.sub.2 O.sub.3, 0-2% MnO, 0-0.05% MgO, 0-0.5% TiO.sub.3, 0-0.2% SnO.sub.2, 0-0.02% B.sub.2 O.sub.3, balance ZnO.

  18. Synthesis and characterization of magnesium doped cerium oxide for the fuel cell application

    NASA Astrophysics Data System (ADS)

    Kumar, Amit; Kumari, Monika; Kumar, Mintu; Kumar, Sacheen; Kumar, Dinesh

    2016-05-01

    Cerium oxide has attained much attentions in global nanotechnology market due to valuable application for catalytic, fuel additive, and widely as electrolyte in solid oxide fuel cell. Doped cerium oxide has large oxygen vacancies that allow for greater reactivity and faster ion transport. These properties make cerium oxide suitable material for SOFCs application. Cerium oxide electrolyte requires lower operation temperature which shows improvement in processing and the fabrication technique. In our work, we synthesized magnesium doped cerium oxide by the co-precipitation method. With the magnesium doping catalytic reactivity of CeO2 was increased. Synthesized nanoparticle were characterized by the XRD and UV absorption techniques.

  19. Fluorescent Nanocomposite of Embedded Ceria Nanoparticles in Electrospun Chitosan Nanofibers.

    PubMed

    Shehata, Nader; Samir, Effat; Gaballah, Soha; Hamed, Aya; Saad, Marwa; Salah, Mohammed

    2017-03-01

    This paper introduces a detailed optical characterization for a novel fluorescent biodegradable nanocomposite of electro-spun chitosan nanofibers with in-situ embedded cerium oxide (ceria) nanoparticles as the nanocomposite optical fluorescent material. Under near ultra-violet excitation, this synthesized nanocomposite emits a visible green wavelength at nearly 520nmwith different intensities according to the concentration of the embedded fluorescent material; i.e. ceria nanoparticles. This emission is due to the synthesized ceria nanoparticles optical tri-valiant cerium ions ce(3+), associated with formed oxygen vacancies with a direct allowed bandgap around 3.5 eV. Optical characteristics such as fluorescence emission intensity, absorbance dispersion, and direct bandgap are presented besides structural characteristics such as FTIR spectroscopy, and SEM analysis. The synthesized optical nanocomposite could be helpful in many further applications such as bio-imaging, biomedical engineering, and environmental optical sensors.

  20. A new symmetric solid oxide fuel cell with a samaria-doped ceria framework and a silver-infiltrated electrocatalyst

    NASA Astrophysics Data System (ADS)

    Lin, Ye; Su, Chao; Huang, Cheng; Kim, Ju Sik; Kwak, Chan; Shao, Zongping

    2012-01-01

    A new symmetric SOFC with an SDC framework and a silver-infiltrated electrocatalyst is presented for the first time in this paper. A three-electrode polarization test shows that the Ag-SDC has a low area specific resistance of 1.07 Ω cm2 at 600 °C, a low activation energy of 85 kJ mol-1 and high exchange current densities of 428.2 and 129.0 mA cm-2 at 750 and 650 °C, respectively, when it is used as an oxygen reduction electrode. It also exhibits low polarization resistance in a humidified hydrogen atmosphere. A symmetric single cell is used in real fuel cell conditions to deliver peak power densities of 200 and 84 mW cm-2 at 750 and 650 °C, respectively, when humidified hydrogen is used as a fuel and ambient air is used as the cathode atmosphere. The cell still reaches a peak power density of 81 mW cm-2 at 750 °C when operating on CO. O2-TPO analysis demonstrates that the Ag-SDC electrode has even better coking resistance than the pure SDC scaffold. The results indicate that Ag-SDC|SDC|Ag-SDC symmetric cells with an infiltrated silver electrocatalyst are a promising new type of fuel cell for use with both hydrogen fuel and carbon-containing fuels.

  1. FETs Based on Doped Polyaniline/Polyethylene Oxide Fibers

    NASA Technical Reports Server (NTRS)

    Theofylaktos, Noulie; Robinson, Daryl; Miranda, Felix; Pinto, Nicholas; Johnson, Alan, Jr.; MacDiarmid, Alan; Mueller, Carl

    2006-01-01

    A family of experimental highly miniaturized field-effect transistors (FETs) is based on exploitation of the electrical properties of nanofibers of polyaniline/ polyethylene oxide (PANi/PEO) doped with camphorsulfonic acid. These polymer-based FETs have the potential for becoming building blocks of relatively inexpensive, low-voltage, highspeed logic circuits that could supplant complementary metal oxide/semiconductor (CMOS) logic circuits. The development of these polymerbased FETs offers advantages over the competing development of FETs based on carbon nanotubes. Whereas it is difficult to control the molecular structures and, hence, the electrical properties of carbon nanotubes, it is easy to tailor the electrical properties of these polymerbased FETs, throughout the range from insulating through semiconducting to metallic, through choices of doping levels and chemical manipulation of polymer side chains. A further advantage of doped PANi/PEO nanofibers is that they can be made to draw very small currents and operate at low voltage levels, and thus are promising for applications in which there are requirements to use many FETs to obtain large computational capabilities while minimizing power demands. Fabrication of an experimental FET in this family begins with the preparation of a substrate as follows: A layer of silicon dioxide between 50 and 200 nm thick is deposited on a highly doped (resistivity 0.01 W.cm) silicon substrate, then gold electrodes/contact stripes are deposited on the oxide. Next, one or more fibers of camphorsulphonic acid-doped PANi/PEO having diameters of the order of 100 nm are electrospun onto the substrate so as to span the gap between the gold electrodes (see Figure 1). Figure 2 depicts measured current-versus-voltage characteristics of the device of Figure 1, showing that saturation channel currents occur at source-todrain potentials that are surprisingly low, relative to those of CMOS FETs. The hole mobility in the depletion regime in

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

    PubMed

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

    2015-01-01

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

  3. Transparent conducting oxides: a δ-doped superlattice approach.

    PubMed

    Cooper, Valentino R; Seo, Sung S Ambrose; Lee, Suyoun; Kim, Jun Sung; Choi, Woo Seok; Okamoto, Satoshi; Lee, Ho Nyung

    2014-08-11

    Metallic states appearing at interfaces between dissimilar insulating oxides exhibit intriguing phenomena such as superconductivity and magnetism. Despite tremendous progress in understanding their origins, very little is known about how to control the conduction pathways and the distribution of charge carriers. Using optical spectroscopic measurements and density-functional theory (DFT) simulations, we examine the effect of SrTiO3 (STO) spacer layer thickness on the optical transparency and carrier distribution in La δ-doped STO superlattices. We experimentally observe that these metallic superlattices remain highly transparent to visible light; a direct consequence of the appropriately large gap between the O 2p and Ti 3d states. In superlattices with relatively thin STO layers, we predict that three-dimensional conduction would occur due to appreciable overlap of quantum mechanical wavefunctions between neighboring δ-doped layers. These results highlight the potential for using oxide heterostructures in optoelectronic devices by providing a unique route for creating novel transparent conducting oxides.

  4. Pure spin current transport in gallium doped zinc oxide

    NASA Astrophysics Data System (ADS)

    Althammer, Matthias; Mukherjee, Joynarayan; Geprägs, Stephan; Goennenwein, Sebastian T. B.; Opel, Matthias; Ramachandra Rao, M. S.; Gross, Rudolf

    2017-01-01

    We study the flow of a pure spin current through zinc oxide by measuring the spin Hall magnetoresistance (SMR) in thin film trilayer samples consisting of bismuth-substituted yttrium iron garnet (Bi:YIG), gallium-doped zinc oxide (Ga:ZnO), and platinum. We investigate the dependence of the SMR magnitude on the thickness of the Ga:ZnO interlayer and compare to a Bi:YIG/Pt bilayer. We find that the SMR magnitude is reduced by almost one order of magnitude upon inserting a Ga:ZnO interlayer and continuously decreases with increasing interlayer thickness. Nevertheless, the SMR stays finite even for a 12 nm thick Ga:ZnO interlayer. These results show that a pure spin current indeed can propagate through a several nm-thick degenerately doped zinc oxide layer. We also observe differences in both the temperature and the field dependence of the SMR when comparing tri- and bilayers. Finally, we compare our data to the predictions of a model based on spin diffusion. This shows that interface resistances play a crucial role for the SMR magnitude in these trilayer structures.

  5. Phase transitions in ferroelectric silicon doped hafnium oxide

    NASA Astrophysics Data System (ADS)

    Böscke, T. S.; Teichert, St.; Bräuhaus, D.; Müller, J.; Schröder, U.; Böttger, U.; Mikolajick, T.

    2011-09-01

    We investigated phase transitions in ferroelectric silicon doped hafnium oxide (FE-Si:HfO2) by temperature dependent polarization and x-ray diffraction measurements. If heated under mechanical confinement, the orthorhombic ferroelectric phase reversibly transforms into a phase with antiferroelectric behavior. Without confinement, a transformation into a monoclinic/tetragonal phase mixture is observed during cooling. These results suggest the existence of a common higher symmetry parent phase to the orthorhombic and monoclinic phases, while transformation between these phases appears to be inhibited by an energy barrier.

  6. Unusual dielectric response in cobalt doped reduced graphene oxide

    SciTech Connect

    Akhtar, Abu Jahid; Gupta, Abhisek; Kumar Shaw, Bikash; Saha, Shyamal K.

    2013-12-09

    Intensive research on cobalt doped reduced graphene oxide (Co-RGO) to investigate the modification in graphene magnetism and spin polarization due to presence of transition metal atom has been carried out, however, its dielectric spectroscopy, particularly, how capacitance changes with impurity levels in graphene is relatively unexplored. In the present work, dielectric spectroscopy along with magneto-dielectric effect are investigated in Co-RGO. Contrary to other materials, here permittivity increases abruptly with frequency in the low frequency region and continues to increase till 10{sup 7} Hz. This unusual behavior is explained on the basis of trap induced capacitance created due to impurity levels.

  7. Luminescent properties of alumina ceramics doped with chromium oxide

    NASA Astrophysics Data System (ADS)

    Kortov, V.; Kiryakov, A.; Pustovarov, V.

    2016-08-01

    Ceramics doped with chromium oxide were synthesized from alumina nanopowder at high heating and cooling rates. XRD analysis of the obtained samples shows that they consist mainly of Al2O3 α-phase. Photoluminescence (PL) spectra in the visible spectral region and thermoluminescence (TL) curves were measured. An effect of the dopant concentration on the intensity and shape of the PL bands as well as on the TL yield was found. Annealing of the quenching defects which emerged during the synthesis changed the PL spectra. The centers responsible for PL and TL in the synthesized ceramics were identified.

  8. Evaluation of yttrium-doped strontium titanium oxide as a solid oxide fuel cell anode

    NASA Astrophysics Data System (ADS)

    Hui, Shiqiang

    2001-07-01

    A number of perovskite oxides, typically, heavily doped SrTiO3 samples, were synthesized and characterized with a view to establishing their potential as anode materials for solid oxide fuel cells (SOFCs). The structure, microstructure, electrical conductivity, reduction-oxidation behavior, phase stability, compatibility with electrolytes, and performance in SOFC operation were assessed. Ceramic samples were prepared with the formula (Sr1-xR x)(Ti1-yTy)O3 (R = rare earth elements, T = transition metals) and with charge balance achieved by A-site deficiency. Electrical conductivities were examined by the do four-probe method and impedance spectroscopy. It was found that yttrium is soluble in SrTiO 3 (SYT) up to 8 mol% and has marked effects on conductivity. Electrical conductivities were observed to increase with increasing donor-doping level, on reduction in low oxygen partial pressures. Electrical conductivity with values as high as 82 S/cm was achieved at 800°C and P(O2) = 10-19 atm. Electrical conductivities were reversible upon reduction and oxidation. The thermal expansion coefficient is compatible with electrolyte materials such as yttria-stabilized ZrO2 and doped LaGaO3. Cobalt-doped SYT, which showed a relatively high resistance to oxidation, was tested as the anode material in a fuel cell. Yttrium-doped SrTiO3 meets the requirements for the anode in SOFCs to a substantial degree, and is a promising alternative anode material.

  9. Iridium-Doped Ruthenium Oxide Catalyst for Oxygen Evolution

    NASA Technical Reports Server (NTRS)

    Valdez, Thomas I.; Narayan, Sri R.; Billings, Keith J.

    2011-01-01

    NASA requires a durable and efficient catalyst for the electrolysis of water in a polymer-electrolyte-membrane (PEM) cell. Ruthenium oxide in a slightly reduced form is known to be a very efficient catalyst for the anodic oxidation of water to oxygen, but it degrades rapidly, reducing efficiency. To combat this tendency of ruthenium oxide to change oxidation states, it is combined with iridium, which has a tendency to stabilize ruthenium oxide at oxygen evolution potentials. The novel oxygen evolution catalyst was fabricated under flowing argon in order to allow the iridium to preferentially react with oxygen from the ruthenium oxide, and not oxygen from the environment. Nanoparticulate iridium black and anhydrous ruthenium oxide are weighed out and mixed to 5 18 atomic percent. They are then heat treated at 300 C under flowing argon (in order to create an inert environment) for a minimum of 14 hours. This temperature was chosen because it is approximately the creep temperature of ruthenium oxide, and is below the sintering temperature of both materials. In general, the temperature should always be below the sintering temperature of both materials. The iridium- doped ruthenium oxide catalyst is then fabricated into a PEM-based membrane- electrode assembly (MEA), and then mounted into test cells. The result is an electrolyzer system that can sustain electrolysis at twice the current density, and at the same efficiency as commercial catalysts in the range of 100-200 mA/sq cm. At 200 mA/sq cm, this new system operates at an efficiency of 85 percent, which is 2 percent greater than commercially available catalysts. Testing has shown that this material is as stable as commercially available oxygen evolution catalysts. This means that this new catalyst can be used to regenerate fuel cell systems in space, and as a hydrogen generator on Earth.

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

    PubMed

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

    2015-10-28

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

  11. Ceria-based SOFC development

    SciTech Connect

    Doshi, R.; Krumpelt, M.

    1996-02-01

    The advantages of lowering the operating temperature of solid oxide fuel cells have led to efforts to develop fuel cells based on electrolytes like ceria which have a higher conductivity than zirconia. Lowering the operating temperature, however, causes increased electrode polarization. The currently used cathode material for higher temperature operation, lanthanum manganite, is inadequate for operation below 650--700{degrees}C. Therefore, to develop fuel cells for operation at 500{degrees}C, new electrode materials need to be. developed. It is recognized that the cathode performance requires the most improvement due to significantly slower oxygen reduction kinetics and/or oxygen diffusion kinetics through the electrode. In fact, for fuel cells made with thin electrolytes, the cathode accounts for up to 90% of the total voltage loss under load. Results on fuel cell tests in methanol and hydrogen and on new cathode materials are reported here. The results on new cathode materials are compared with known material properties, like nonstoichiometry and oxygen diffusion coefficients.

  12. Anodic oxidation with doped diamond electrodes: a new advanced oxidation process.

    PubMed

    Kraft, Alexander; Stadelmann, Manuela; Blaschke, Manfred

    2003-10-31

    Boron-doped diamond anodes allow to directly produce OH* radicals from water electrolysis with very high current efficiencies. This has been explained by the very high overvoltage for oxygen production and many other anodic electrode processes on diamond anodes. Additionally, the boron-doped diamond electrodes exhibit a high mechanical and chemical stability. Anodic oxidation with diamond anodes is a new advanced oxidation process (AOP) with many advantages compared to other known chemical and photochemical AOPs. The present work reports on the use of diamond anodes for the chemical oxygen demand (COD) removal from several industrial wastewaters and from two synthetic wastewaters with malic acid and ethylenediaminetetraacetic (EDTA) acid. Current efficiencies for the COD removal between 85 and 100% have been found. The formation and subsequent removal of by-products of the COD oxidation has been investigated for the first time. Economical considerations of this new AOP are included.

  13. Transparent conducting aerogels of antimony-doped tin oxide.

    PubMed

    Correa Baena, Juan Pablo; Agrios, Alexander G

    2014-11-12

    Bulk antimony-doped tin oxide aerogels are prepared by epoxide-initiated sol-gel processing. Tin and antimony precursors are dissolved in ethanol and water, respectively, and propylene oxide is added to cause rapid gelation of the sol, which is then dried supercritically. The Sb:Sn precursor mole ratio is varied from 0 to 30% to optimize the material conductivity and absorbance. The materials are characterized by electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy (XPS), nitrogen physisorption analysis, a four-point probe resistivity measurement, and UV-vis diffuse reflectance spectroscopy. The samples possess morphology typical of aerogels without significant change with the amount of doping. Calcination at 450 °C produces a cassiterite crystal structure in all aerogel samples. Introduction of Sb at 15% in the precursor (7.6% Sb by XPS) yields a resistivity more than 3 orders of magnitude lower than an undoped SnO2 aerogel. Calcination at 800 °C reduces the resistivity by an additional 2 orders of magnitude to 30 Ω·cm, but results in a significant decrease in surface area and pore volume.

  14. In situ trapping of As, Sb and Se hydrides on nanometer-sized ceria-coated iron oxide-silica and slurry suspension introduction to ICP-OES.

    PubMed

    Dados, A; Kartsiouli, E; Chatzimitakos, Th; Papastephanou, C; Stalikas, C D

    2014-12-01

    A procedure is developed for the analysis of sub-μg L(-1) levels of arsenic, antimony and selenium after preconcentration of their hydrides. The study highlights the capability of an aqueous suspension of a nanometer-sized magnetic ceria, in the presence of iodide, to function as a sorbent for the in situ trapping and preconcentration of the hydrides of certain metalloids. After extraction, the material is magnetically separated from the trapping solution and analyzed. A slurry suspension sampling approach with inductively coupled plasma-optical emission spectrometry (ICP-OES) is employed for measurements, as the quantitative elution of the adsorbed metalloids is not feasible. The whole analytical procedure consists of five steps: (i) pre-reduction of As, Sb and Se, (ii) generation of the hydrides AsH3, SbH3 and SeH2, (iii) in situ collection in the trapping suspension of magnetic ceria, (iv) isolation of the particles by applying a magnetic field, and (v) measurement of As, Sb and Se concentrations using ICP-OES. Under the established experimental conditions, the efficiency of trapping accounted for 94 ± 2%, 89 ± 2% and 98 ± 3% for As, Sb and Se, respectively, signifying the effective implementation of the overall procedure. The applicability of the procedure has been demonstrated by analyzing tap and lake water and a reference material (soft drinking water). The obtained analytical figures of merit were satisfactory for the analysis of the above metalloids in natural waters by ICP-OES.

  15. Effect of doping of tin on optoelectronic properties of indium oxide: DFT study

    SciTech Connect

    Tripathi, Madhvendra Nath

    2015-06-24

    Indium tin oxide is widely used transparent conductor. Experimentally observed that 6% tin doping in indium oxide is suitable for optoelectronic applications and more doping beyond this limit degrades the optoelectronic property. The stoichiometry (In{sub 32-x}Sn{sub x}O{sub 48+x/2}; x=0-6) is taken to understand the change in lattice parameter, electronic structure, and optical property of ITO. It is observed that lattice parameter increases and becomes constant after 6% tin doping that is in good agreement of the experimental observation. The electronic structure calculation shows that the high tin doping in indium oxide adversely affects the dispersive nature of the bottom of conduction band of pure indium oxide and decreases the carrier mobility. Optical calculations show that transmittance goes down upto 60% for the tin concentration more than 6%. The present paper shows that how more than 6% tin doping in indium oxide adversely affects the optoelectronic property of ITO.

  16. Nanostructured gadolinium-doped ceria microsphere synthesis from ion exchange resin: Multi-scale in-situ studies of solid solution formation

    SciTech Connect

    Caisso, Marie; Lebreton, Florent; Horlait, Denis; Neuville, Daniel R.; Dardenne, Kathy; Rothe, Jörg; Delahaye, Thibaud

    2014-10-15

    In the current nano-sized material revolution, the main limitations to a large-scale deployment of nanomaterials involve health concerns related to nano-dissemination via air. Developing new chemical routes benefiting from nano-size advantages while avoiding their hazards could overcome these limitations. Addressing this need, a chemical route leading to soft nano-particle agglomerates, i.e., macroscopic precursors presenting the ability to be decomposed into nano-sized materials, was developed and applied to Ce{sub 0.8}Gd{sub 0.2}O{sub 2−δ}. Using cerium/gadolinium-loaded ion exchange resin, the Ce{sub 0.8}Gd{sub 0.2}O{sub 2−δ} solid solution formation as a function of temperature was studied in-situ through X-ray diffraction, X-ray absorption spectroscopy and Raman spectroscopy. Temperatures corresponding to the organic skeleton decomposition and to the mixed oxide crystallization were identified. An optimal heat treatment, leading to nanostructured soft agglomerates, was established. Microsphere processing capabilities were evaluated and particle size distribution measurements were recorded. A very low fracture strength was calculated, and a nanometric particle size distribution (170 nm) was determined. - Graphical abstract: The elaboration of micro-spherical precursors leading to the formation of nano-oxide soft agglomerates was studied and approved through the use of ion exchange resin loaded with cerium and gadolinium. The formation of the solid solution was followed through in-situ measurements such as XAS, XRD, Raman, TGA and DSC. Key temperatures were identified for the formation of the mixed-oxide. Following this study, the microstructure and particle size of oxide microspheres formed highlight the formation of soft nano-arrangments. - Highlights: • Soft microspherical agglomerates able to be decomposed into nano-sized materials. • In situ study of cerium/gadolinium-loaded ion exchange resin conversion in oxide. • In situ multi-scale study

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

    PubMed

    Nolan, Michael

    2013-11-14

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

  18. Method of preparing doped oxide catalysts for lean NOx exhaust

    DOEpatents

    Park, Paul W.

    2004-03-09

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

  19. High power density solid oxide fuel cells

    DOEpatents

    Pham, Ai Quoc; Glass, Robert S.

    2004-10-12

    A method for producing ultra-high power density solid oxide fuel cells (SOFCs). The method involves the formation of a multilayer structure cells wherein a buffer layer of doped-ceria is deposited intermediate a zirconia electrolyte and a cobalt iron based electrode using a colloidal spray deposition (CSD) technique. For example, a cobalt iron based cathode composed of (La,Sr)(Co,Fe)O (LSCF) may be deposited on a zirconia electrolyte via a buffer layer of doped-ceria deposited by the CSD technique. The thus formed SOFC have a power density of 1400 mW/cm.sup.2 at 600.degree. C. and 900 mW/cm.sup.2 at 700.degree. C. which constitutes a 2-3 times increased in power density over conventionally produced SOFCs.

  20. Kinetics of CO/CO2 and H2/H2O reactions at Ni-based and ceria-based solid-oxide-cell electrodes.

    PubMed

    Graves, Christopher; Chatzichristodoulou, Christodoulos; Mogensen, Mogens B

    2015-01-01

    The solid oxide electrochemical cell (SOC) is an energy conversion technology that can be operated reversibly, to efficiently convert chemical fuels to electricity (fuel cell mode) as well as to store electricity as chemical fuels (electrolysis mode). The SOC fuel-electrode carries out the electrochemical reactions CO2 + 2e(-) ↔ CO + O(2-) and H2O + 2e(-) ↔ H2 + O(2-), for which the electrocatalytic activities of different electrodes differ considerably. The relative activities in CO/CO2 and H2/H2O and the nature of the differences are not well studied, even for the most common fuel-electrode material, a composite of nickel and yttria/scandia stabilized zirconia (Ni-SZ). Ni-SZ is known to be more active for H2/H2O than for CO/CO2 reactions, but the reported relative activity varies widely. Here we compare AC impedance and DC current-overpotential data measured in the two gas environments for several different electrodes comprised of Ni-SZ, Gd-doped CeO2 (CGO), and CGO nanoparticles coating Nb-doped SrTiO3 backbones (CGOn/STN). 2D model and 3D porous electrode geometries are employed to investigate the influence of microstructure, gas diffusion and impurities.Comparing model and porous Ni-SZ electrodes, the ratio of electrode polarization resistance in CO/CO2vs. H2/H2O decreases from 33 to 2. Experiments and modelling suggest that the ratio decreases due to a lower concentration of impurities blocking the three phase boundary and due to the nature of the reaction zone extension into the porous electrode thickness. Besides showing higher activity for H2/H2O reactions than CO/CO2 reactions, the Ni/SZ interface is more active for oxidation than reduction. On the other hand, we find the opposite behaviour in both cases for CGOn/STN model electrodes, reporting for the first time a higher electrocatalytic activity of CGO nanoparticles for CO/CO2 than for H2/H2O reactions in the absence of gas diffusion limitations. We propose that enhanced surface reduction at the

  1. Growth study and photocatalytic properties of Co-doped tungsten oxide mesocrystals

    SciTech Connect

    Sun, Shibin; Chang, Xueting; Li, Zhenjiang

    2012-11-15

    Cobalt-doped tungsten oxide mesocrystals with different morphologies have been successfully generated using a solvothermal method with tungsten hexachloride and cobalt chloride salts as precursors. The resulting mesocrystals were characterized by X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, Brunauer-Emmet-Teller analysis of nitrogen sorptometer, and UV-vis diffuse reflectance spectroscopy. The photocatalytic properties of the cobalt-doped tungsten oxide mesocrystals were evaluated on the basis of their ability to degrade methyl orange in an aqueous solution under simulated sunlight irradiation. Results showed that the cobalt doping had obvious effect on the morphologies of the final products, and lenticular and blocky cobalt-doped tungsten oxide mesocrystals could be obtained with 1.0 wt.% and 2.0 wt.% cobalt doping, respectively. The cobalt-doped tungsten oxides exhibited superior photocatalytic activities to that of the undoped tungsten oxide. - Graphical abstract: Schematic illustrations of the growth of the bundled nanowires, lenticular mesocrystals, and blocky mesocrystals. Highlights: Black-Right-Pointing-Pointer Co-doped W{sub 18}O{sub 49} mesocrystals were synthesized using a solvothermal method. Black-Right-Pointing-Pointer The Co doping has obvious effect on the morphology of the final mesocrystals. Black-Right-Pointing-Pointer The Co-doped W{sub 18}O{sub 49} exhibited superior photocatalytic activity to the undoped W{sub 18}O{sub 49}.

  2. High dielectric constant nickel-doped titanium oxide films prepared by liquid-phase deposition

    NASA Astrophysics Data System (ADS)

    Lee, Ming-Kwei; Yen, Chih-Feng; Fan, Cho-Han

    2014-09-01

    The electrical characteristics of nickel-doped titanium oxide films prepared by liquid-phase deposition on p-type (100) silicon substrate were investigated. The aqueous solutions of ammonium hexafluorotitanate and boric acid were used as precursors for the growth of titanium oxide films and the dielectric constant is 29. The dielectric constant can be improved to 94 by nickel doping at the thermal annealing at 700 °C in nitrous oxide.

  3. Stabilizing the ferroelectric phase in doped hafnium oxide

    NASA Astrophysics Data System (ADS)

    Hoffmann, M.; Schroeder, U.; Schenk, T.; Shimizu, T.; Funakubo, H.; Sakata, O.; Pohl, D.; Drescher, M.; Adelmann, C.; Materlik, R.; Kersch, A.; Mikolajick, T.

    2015-08-01

    The ferroelectric properties and crystal structure of doped HfO2 thin films were investigated for different thicknesses, electrode materials, and annealing conditions. Metal-ferroelectric-metal capacitors containing Gd:HfO2 showed no reduction of the polarization within the studied thickness range, in contrast to hafnia films with other dopants. A qualitative model describing the influence of basic process parameters on the crystal structure of HfO2 was proposed. The influence of different structural parameters on the field cycling behavior was examined. This revealed the wake-up effect in doped HfO2 to be dominated by interface induced effects, rather than a field induced phase transition. TaN electrodes were shown to considerably enhance the stabilization of the ferroelectric phase in HfO2 compared to TiN electrodes, yielding a Pr of up to 35 μC/cm2. This effect was attributed to the interface oxidation of the electrodes during annealing, resulting in a different density of oxygen vacancies in the Gd:HfO2 films. Ab initio simulations confirmed the influence of oxygen vacancies on the phase stability of ferroelectric HfO2.

  4. Strontium adsorption on tantalum-doped hexagonal tungsten oxide.

    PubMed

    Li, Xingliang; Mu, Wanjun; Xie, Xiang; Liu, Bijun; Tang, Hui; Zhou, Guanhong; Wei, Hongyuan; Jian, Yuan; Luo, Shunzhong

    2014-01-15

    Hexagonal tungsten oxide (hex-WO3) has the potential to separate (137)Cs and (90)Sr from nuclear power plant or fission (99)Mo production waste. This study aims to increase the capacity of hex-WO3 to adsorb Sr(2+). Ta-doped hex-WO3 was synthesized by the hydrothermal treatment of sodium tungstate dihydrate and tantalum chloride in concentrated HCl, in the presence of ammonium sulfate. Incorporating Ta into the WO3 framework caused the interlayer spacing to expand, and the band gap to shift to higher energy. The Sr(2+) adsorption capacity of Ta-doped hex-WO3 was significantly higher than that of hex-WO3. Sr(2+) adsorption reached equilibrium within 2h in acidic solution. Maximum Sr(2+) removal occurred at pH 4. Sr(2+) uptake by hex-WO3 was described better by the Freundlich model than by the Langmuir model. Sr(2+) adsorption on hex-WO3 was spontaneous under the studied conditions.

  5. Stabilizing the ferroelectric phase in doped hafnium oxide

    SciTech Connect

    Hoffmann, M.; Schroeder, U.; Schenk, T.; Shimizu, T.; Funakubo, H.; Sakata, O.; Pohl, D.; Drescher, M.; Adelmann, C.; Materlik, R.; Kersch, A.; Mikolajick, T.

    2015-08-21

    The ferroelectric properties and crystal structure of doped HfO{sub 2} thin films were investigated for different thicknesses, electrode materials, and annealing conditions. Metal-ferroelectric-metal capacitors containing Gd:HfO{sub 2} showed no reduction of the polarization within the studied thickness range, in contrast to hafnia films with other dopants. A qualitative model describing the influence of basic process parameters on the crystal structure of HfO{sub 2} was proposed. The influence of different structural parameters on the field cycling behavior was examined. This revealed the wake-up effect in doped HfO{sub 2} to be dominated by interface induced effects, rather than a field induced phase transition. TaN electrodes were shown to considerably enhance the stabilization of the ferroelectric phase in HfO{sub 2} compared to TiN electrodes, yielding a P{sub r} of up to 35 μC/cm{sup 2}. This effect was attributed to the interface oxidation of the electrodes during annealing, resulting in a different density of oxygen vacancies in the Gd:HfO{sub 2} films. Ab initio simulations confirmed the influence of oxygen vacancies on the phase stability of ferroelectric HfO{sub 2}.

  6. Oxidative unzipping of stacked nitrogen-doped carbon nanotube cups.

    PubMed

    Dong, Haifeng; Zhao, Yong; Tang, Yifan; Burkert, Seth C; Star, Alexander

    2015-05-27

    We demonstrate a facile synthesis of different nanostructures by oxidative unzipping of stacked nitrogen-doped carbon nanotube cups (NCNCs). Depending on the initial number of stacked-cup segments, this method can yield graphene nanosheets (GNSs) or hybrid nanostructures comprised of graphene nanoribbons partially unzipped from a central nanotube core. Due to the stacked-cup structure of as-synthesized NCNCs, preventing complete exposure of graphitic planes, the unzipping mechanism is hindered, resulting in incomplete unzipping; however, individual, separated NCNCs are completely unzipped, yielding individual nitrogen-doped GNSs. Graphene-based materials have been employed as electrocatalysts for many important chemical reactions, and it has been proposed that increasing the reactive edges results in more efficient electrocatalysis. In this paper, we apply these graphene conjugates as electrocatalysts for the oxygen reduction reaction (ORR) to determine how the increase in reactive edges affects the electrocatalytic activity. This investigation introduces a new method for the improvement of ORR electrocatalysts by using nitrogen dopants more effectively, allowing for enhanced ORR performance with lower overall nitrogen content. Additionally, the GNSs were functionalized with gold nanoparticles (GNPs), resulting in a GNS/GNP hybrid, which shows efficient surface-enhanced Raman scattering and expands the scope of its application in advanced device fabrication and biosensing.

  7. Complex oxide ferroelectrics: Electrostatic doping by domain walls

    DOE PAGES

    Maksymovych, Petro

    2015-06-19

    Electrically conducting interfaces can form, rather unexpectedly, by breaking the translational symmetry of electrically insulating complex oxides. For example, a nanometre-thick heteroepitaxial interface between electronically insulating LaAlO3 and SrTiO3 supports a 2D electron gas1 with high mobility of >1,000 cm2 V-1 s-1 (ref. 2). Such interfaces can exhibit magnetism, superconductivity and phase transitions that may form the functional basis of future electronic devices2. A peculiar conducting interface can be created within a polar ferroelectric oxide by breaking the translational symmetry of the ferroelectric order parameter and creating a so-called ferroelectric domain wall (Fig. 1a,b). If the direction of atomic displacementsmore » changes at the wall in such a way as to create a discontinuity in the polarization component normal to the wall (Fig. 1a), the domain wall becomes electrostatically charged. It may then attract compensating mobile charges of opposite sign produced by dopant ionization, photoexcitation or other effects, thereby locally, electrostatically doping the host ferroelectric film. In contrast to conductive interfaces between epitaxially grown oxides, domain walls can be reversibly created, positioned and shaped by electric fields, enabling reconfigurable circuitry within the same volume of the material. Now, writing in Nature Nanotechnology, Arnaud Crassous and colleagues at EPFL and University of Geneva demonstrate control and stability of charged conducting domain walls in ferroelectric thin films of BiFeO3 down to the nanoscale.« less

  8. Conductivity study of nitrogen-doped calcium zinc oxide prepared by spray pyrolysis

    NASA Astrophysics Data System (ADS)

    Hsu, Yu-Ting; Lan, Wen-How; Huang, Kai-Feng; Lin, Jia-Ching; Chang, Kuo-Jen

    2016-01-01

    In this study, the spray pyrolysis method was used to prepare unintentionally doped and nitrogen-doped calcium zinc oxide films by using zinc acetate, calcium nitrate precursor, and ammonium acetate precursor. Morphological and structural analyses were conducted using scanning electron microscopy and X-ray diffraction. The results indicated that film grain size decreased as the nitrogen doping was increased. Both calcium oxide and zinc oxide structures were identified in the unintentionally doped calcium zinc oxide. When nitrogen doping was introduced, the film mainly exhibited a zinc oxide structure with preferred (002) and (101) orientations. The concentration and mobility were investigated using a Hall measurement system. P-type films with a mobility and concentration of 10.6 cm2 V-1 s-1 and 2.8×1017 cm-3, respectively, were obtained. Moreover, according to a temperature-dependent conductivity analysis, an acceptor state with activation energy 0.266 eV dominated the p-type conduction for the unintentionally doped calcium zinc oxide. By contrast, a grain boundary with a barrier height of 0.274-0.292 eV dominated the hole conduction for the nitrogen-doped calcium zinc oxide films.

  9. Doped titanium oxide photcatalysts: Preparation, structure and interaction with viruses

    NASA Astrophysics Data System (ADS)

    Li, Qi

    Since the discovery of photoelectrochemical splitting of water on n-titanium oxide (n-TiO2) electrodes by Fujishima and Honda in 1972, there has been much interest in semiconductor-based materials as photocatalysts for both solar energy conversion and environmental applications in the past several decades. Among various semiconductor-based photocatalysts, TiO2 is the only candidate suitable for industrial use because of its high chemical stability, good photoactivity, relatively low cost, and nontoxicity. However, the photocatalytic capability of TiO 2 is limited to only ultraviolet (UV) light (wavelength, lambda, < 400 nm), seriously limiting its solar efficiency. In this study, both chemical and physical modification approaches were developed to extend the absorption band-edge of TiO2 into the visible light region with improved stability, photocatalytic efficiency and ease of the doping process. Two major approaches were used in the material synthesis and processing, including the ion-beam-assisted-deposition (IBAD) technique and sol-gel based processes. Both nitrogen-doped TiO2 (TiON) and nitrogen/palladium co-doped TiO2 (TiON/PdO) photocatalysts were created and their photocatalytic activity was investigated by the degradation of methylene blue (MB) and disinfection of bacteria and viruses under visible light illumination. The sol-gel process was optimized to produce high quality TiON-based photocatalysts by carefully modulating the precursor ratio and calcination temperature. A TiON inverse opal structure was created, which demonstrated enhanced visible light absorption and subsequently improved photocatalytic efficiency by the combination of chemical and physical modifications on n-TiO2. The effect of palladium dopant on the optical and photocatalytic properties of TiON/PdO photocatalyst was examined, which suggests that a careful optimization of the transition metal ion dopant concentration is needed to achieve high photocatalytic efficiency in these anion

  10. Direct Single-Enzyme Biomineralization of Catalytically Active Ceria and Ceria-Zirconia Nanocrystals.

    PubMed

    Curran, Christopher D; Lu, Li; Jia, Yue; Kiely, Christopher J; Berger, Bryan W; McIntosh, Steven

    2017-02-21

    Biomineralization is an intriguing approach to the synthesis of functional inorganic materials for energy applications whereby biological systems are engineered to mineralize inorganic materials and control their structure over multiple length scales under mild reaction conditions. Herein we demonstrate a single-enzyme-mediated biomineralization route to synthesize crystalline, catalytically active, quantum-confined ceria (CeO2-x) and ceria-zirconia (Ce1-yZryO2-x) nanocrystals for application as environmental catalysts. In contrast to typical anthropogenic synthesis routes, the crystalline oxide nanoparticles are formed at room temperature from an otherwise inert aqueous solution without the addition of a precipitant or additional reactant. An engineered form of silicatein, rCeSi, as a single enzyme not only catalyzes the direct biomineralization of the nanocrystalline oxides but also serves as a templating agent to control their morphological structure. The biomineralized nanocrystals of less than 3 nm in diameter are catalytically active toward carbon monoxide oxidation following an oxidative annealing step to remove carbonaceous residue. The introduction of zirconia into the nanocrystals leads to an increase in Ce(III) concentration, associated catalytic activity, and the thermal stability of the nanocrystals.

  11. Corrosion evaluation of zirconium doped oxide coatings on aluminum formed by plasma electrolytic oxidation.

    PubMed

    Bajat, Jelena; Mišković-Stanković, Vesna; Vasilić, Rastko; Stojadinović, Stevan

    2014-01-01

    The plasma electrolytic oxidation (PEO) of aluminum in sodium tungstate (Na(2)WO(4) · (2)H(2)O) and Na(2)WO(4) · (2)H(2)O doped with Zr was analyzed in order to obtain oxide coatings with improved corrosion resistance. The influence of current density in PEO process and anodization time was investigated, as well as the influence of Zr, with the aim to find out how they affect the chemical content, morphology, surface roughness, and corrosion stability of oxide coatings. It was shown that the presence of Zr increases the corrosion stability of oxide coatings for all investigated PEO times. Evolution of EIS spectra during the exposure to 3% NaCl, as a strong corrosive agent, indicated the highest corrosion stability for PEO coating formed on aluminum at 70 mA/cm(2) for 2 min in a zirconium containing electrolyte.

  12. Deep eutectic-solvothermal synthesis of nanostructured ceria

    PubMed Central

    Hammond, Oliver S.; Edler, Karen J.; Bowron, Daniel T.; Torrente-Murciano, Laura

    2017-01-01

    Ceria is a technologically important material with applications in catalysis, emissions control and solid-oxide fuel cells. Nanostructured ceria becomes profoundly more active due to its enhanced surface area to volume ratio, reactive surface oxygen vacancy concentration and superior oxygen storage capacity. Here we report the synthesis of nanostructured ceria using the green Deep Eutectic Solvent reline, which allows morphology and porosity control in one of the less energy-intensive routes reported to date. Using wide Q-range liquid-phase neutron diffraction, we elucidate the mechanism of reaction at a molecular scale at considerably milder conditions than the conventional hydrothermal synthetic routes. The reline solvent plays the role of a latent supramolecular catalyst where the increase in reaction rate from solvent-driven pre-organization of the reactants is most significant. This fundamental understanding of deep eutectic-solvothermal methodology will enable future developments in low-temperature synthesis of nanostructured ceria, facilitating its large-scale manufacturing using green, economic, non-toxic solvents. PMID:28120829

  13. Deep eutectic-solvothermal synthesis of nanostructured ceria

    NASA Astrophysics Data System (ADS)

    Hammond, Oliver S.; Edler, Karen J.; Bowron, Daniel T.; Torrente-Murciano, Laura

    2017-01-01

    Ceria is a technologically important material with applications in catalysis, emissions control and solid-oxide fuel cells. Nanostructured ceria becomes profoundly more active due to its enhanced surface area to volume ratio, reactive surface oxygen vacancy concentration and superior oxygen storage capacity. Here we report the synthesis of nanostructured ceria using the green Deep Eutectic Solvent reline, which allows morphology and porosity control in one of the less energy-intensive routes reported to date. Using wide Q-range liquid-phase neutron diffraction, we elucidate the mechanism of reaction at a molecular scale at considerably milder conditions than the conventional hydrothermal synthetic routes. The reline solvent plays the role of a latent supramolecular catalyst where the increase in reaction rate from solvent-driven pre-organization of the reactants is most significant. This fundamental understanding of deep eutectic-solvothermal methodology will enable future developments in low-temperature synthesis of nanostructured ceria, facilitating its large-scale manufacturing using green, economic, non-toxic solvents.

  14. Deep eutectic-solvothermal synthesis of nanostructured ceria.

    PubMed

    Hammond, Oliver S; Edler, Karen J; Bowron, Daniel T; Torrente-Murciano, Laura

    2017-01-25

    Ceria is a technologically important material with applications in catalysis, emissions control and solid-oxide fuel cells. Nanostructured ceria becomes profoundly more active due to its enhanced surface area to volume ratio, reactive surface oxygen vacancy concentration and superior oxygen storage capacity. Here we report the synthesis of nanostructured ceria using the green Deep Eutectic Solvent reline, which allows morphology and porosity control in one of the less energy-intensive routes reported to date. Using wide Q-range liquid-phase neutron diffraction, we elucidate the mechanism of reaction at a molecular scale at considerably milder conditions than the conventional hydrothermal synthetic routes. The reline solvent plays the role of a latent supramolecular catalyst where the increase in reaction rate from solvent-driven pre-organization of the reactants is most significant. This fundamental understanding of deep eutectic-solvothermal methodology will enable future developments in low-temperature synthesis of nanostructured ceria, facilitating its large-scale manufacturing using green, economic, non-toxic solvents.

  15. Growth of Ce+3 Doped Oxides by the Traveling Solvent Zone Technique.

    DTIC Science & Technology

    1983-06-01

    AD-A130 566 GROWTH OF CE-3 DOPED OXIDES BY THE TRAVELINO SOLVENT Il ZONE TECHNIQUE(U) EIC CORP NEWTON MASS R D RAUHI ET AL. JUN 83 C-718F NODS 4-82-C...NATIONAL BUREAU OF SIANDARID 1%, A I Report N00014i-82-C-0629 I GROWTH OF Ce + 3 DOPED OXIDES BY THE TRAVELING SOLVENT ZONE TECHNIQUEI, I I " R. David...TLEa (dad INBIitA) S YEO EOT&PRO OEE FINAL REPORT GRa*iI op Ce+3 DOPED OXIDES By THE 2 Aug 82-1 Apr 83 TRAVELING SOLVENT ZONIE TECHNIQUE T. PERFORMING

  16. Performance studies of copper-iron/ceria-yttria stabilized zirconia anode for electro-oxidation of butane in solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Kaur, Gurpreet; Basu, Suddhasatwa

    2013-11-01

    Addition of second metal to Cu is useful for electro-oxidation of hydrocarbons in solid oxide fuel cells (SOFC). In this work, electro-catalysts based on Cu-Fe bimetallic anode for use of both H2 and n-C4H10 in SOFC is prepared by wet impregnation method into a porous CeO2-YSZ matrix. The prepared Cu-Fe/CeO2-YSZ anodes are then characterized by thermo-gravimetric analysis (TGA), X-ray diffraction (XRD), elemental dispersive X-ray (EDX) and scanning electron microscopy (SEM). Carbonaceous deposits formed on Cu-Fe/CeO2-YSZ anodes after exposure to n-C4H10 are studied using a combination of i-V characteristics and TGA measurements. It is observed that the addition of Fe to Cu in CeO2-YSZ cermet anode enhance the performance in H2 and n-C4H10 fuels. The performance of cell having molar ratio of Cu-Fe of 1:1 in Cu-Fe/CeO2-YSZ anode shows power density of 240 mW cm-2 and 260 mW cm-2 in n-C4H10 and in H2 after n-C4H10 flow at 800 °C. The i-V curve shows that the conductivity of the anode improves after exposure to n-C4H10. No apparent degradation in performance is observed after n-C4H10 flow except for carbon fibre formation indicating Cu-Fe bimetallic is worth considering as an anode for direct butane SOFC.

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

    SciTech Connect

    Jones, John; Xiong, Haifeng; DelaRiva, Andrew; Peterson, Eric J.; Pham, Hien; Challa, Sivakumar R.; Qi, Gongshin; Oh, Se H.; Wiebenga, Michelle H.; Pereira Hernandez, Xavier I.; Wang, Yong; Datye, Abhaya K.

    2016-07-08

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

  18. Control of metal nanocrystal size reveals metal-support interface role for ceria catalysts.

    PubMed

    Cargnello, Matteo; Doan-Nguyen, Vicky V T; Gordon, Thomas R; Diaz, Rosa E; Stach, Eric A; Gorte, Raymond J; Fornasiero, Paolo; Murray, Christopher B

    2013-08-16

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

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

    SciTech Connect

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

    2013-08-15

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

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

    PubMed

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

    2016-07-08

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

  1. Tailoring the refractive index of aluminum doped zinc oxide thin films by co-doping with titanium

    NASA Astrophysics Data System (ADS)

    Wei, Tiefeng; Lan, Pinjun; Yang, Ye; Zhang, Xianpeng; Tan, Ruiqin; Li, Yong; Song, Weijie

    2012-12-01

    The refractive index of transparent conductive oxides has a direct effect on the transmission of lights into thin film solar cells. Here we report the study of improving the refractive index of aluminum doped zinc oxide through titanium co-doping. The Al-Ti co-doped zinc oxide (ATZO) thin films with different Ti doping concentration were deposited on glass substrates by radio frequency magnetron sputtering with ATZO targets in an argon atmosphere. The structural, optical and electrical properties of the thin films were investigated using X-ray diffraction, ultraviolet-visible-near-infrared spectroscopy and hall measurements, respectively. The results showed that the as-deposited thin films were all textured along c-axis and perpendicular to the surface of substrate. The average transmittance in the visible region were more than 80% for all the ATZO thin films. The minimum resistivity of the obtained ATZO (1 wt% TiO2 doping) thin films were 2.6 × 10-3 Ω cm and 1.4 × 10-3 Ω cm before and after annealing in vacuum, respectively. The refractive index of the thin films (at λ0 = 550 nm) increased from 1.91 to 2.05 as the TiO2 content increased from 0 wt% to 3 wt%.

  2. Rice husk ash/calcium oxide/ceria sorbent for simultaneous removal of sulfur dioxide and nitric oxide from flue gas at low temperature

    SciTech Connect

    Dahlan, I.; Lee, K.T.; Kamaruddin, A.H.; Mohamed, A.R.

    2009-06-15

    The reduction of sulfur dioxide (SO{sub 2}) and nitric oxide (NO) emissions has become an isssue of great importance to government regulatory agencies and general public due to their negative effect towards the environment and human health. In this work, the simultaneous removal of sulfur dioxide (SO{sub 2}) and nitric oxide (NO) from simulated flue gas was investigated in a fixed-bed reactor using rice husk ash (RHA)/CaO/CeO{sub 2} sorbent. Attention was focused on the major reactor operation parameters affecting sorption capacity of RHA/CaO/CeO{sub 2} sorbent, which include feed concentration of SO{sub 2} and NO, relative humidity (RH), operating temperature and space velocity (GHSV). This is because such information is unavailable for RHA-based sorbent and the effects of these parameters reported in the literature are also not reliable. Enhancement effect of NO on removal of SO{sub 2} was observed and the presence of SO{sub 2} was essential to the removal of NO. However, at a high level of SO{sub 2}/NO concentration, competition in the sorption of NO and SO{sub 2} on the sorbent active sites might have occurred. RH was found to significantly enhance the SO{sub 2} sorption of the RHA/CaO/CeO{sub 2} sorbent. By contrast, NO sorption capacity decreases when RH was further introduced, as it was not easy to sorb NO in the presence of water. Apart from that, the results also shows that there was a threshold value for the RH to ensure higher SO{sub 2} and NO removal and this value was observed at 50% RH. Higher operating temperatures were favored for SO{sub 2} and NO removal. Nevertheless, beyond 150 degrees C the SO{sub 2} removal was found to decrease. On the other hand, a lower space velocity resulted in a higher SO{sub 2} and NO removal.

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

    SciTech Connect

    Samiee, Sara; Goharshadi, Elaheh K.

    2012-04-15

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

  4. Magnesium oxide doping reduces acoustic wave attenuation in lithium metatantalate and lithium metaniobate crystals

    NASA Technical Reports Server (NTRS)

    Croft, W.; Damon, R.; Kedzie, R.; Kestigian, M.; Smith, A.; Worley, J.

    1970-01-01

    Single crystals of lithium metatantalate and lithium metaniobate, grown from melts having different stoichiometries and different amounts of magnesium oxide, show that doping lowers temperature-independent portion of attenuation of acoustic waves. Doped crystals possess optical properties well suited for electro-optical and photoelastic applications.

  5. A positron annihilation spectroscopic investigation of europium-doped cerium oxide nanoparticles.

    PubMed

    Thorat, Atul V; Ghoshal, Tandra; Holmes, Justin D; Nambissan, P M G; Morris, Michael A

    2014-01-07

    Doping in ceria (CeO2) nanoparticles with europium (Eu) of varying concentrations (0, 0.1, 0.5, …, 50 atom%) is studied using complementary experimental techniques and novel observations were made during the investigation. The immediate observable effect was a distinct reduction in particle sizes with increasing Eu concentration attributed to the relaxation of strain introduced due to the replacement of Ce(4+) ions by Eu(3+) ions of larger radius. However, this general trend was reversed in the doping concentration range of 0.1-1 atom% due to the reduction of Ce(4+) to Ce(3+) and the formation of anion vacancies. Quantum confinement effects became evident with the increase of band gap energy when the particle sizes reduced below 7-8 nm. Positron annihilation studies indicated the presence of vacancy type defects in the form of vacancy clusters within the nanoparticles. Some positron annihilation was also seen on the surface of crystallites as a result of diffusion of thermalized positrons before annihilation. Coincidence Doppler broadening measurements indicated the annihilation of positrons with electrons of different species of atoms and the characteristic S-W plot showed a kink-like feature at the particle sizes where quantum confinement effects began.

  6. Enhancing Sulfur Tolerance of Ni-Based Cermet Anodes of Solid Oxide Fuel Cells by Ytterbium-Doped Barium Cerate Infiltration.

    PubMed

    Li, Meng; Hua, Bin; Luo, Jing-Li; Jiang, San Ping; Pu, Jian; Chi, Bo; Li, Jian

    2016-04-27

    Conventional anode materials for solid oxide fuel cells (SOFCs) are Ni-based cermets, which are highly susceptible to deactivation by contaminants in hydrocarbon fuels. Hydrogen sulfide is one of the commonly existed contaminants in readily available natural gas and gasification product gases of pyrolysis of biomasses. Development of sulfur tolerant anode materials is thus one of the critical challenges for commercial viability and practical application of SOFC technologies. Here we report a viable approach to enhance substantially the sulfur poisoning resistance of a Ni-gadolinia-doped ceria (Ni-GDC) anode through impregnation of proton conducting perovskite BaCe0.9Yb0.1O3-δ (BCYb). The impregnation of BCYb nanoparticles improves the electrochemical performance of the Ni-GDC anode in both H2 and H2S containing fuels. Moreover, more importantly, the enhanced stability is observed in 500 ppm of H2S/H2. The SEM and XPS analysis indicate that the infiltrated BCYb fine particles inhibit the adsorption of sulfur and facilitate sulfur removal from active sites, thus preventing the detrimental interaction between sulfur and Ni-GDC and the formation of cerium sulfide. The preliminary results of the cell with the BCYb+Ni-GDC anode in methane fuel containing 5000 ppm of H2S show the promising potential of the BCYb infiltration approach in the development of highly active and stable Ni-GDC-based anodes fed with hydrocarbon fuels containing a high concentration of sulfur compounds.

  7. Water Oxidation and Oxygen Monitoring by Cobalt-Modified Fluorine-Doped Tin Oxide Electrodes

    SciTech Connect

    Kent, CA; Concepcion, JJ; Dares, CJ; Torelli, DA; Rieth, AJ; Miller, AS; Hoertz, PG; Meyer, TJ

    2013-06-12

    Electrocatalytic water oxidation occurs at fluoride-doped tin oxide (FTO) electrodes that have been surface-modified by addition of Co(II). On the basis of X-ray photoelectron spectroscopy and transmission electron microscopy measurements, the active surface site appears to be a single site or small-molecule assembly bound as Co(II), with no evidence for cobalt oxide film or cluster formation. On the basis of cyclic voltammetry measurements, surface-bound Co(II) undergoes a pH-dependent 1e(-)/1H(+) oxidation to Co(III), which is followed by pH-dependent catalytic water oxidation. O-2 reduction at FTO occurs at -0.33 V vs NHE, allowing for in situ detection of oxygen as it is formed by water oxidation on the surface. Controlled-potential electrolysis at 1.61 V vs NHE at pH 7.2 resulted in sustained water oxidation catalysis at a current density of 0.16 mA/cm(2) with 29 000 turnovers per site over an electrolysis period of 2 h. The turnover frequency for oxygen production per Co site was 4 s(-1) at an overpotential of 800 mV at pH 7.2. Initial experiments with Co(II) on a mesoporous, high-surface-area nanoFTO electrode increased the current density by a factor of similar to 5

  8. Boron-doped cobalt oxide thin films and its electrochemical properties

    NASA Astrophysics Data System (ADS)

    Kerli, S.

    2016-09-01

    The cobalt oxide and boron-doped cobalt oxide thin films were produced by spray deposition method. All films were obtained onto glass and fluorine-doped tin oxide (FTO) substrates at 400∘C and annealed at 550∘C. We present detailed analysis of the morphological and optical properties of films. XRD results show that boron doping disrupts the structure of the films. Morphologies of the films were investigated by using a scanning electron microscopy (SEM). Optical measurements indicate that the band gap energies of the films change with boron concentrations. The electrochemical supercapacitor performance test has been studied in aqueous 6 M KOH electrolyte and with scan rate of 5 mV/s. Measurements show that the largest capacitance is obtained for 3% boron-doped cobalt oxide film.

  9. Ceria-based electrospun fibers for renewable fuel production via two-step thermal redox cycles for carbon dioxide splitting.

    PubMed

    Gibbons, William T; Venstrom, Luke J; De Smith, Robert M; Davidson, Jane H; Jackson, Gregory S

    2014-07-21

    Zirconium-doped ceria (Ce(1-x)Zr(x)O2) was synthesized through a controlled electrospinning process as a promising approach to cost-effective, sinter-resistant material structures for high-temperature, solar-driven thermochemical redox cycles. To approximate a two-step redox cycle for solar fuel production, fibrous Ce(1-x)Zr(x)O2 with relatively low levels of Zr-doping (0 < x < 0.1) were cycled in an infrared-imaging furnace with high-temperature (up to 1500 °C) partial reduction and lower-temperature (∼800 °C) reoxidation via CO2 splitting to produce CO. Increases in Zr content improve reducibility and sintering resistance, and, for x≤ 0.05, do not significantly slow reoxidation kinetics for CO production. Cycle stability of the fibrous Ce(1-x)Zr(x)O2 (with x = 0.025) was assessed for a range of conditions by measuring rates of O2 release during reduction and CO production during reoxidation and by assessing post-cycling fiber crystallite sizes and surface areas. Sintering increases with reduction temperature but occurs primarily along the fiber axes. Even after 108 redox cycles with reduction at 1400 °C and oxidation with CO2 at 800 °C, the fibers maintain their structure with surface areas of ∼0.3 m(2) g(-1), higher than those observed in the literature for other ceria-based structures operating at similarly high temperature conditions. Total CO production and peak production rate stabilize above 3.0 mL g(-1) and 13.0 mL min(-1) g(-1), respectively. The results show the potential for electrospun oxides as sinter-resistant material structures with adequate surface area to support rapid CO2 splitting in solar thermochemical redox cycles.

  10. Complex oxide ferroelectrics: Electrostatic doping by domain walls

    SciTech Connect

    Maksymovych, Petro

    2015-06-19

    Electrically conducting interfaces can form, rather unexpectedly, by breaking the translational symmetry of electrically insulating complex oxides. For example, a nanometre-thick heteroepitaxial interface between electronically insulating LaAlO3 and SrTiO3 supports a 2D electron gas1 with high mobility of >1,000 cm2 V-1 s-1 (ref. 2). Such interfaces can exhibit magnetism, superconductivity and phase transitions that may form the functional basis of future electronic devices2. A peculiar conducting interface can be created within a polar ferroelectric oxide by breaking the translational symmetry of the ferroelectric order parameter and creating a so-called ferroelectric domain wall (Fig. 1a,b). If the direction of atomic displacements changes at the wall in such a way as to create a discontinuity in the polarization component normal to the wall (Fig. 1a), the domain wall becomes electrostatically charged. It may then attract compensating mobile charges of opposite sign produced by dopant ionization, photoexcitation or other effects, thereby locally, electrostatically doping the host ferroelectric film. In contrast to conductive interfaces between epitaxially grown oxides, domain walls can be reversibly created, positioned and shaped by electric fields, enabling reconfigurable circuitry within the same volume of the material. Now, writing in Nature Nanotechnology, Arnaud Crassous and colleagues at EPFL and University of Geneva demonstrate control and stability of charged conducting domain walls in ferroelectric thin films of BiFeO3 down to the nanoscale.

  11. Spectroscopic Properties of Neodymium and Erbium-Doped Magnesium Oxide Ceramics

    DTIC Science & Technology

    2015-09-01

    ARL-TR-7441 ● SEPT 2015 US Army Research Laboratory Spectroscopic Properties of Neodymium and Erbium-Doped Magnesium Oxide...Laboratory Spectroscopic Properties of Neodymium and Erbium-Doped Magnesium Oxide Ceramics by T Sanamyan and M Dubinskii Sensors and...REPORT DATE (DD-MM-YYYY) Sep 2015 2. REPORT TYPE Final 3. DATES COVERED (From - To) 4. TITLE AND SUBTITLE Spectroscopic Properties of Neodymium

  12. Novel Carbon Dioxide Microsensor Based on Tin Oxide Nanomaterial Doped With Copper Oxide

    NASA Technical Reports Server (NTRS)

    Xu, Jennifer C.; Hunter, Gary W.; Lukco, Dorothy; Liu, Chung-Chiun; Ward, Benjamin J.

    2008-01-01

    Carbon dioxide (CO2) is one of the major indicators of fire and therefore its measurement is very important for low-false-alarm fire detection and emissions monitoring. However, only a limited number of CO2 sensing materials exist due to the high chemical stability of CO2. In this work, a novel CO2 microsensor based on nanocrystalline tin oxide (SnO2) doped with copper oxide (CuO) has been successfully demonstrated. The CuO-SnO2 based CO2 microsensors are fabricated by means of microelectromechanical systems (MEMS) technology and sol-gel nanomaterial-synthesis processes. At a doping level of CuO: SnO2 = 1:8 (molar ratio), the resistance of the sensor has a linear response to CO2 concentrations for the range of 1 to 4 percent CO2 in air at 450 C. This approach has demonstrated the use of SnO2, typically used for the detection of reducing gases, in the detection of an oxidizing gas.

  13. 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.

  14. Different properties of aluminum doped zinc oxide nanostructured thin films prepared by radio frequency magnetron sputtering

    SciTech Connect

    Bidmeshkipour, Samina Shahtahmasebi, Nasser

    2013-06-15

    Aluminium doped zinc oxide (AZO) nanostructured thin films are prepared by radio frequency magnetron sputtering on glass substrate using specifically designed ZnO target containing different amount of Al{sub 2}O{sub 3} powder as the Al doping source. The optical properties of the aluminium doped zinc oxide films are investigated. The topography of the deposited films were investigated by Atomic Force Microscopy. Variation of the refractive index by annealing temperature are considered and it is seen that the refractive index increases by increasing the annealing temperature.

  15. Reduced ceria nanofilms from structure prediction.

    PubMed

    Kozlov, Sergey M; Demiroglu, Ilker; Neyman, Konstantin M; Bromley, Stefan T

    2015-03-14

    Experimentally, Ce2O3 films are used to study cerium oxide in its fully or partially reduced state, as present in many applications. We have explored the space of low energy Ce2O3 nanofilms using structure prediction and density functional calculations, yielding more than 30 distinct nanofilm structures. First, our results help to rationalize the roles of thermodynamics and kinetics in the preparation of reduced ceria nanofilms with different bulk crystalline structures (e.g. A-type or bixbyite) depending on the support used. Second, we predict a novel, as yet experimentally unresolved, nanofilm which has a structure that does not correspond to any previously reported bulk A2B3 phase and which has an energetic stability between that of A-type and bixbyite. To assist identification and fabrication of this new Ce2O3 nanofilm we calculate some observable properties and propose supports for its epitaxial growth.

  16. Carbon dioxide activation and dissociation on ceria (110): a density functional theory study.

    PubMed

    Cheng, Zhuo; Sherman, Brent J; Lo, Cynthia S

    2013-01-07

    Ceria (CeO(2)) is a promising catalyst for the reduction of carbon dioxide (CO(2)) to liquid fuels and commodity chemicals, in part because of its high oxygen storage capacity, yet the fundamentals of CO(2) adsorption, activation, and reduction on ceria surfaces remain largely unknown. We use density functional theory, corrected for onsite Coulombic interactions (GGA+U), to explore various adsorption sites and configurations for CO(2) on stoichiometric and reduced ceria (110), the latter with either an in-plane oxygen vacancy or a split oxygen vacancy. We find that CO(2) adsorption on both reduced ceria (110) surfaces is thermodynamically favored over the corresponding adsorption on stoichiometric ceria (110), but the most stable adsorption configuration consists of CO(2) adsorbed parallel to the reduced ceria (110) surface at a split oxygen vacancy. Structural changes in the CO(2) molecule are also observed upon adsorption. At the split vacancy, the molecule bends out of plane to form a unidentate carbonate with the remaining oxygen anion at the surface; this is in stark contrast to the bridged carbonate observed for CO(2) adsorption at the in-plane vacancy. Also, we analyze the pathways for CO(2) conversion to CO on reduced ceria (110). The subtle difference in the energies of activation for the elementary steps suggest that CO(2) dissociation is favored on the split vacancy, while the reverse process of CO oxidation may favor the formation of the in-plane vacancy. We thus show how the structure and properties of the ceria catalyst govern the mechanism of CO(2) activation and reduction.

  17. Electrochromic characteristics of niobium-doped titanium oxide film on indium tin oxide/glass by liquid phase deposition

    NASA Astrophysics Data System (ADS)

    Lee, Ming-Kwei; Lee, Chia-Jung

    2015-10-01

    Ammonium hexafluorotitanate and boric acid aqueous solutions were used as precursors for the growth of titanium oxide films on indium tin oxide (ITO)/glass substrate. For as-grown titanium oxide film used in an electrochromic device, Li+ ions from electrolyte will be trapped to hydroxyl groups and degrade the electrochromic durability during the cyclic voltammogram characterization. For niobium doped titanium oxide film, lower growth rate from more HF incorporation from the niobium doped solution and rougher surface morphology from the formation of nanocrystals were obtained. However, niobium doping reduces hydroxyl groups and the electrochromic durability is enhanced from 5 × 103 to 1 × 104 times. The transmittance is enhanced from 37 to 51% at the wavelength of 550 nm.

  18. Defects and transport properties of molybdenum doped indium oxide

    NASA Astrophysics Data System (ADS)

    Yoshida, Yuki; Gessert, Timothy; Wood, David; Coutts, Timothy

    2004-03-01

    Mo-doped indium oxide (IMO) films were deposited using an r.f. magnetron sputtering system under various oxygen concentrations. Using the `method of four coefficients', the conductivity, Hall, Nernst, and Seebeck coefficients were measured for IMO. These coefficients can be used with solutions to the Boltzmann transport equation to extract the carrier density-of-states effective mass, the Fermi level relative to the conduction-band minimum, and an energy-dependent scattering parameter related to the scattering mechanism. We find the conduction band is parabolic with a band effective mass of ˜ 0.32 me over a carrier concentration range from 4×10^19 to 5× 10^20 cm-3, indicating that relaxation time controls mobility in IMO. Temperature-dependent Hall measurements show that phonon and ionized-impurity scattering dominate at high mobility and high carrier concentration, respectively. We will also discuss possible defects in the film using XPS and electrical property data.

  19. The effect of sub-oxide phases on the transparency of tin-doped gallium oxide

    SciTech Connect

    Lim, K.; Schelhas, L. T.; Siah, S. C.; Brandt, R. E.; Zakutayev, A.; Lany, S.; Gorman, B.; Sun, C. J.; Ginley, D.; Buonassisi, T.; Toney, M. F.

    2016-10-03

    There have been a number of studies on the fabrication of Sn-doped gallium oxide (Ga2O3:Sn) films with both conductive and transparent properties using a variety of deposition methods. However, often, synthesis results in films that are not transparent. In this paper, we examine the mechanisms underlying these results in Ga2O3:Sn thin films prepared at various growth temperatures, Sn concentrations, and oxygen partial pressures. With X-ray absorption spectroscopy, transmission electron microscopy and energy dispersive spectroscopy, we find that when films are grown under the oxygen deficient conditions there are Ga sub-oxide and SnOx phases in the Ga2O3:Sn thin film. These Ga sub-oxide phases are only found in non-transparent films, and so we infer that the Ga sub-oxide is responsible for the non-transparency. These observations suggest that to obtain transparent Ga2O3:Sn, films deposition or subsequent annealing must be carefully controlled in both temperature and oxygen partial pressure to avoid the formation of Ga sub-oxide phases.

  20. The effect of sub-oxide phases on the transparency of tin-doped gallium oxide

    SciTech Connect

    Lim, K.; Schelhas, L. T.; Siah, S. C.; Brandt, R. E.; Zakutayev, A.; Lany, S.; Gorman, B.; Sun, C. J.; Ginley, D.; Buonassisi, T.; Toney, M. F.

    2016-10-03

    There have been a number of studies on the fabrication of Sn-doped gallium oxide (Ga2O3:Sn) films with both conductive and transparent properties using a variety of deposition methods. However, often, synthesis results in films that are not transparent. In this paper, we examine the mechanisms underlying these results in Ga2O3:Sn thin films prepared at various growth temperatures, Sn concentrations, and oxygen partial pressures. With X-ray absorption spectroscopy, transmission electron microscopy and energy dispersive spectroscopy, we find that when films are grown under the oxygen deficient conditions there are Ga sub-oxide and SnOx phases in the Ga2O3:Sn thin film. These Ga sub-oxide phases are only found in non-transparent films, and so we infer that the Ga sub-oxide is responsible for the non-transparency. These observations suggest that to obtain transparent Ga2O3:Sn, films deposition or subsequent annealing must be carefully controlled in both temperature and oxygen partial pressure to avoid the formation of Ga sub-oxide phases.

  1. Cobalt-phosphate-assisted photoelectrochemical water oxidation by arrays of molybdenum-doped zinc oxide nanorods.

    PubMed

    Lin, Yan-Gu; Hsu, Yu-Kuei; Chen, Ying-Chu; Lee, Bing-Wei; Hwang, Jih-Shang; Chen, Li-Chyong; Chen, Kuei-Hsien

    2014-09-01

    We report the first demonstration of cobalt phosphate (Co-Pi)-assisted molybdenum-doped zinc oxide nanorods (Zn(1-x)Mo(x)O NRs) as visible-light-sensitive photofunctional electrodes to fundamentally improve the performance of ZnO NRs for photoelectrochemical (PEC) water splitting. A maximum photoconversion efficiency as high as 1.05% was achieved, at a photocurrent density of 1.4 mA cm(-2). More importantly, in addition to achieve the maximum incident photon to current conversion efficiency (IPCE) value of 86%, it could be noted that the IPCE of Zn(1-x)Mo(x)O photoanodes under monochromatic illumination (450 nm) is up to 12%. Our PEC performances are comparable to those of many oxide-based photoanodes in recent reports. The improvement in photoactivity of PEC water splitting may be attributed to the enhanced visible-light absorption, increased charge-carrier densities, and improved interfacial charge-transfer kinetics due to the combined effect of molybdenum incorporation and Co-Pi modification, contributing to photocatalysis. The new design of constructing highly photoactive Co-Pi-assisted Zn(1-x)Mo(x)O photoanodes enriches knowledge on doping and advances the development of high-efficiency photoelectrodes in the solar-hydrogen field.

  2. Crystalline structure of ceria particles controlled by the oxygen partial pressure and STI CMP performances.

    PubMed

    Kim, Ye-Hwan; Kim, Sang-Kyun; Kim, Namsoo; Park, Jea-Gun; Paik, Ungyu

    2008-09-01

    The effect of the crystalline structures of nano-sized ceria particles on shallow trench isolation (STI) chemical mechanical planarization (CMP) performance was investigated. The ceria particles were synthesized via a solid-state displacement reaction method, and their crystalline structure was controlled by regulating the oxygen partial pressure at the reaction site on the precursor. The crystalline structures of ceria particles were analyzed by the high-resolution TEM nano-beam diffraction pattern. In a calcination process with a high oxygen concentration, the synthesized ceria particles had a cubic fluorite structure (CeO(2)), because of the decarbonation of the cerium precursor. However, a low oxygen concentration results in a hexagonal phase cerium oxide (Ce(2)O(3)) rather than the cubic phase due to the insufficient oxidation of Ce(3+) to Ce(4+). In the STI CMP evaluation, the ceria slurry prepared with the cubic CeO(2) shows enhanced performances of the oxide-to-nitride removal selectivity.

  3. Doped and Undoped Zinc Oxide Nanostructures on Silicon Wafers

    NASA Astrophysics Data System (ADS)

    Chubenko, E.; Bondarenko, V.

    2013-05-01

    We present results of hydrothermal deposition of undoped and Al doped ZnO nanocrystals on nanocrystalline silicon. ZnO nanocrystals were deposited in an equimolar zinc nitride and hexamethylenetetramine solution. Aluminum nitride was used as Al precursor. The difference of the morphology of doped and undoped ZnO nanocrystals is discussed. Photoluminescence properties of the obtained nanocrystals are shown.

  4. 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

  5. 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.

  6. 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.

  7. Catalytic wet air oxidation with Ni- and Fe-doped mixed oxides derived from hydrotalcites.

    PubMed

    Ovejero, G; Rodríguez, A; Vallet, A; Gómez, P; García, J

    2011-01-01

    Catalytic wet air oxidation of Basic Yellow 11 (BY11), a basic dye, was studied in a batch reactor. Layered double hydroxides with the hydrotalcite-like structure containing nickel or iron cations have been prepared by coprecipitation and subsequently calcined leading to Ni- and Fe-doped mixed oxides, respectively. Compared with the results in the wet air oxidation of BY11, these catalysts showed high activity for total organic carbon (TOC), toxicity and dye removal at 120 degrees C and 50 bars after 120 min. It has been demonstrated that the activity depended strongly on the presence of catalyst. The results show that catalysts containing nickel provide a higher extent of oxidation of the dye whereas the reaction carried out with the iron catalyst is faster. The Ni and Fe dispersion determined from the TPR results was higher for the catalysts with a lower Ni or Fe content and decreased for higher Ni or Fe contents. On the basis of activity and selectivity, the Ni containing catalyst with the medium (3%) Ni content was found to be the best catalyst. Finally, a relationship between metal content of the catalyst and reaction rate has been established.

  8. Raman spectroscopy as a probe of temperature and oxidation state for gadolinium-doped ceria used in solid oxide fuel cells.

    PubMed

    Maher, R C; Cohen, L F; Lohsoontorn, P; Brett, D J L; Brandon, N P

    2008-02-21

    Raman spectroscopy is a noninvasive and highly sensitive analytical technique capable of identifying chemical compounds in environments that can mimic SOFC operating conditions. Here we demonstrate the use of Raman spectroscopy to perform local thermal and temporal measurements, both of which are essential if phase formation diagrams are to be mapped out and compared to thermodynamic phase stability predictions. We find that the time resolution of the Raman technique is more than sufficient to capture essential dynamic effects associated with a change of chemical composition.

  9. Sol-gel deposited aluminum-doped and gallium-doped zinc oxide thin-film transparent conductive electrodes with a protective coating of reduced graphene oxide

    NASA Astrophysics Data System (ADS)

    Zhu, Zhaozhao; Mankowski, Trent; Balakrishnan, Kaushik; Shikoh, Ali Sehpar; Touati, Farid; Benammar, Mohieddine A.; Mansuripur, Masud; Falco, Charles M.

    2016-04-01

    Using a traditional sol-gel deposition technique, we successfully fabricated aluminum-doped zinc oxide (AZO) and gallium-doped zinc oxide (GZO) thin films on glass substrates. Employing a plasma treatment method as the postannealing process, we produced thin-film transparent conductive electrodes exhibiting excellent optical and electrical properties, with transmittance greater than 90% across the entire visible spectrum and the near-infrared range, as well as good sheet resistance under 200 Ω/sq. More importantly, to improve the resilience of our fabricated thin-film samples at elevated temperatures and in humid environments, we deposited a layer of reduced graphene oxide (rGO) as protective overcoating. The stability of our composite AZO/rGO and GZO/rGO samples improved substantially compared to that of their counterparts with no rGO coating.

  10. Surface versus volume effects in luminescent ceria nanocrystals synthesized by an oil-in-water microemulsion method.

    PubMed

    Tiseanu, Carmen; Parvulescu, Vasile I; Boutonnet, Magali; Cojocaru, Bogdan; Primus, Philipp A; Teodorescu, Cristian M; Solans, Conchita; Sanchez Dominguez, Margarita

    2011-10-14

    Pure and europium (Eu(3+)) doped cerium dioxide (CeO(2)) nanocrystals have been synthesized by a novel oil-in-water microemulsion reaction method under soft conditions. In-situ X-ray diffraction and RAMAN spectroscopy, high-resolution transmission electron microscopy, UV/Vis diffuse-reflectance and Fourier transform infrared spectroscopy as well as time-resolved photoluminescence spectroscopy were used to characterize the nanaocrystals. The as-synthesized powders are nanocrystalline and have a narrow size distribution centered on 3 nm and high surface area of ~250 m(2) g(-1). Only a small fraction of the europium ions substitutes for the bulk, cubic Ce(4+) sites in the europium-doped ceria nanocrystals. Upon calcination up to 1000 °C, a remarkable high surface area of ~120 m(2) g(-1) is preserved whereas an enrichment of the surface Ce(4+) relative to Ce(3+) ions and relative strong europium emission with a lifetime of ~1.8 ms and FWHM as narrow as 10 cm(-1) are measured. Under excitation into the UV and visible spectral range, the europium doped ceria nanocrystals display a variable emission spanning the orange-red wavelengths. The tunable emission is explained by the heterogeneous distribution of the europium dopants within the ceria nanocrystals coupled with the progressive diffusion of the europium ions from the surface to the inner ceria sites and the selective participation of the ceria host to the emission sensitization. Effects of the bulk-doping and impregnation with europium on the ceria host structure and optical properties are also discussed.

  11. Iodine doping effects on the lattice thermal conductivity of oxidized polyacetylene nanofibers

    SciTech Connect

    Bi, Kedong E-mail: kedongbi@seu.edu.cn; Weathers, Annie; Pettes, Michael T.; Shi, Li E-mail: kedongbi@seu.edu.cn; Matsushita, Satoshi; Akagi, Kazuo; Goh, Munju

    2013-11-21

    Thermal transport in oxidized polyacetylene (PA) nanofibers with diameters in the range between 74 and 126 nm is measured with the use of a suspended micro heater device. With the error due to both radiation and contact thermal resistance corrected via a differential measurement procedure, the obtained thermal conductivity of oxidized PA nanofibers varies in the range between 0.84 and 1.24 W m{sup −1} K{sup −1} near room temperature, and decreases by 40%–70% after iodine doping. It is also found that the thermal conductivity of oxidized PA nanofibers increases with temperature between 100 and 350 K. Because of exposure to oxygen during sample preparation, the PA nanofibers are oxidized to be electrically insulating before and after iodine doping. The measurement results reveal that iodine doping can result in enhanced lattice disorder and reduced lattice thermal conductivity of PA nanofibers. If the oxidation issue can be addressed via further research to increase the electrical conductivity via doping, the observed suppressed lattice thermal conductivity in doped polymer nanofibers can be useful for the development of such conducting polymer nanostructures for thermoelectric energy conversion.

  12. Plasma-induced highly efficient synthesis of boron doped reduced graphene oxide for supercapacitors.

    PubMed

    Li, Shaobo; Wang, Zhaofeng; Jiang, Hanmei; Zhang, Limei; Ren, Jingzheng; Zheng, Mingtao; Dong, Lichun; Sun, Luyi

    2016-09-21

    In this work, we presented a novel route to synthesize boron doped reduced graphene oxide (rGO) by using the dielectric barrier discharge (DBD) plasma technology under ambient conditions. The doping of boron (1.4 at%) led to a significant improvement in the capacitance of rGO and supercapacitors based on the as-synthesized B-rGO exhibited an outstanding specific capacitance.

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

    PubMed

    Wu, Xin-Ping; Gong, Xue-Qing

    2015-10-21

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

  14. Effects of erbium doping of indium tin oxide electrode in resistive random access memory

    NASA Astrophysics Data System (ADS)

    Chen, Po-Hsun; Chang, Kuan-Chang; Chang, Ting-Chang; Tsai, Tsung-Ming; Pan, Chih-Hung; Lin, Chih-Yang; Jin, Fu-Yuan; Chen, Min-Chen; Huang, Hui-Chun; Lo, Ikai; Zheng, Jin-Cheng; Sze, Simon M.

    2016-03-01

    Identical insulators and bottom electrodes were fabricated and capped by an indium tin oxide (ITO) film, either undoped or doped with erbium (Er), as a top electrode. This distinctive top electrode dramatically altered the resistive random access memory (RRAM) characteristics, for example, lowering the operation current and enlarging the memory window. In addition, the RESET voltage increased, whereas the SET voltage remained almost the same. A conduction model of Er-doped ITO is proposed through current-voltage (I-V) measurement and current fitting to explain the resistance switching mechanism of Er-doped ITO RRAM and is confirmed by material analysis and reliability tests.

  15. Controlled Growth of Ceria Nanoarrays on Anatase Titania Powder: A Bottom-up Physical Picture.

    PubMed

    Kim, Hyun You; Hybertsen, Mark S; Liu, Ping

    2017-01-11

    The leading edge of catalysis research motivates physical understanding of the growth of nanoscale oxide structures on different supporting oxide materials that are themselves also nanostructured. This research opens up for consideration a diverse range of facets on the support material, versus the single facet typically involved in wide-area growth of thin films. Here, we study the growth of ceria nanoarchitectures on practical anatase titania powders as a showcase inspired by recent experiments. Density functional theory (DFT)-based methods are employed to characterize and rationalize the broad array of low energy nanostructures that emerge. Using a bottom-up approach, we are able to identify and characterize the underlying mechanisms for the facet-dependent growth of various ceria motifs on anatase titania based on formation energy. These motifs include 0D clusters, 1D chains, 2D plates, and 3D nanoparticles. The ceria growth mode and morphology are determined by the interplay of several factors including the role of the common cation valence, the interface template effect for different facets of the anatase support, enhanced ionic binding for more compact ceria motifs, and the local structural flexibility of oxygen ions in bridging the interface between anatase and ceria structures.

  16. Gas-generated thermal oxidation of a coordination cluster for an anion-doped mesoporous metal oxide

    PubMed Central

    Hirai, Kenji; Isobe, Shigehito; Sada, Kazuki

    2015-01-01

    Central in material design of metal oxides is the increase of surface area and control of intrinsic electronic and optical properties, because of potential applications for energy storage, photocatalysis and photovoltaics. Here, we disclose a facile method, inspired by geochemical process, which gives rise to mesoporous anion-doped metal oxides. As a model system, we demonstrate that simple calcination of a multinuclear coordination cluster results in synchronic chemical reactions: thermal oxidation of Ti8O10(4-aminobenzoate)12 and generation of gases including amino-group fragments. The gas generation during the thermal oxidation of Ti8O10(4-aminobenzoate)12 creates mesoporosity in TiO2. Concurrently, nitrogen atoms contained in the gases are doped into TiO2, thus leading to the formation of mesoporous N-doped TiO2. The mesoporous N-doped TiO2 can be easily synthesized by calcination of the multinuclear coordination cluster, but shows better photocatalytic activity than the one prepared by a conventional sol-gel method. Owing to an intrinsic designability of coordination compounds, this facile synthetic will be applicable to a wide range of metal oxides and anion dopants. PMID:26681104

  17. Gas-generated thermal oxidation of a coordination cluster for an anion-doped mesoporous metal oxide

    NASA Astrophysics Data System (ADS)

    Hirai, Kenji; Isobe, Shigehito; Sada, Kazuki

    2015-12-01

    Central in material design of metal oxides is the increase of surface area and control of intrinsic electronic and optical properties, because of potential applications for energy storage, photocatalysis and photovoltaics. Here, we disclose a facile method, inspired by geochemical process, which gives rise to mesoporous anion-doped metal oxides. As a model system, we demonstrate that simple calcination of a multinuclear coordination cluster results in synchronic chemical reactions: thermal oxidation of Ti8O10(4-aminobenzoate)12 and generation of gases including amino-group fragments. The gas generation during the thermal oxidation of Ti8O10(4-aminobenzoate)12 creates mesoporosity in TiO2. Concurrently, nitrogen atoms contained in the gases are doped into TiO2, thus leading to the formation of mesoporous N-doped TiO2. The mesoporous N-doped TiO2 can be easily synthesized by calcination of the multinuclear coordination cluster, but shows better photocatalytic activity than the one prepared by a conventional sol-gel method. Owing to an intrinsic designability of coordination compounds, this facile synthetic will be applicable to a wide range of metal oxides and anion dopants.

  18. A thermochemical study of ceria: exploiting an old material for new modes of energy conversion and CO2 mitigation.

    PubMed

    Chueh, William C; Haile, Sossina M

    2010-07-28

    We present a comprehensive thermodynamic and kinetic analysis of the suitability of cerium oxide (ceria) for thermochemical fuel production. Both portions of the two-step cycle, (i) oxygen release from the oxide at 1773 and 1873 K under inert atmosphere, and (ii) hydrogen release upon hydrolysis at 1073 K, are examined theoretically as well as experimentally. We observe gravimetric fuel productivity that is in quantitative agreement with equilibrium, thermogravimetric studies of ceria. Despite the non-stoichiometric nature of the redox cycle, in which only a portion of the cerium atoms change their oxidation state, the fuel productivity of 8.5-11.8 ml of H(2) per gram of ceria is competitive with that of other solid-state thermochemical cycles currently under investigation. The fuel production rate, which is also highly attractive, at a rate of 4.6-6.2 ml of H(2) per minute per gram of ceria, is found to be limited by a surface-reaction step rather than by ambipolar bulk diffusion of oxygen through the solid ceria. An evaluation of the thermodynamic efficiency of the ceria-based thermochemical cycle suggests that, even in the absence of heat recovery, solar-to-fuel conversion efficiencies of 16 to 19 per cent can be achieved, assuming a suitable method for obtaining an inert atmosphere for the oxygen release step.

  19. Tin doping speeds up hole transfer during light-driven water oxidation at hematite photoanodes.

    PubMed

    Dunn, Halina K; Feckl, Johann M; Müller, Alexander; Fattakhova-Rohlfing, Dina; Morehead, Samuel G; Roos, Julian; Peter, Laurence M; Scheu, Christina; Bein, Thomas

    2014-11-28

    Numerous studies have shown that the performance of hematite photoanodes for light-driven water splitting is improved substantially by doping with various metals, including tin. Although the enhanced performance has commonly been attributed to bulk effects such as increased conductivity, recent studies have noted an impact of doping on the efficiency of the interfacial transfer of holes involved in the oxygen evolution reaction. However, the methods used were not able to elucidate the origin of this improved efficiency, which could originate from passivation of surface electron-hole recombination or catalysis of the oxygen evolution reaction. The present study used intensity-modulated photocurrent spectroscopy (IMPS), which is a powerful small amplitude perturbation technique that can de-convolute the rate constants for charge transfer and recombination at illuminated semiconductor electrodes. The method was applied to examine the kinetics of water oxidation on thin solution-processed hematite model photoanodes, which can be Sn-doped without morphological change. We observed a significant increase in photocurrent upon Sn-doping, which is attributed to a higher transfer efficiency. The kinetic data obtained using IMPS show that Sn-doping brings about a more than tenfold increase in the rate constant for water oxidation by photogenerated holes. This result provides the first demonstration that Sn-doping speeds up water oxidation on hematite by increasing the rate constant for hole transfer.

  20. Electrocatalytic oxidation of Epinephrine and Norepinephrine at metal oxide doped phthalocyanine/MWCNT composite sensor

    NASA Astrophysics Data System (ADS)

    Mphuthi, Ntsoaki G.; Adekunle, Abolanle S.; Ebenso, Eno E.

    2016-06-01

    Glassy carbon electrode (GCE) was modified with metal oxides (MO = Fe3O4, ZnO) nanoparticles doped phthalocyanine (Pc) and functionalized MWCNTs, and the electrocatalytic properties were studied. Successful synthesis of the metal oxide nanoparticles and the MO/Pc/MWCNT composite were confirmed using FTIR, Raman and SEM techniques. The electrodes were characterized using cyclic voltammetry (CV) technique. The electrocatalytic behaviour of the electrode towards epinephrine (EP) and norepinephrine (NE) oxidation was investigated using CV and DPV. Result showed that GCE-MWCNT/Fe3O4/2,3-Nc, GCE-MWCNT/Fe3O429H,31H-Pc, GCE-MWCNT/ZnO/2,3-Nc and GCE-MWCNT/ZnO/29H,31H-Pc electrodes gave enhanced EP and NE current response. Stability study indicated that the four GCE-MWCNT/MO/Pc modified electrodes were stable against electrode fouling effect with the percentage NE current drop of 5.56–5.88% after 20 scans. GCE-MWCNT/Fe3O4/29H,31H-Pc gave the lowest limit of detection (4.6 μM) towards EP while MWCNT/ZnO/29H,31H-Pc gave the lowest limit of detection (1.7 μM) towards NE. The limit of detection and sensitivity of the electrodes compared well with literature. Electrocatalytic oxidation of EP and NE on GCE-MWCNT/MO/Pc electrodes was diffusion controlled with some adsorption of electro-oxidation reaction intermediates products. The electrodes were found to be electrochemically stable, reusable and can be used for the analysis of EP and NE in real life samples.

  1. Electrocatalytic oxidation of Epinephrine and Norepinephrine at metal oxide doped phthalocyanine/MWCNT composite sensor

    PubMed Central

    Mphuthi, Ntsoaki G.; Adekunle, Abolanle S.; Ebenso, Eno E.

    2016-01-01

    Glassy carbon electrode (GCE) was modified with metal oxides (MO = Fe3O4, ZnO) nanoparticles doped phthalocyanine (Pc) and functionalized MWCNTs, and the electrocatalytic properties were studied. Successful synthesis of the metal oxide nanoparticles and the MO/Pc/MWCNT composite were confirmed using FTIR, Raman and SEM techniques. The electrodes were characterized using cyclic voltammetry (CV) technique. The electrocatalytic behaviour of the electrode towards epinephrine (EP) and norepinephrine (NE) oxidation was investigated using CV and DPV. Result showed that GCE-MWCNT/Fe3O4/2,3-Nc, GCE-MWCNT/Fe3O429H,31H-Pc, GCE-MWCNT/ZnO/2,3-Nc and GCE-MWCNT/ZnO/29H,31H-Pc electrodes gave enhanced EP and NE current response. Stability study indicated that the four GCE-MWCNT/MO/Pc modified electrodes were stable against electrode fouling effect with the percentage NE current drop of 5.56–5.88% after 20 scans. GCE-MWCNT/Fe3O4/29H,31H-Pc gave the lowest limit of detection (4.6 μM) towards EP while MWCNT/ZnO/29H,31H-Pc gave the lowest limit of detection (1.7 μM) towards NE. The limit of detection and sensitivity of the electrodes compared well with literature. Electrocatalytic oxidation of EP and NE on GCE-MWCNT/MO/Pc electrodes was diffusion controlled with some adsorption of electro-oxidation reaction intermediates products. The electrodes were found to be electrochemically stable, reusable and can be used for the analysis of EP and NE in real life samples. PMID:27245690

  2. Soot Combustion over Nanostructured Ceria with Different Morphologies

    PubMed Central

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

    2016-01-01

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

  3. Soot Combustion over Nanostructured Ceria with Different Morphologies

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

  4. Soot Combustion over Nanostructured Ceria with Different Morphologies.

    PubMed

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

    2016-06-29

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

  5. Method of Fabrication of High Power Density Solid Oxide Fuel Cells

    DOEpatents

    Pham, Ai Quoc; Glass, Robert S.

    2008-09-09

    A method for producing ultra-high power density solid oxide fuel cells (SOFCs). The method involves the formation of a multilayer structure cells wherein a buffer layer of doped-ceria is deposited intermediate a zirconia electrolyte and a cobalt iron based electrode using a colloidal spray deposition (CSD) technique. For example, a cobalt iron based cathode composed of (La,Sr)(Co,Fe)O(LSCF) may be deposited on a zirconia electrolyte via a buffer layer of doped-ceria deposited by the CSD technique. The thus formed SOFC have a power density of 1400 mW/cm.sup.2 at 600.degree. C. and 900 mW/cm.sup.2 at 700.degree. C. which constitutes a 2-3 times increased in power density over conventionally produced SOFCs.

  6. Multi-wavelength Raman scattering of nanostructured Al-doped zinc oxide

    SciTech Connect

    Russo, V.; Ghidelli, M.; Gondoni, P.

    2014-02-21

    In this work we present a detailed Raman scattering investigation of zinc oxide and aluminum-doped zinc oxide (AZO) films characterized by a variety of nanoscale structures and morphologies and synthesized by pulsed laser deposition under different oxygen pressure conditions. The comparison of Raman spectra for pure ZnO and AZO films with similar morphology at the nano/mesoscale allows to investigate the relation between Raman features (peak or band positions, width, relative intensity) and material properties such as local structural order, stoichiometry, and doping. Moreover Raman measurements with three different excitation lines (532, 457, and 325 nm) point out a strong correlation between vibrational and electronic properties. This observation confirms the relevance of a multi-wavelength Raman investigation to obtain a complete structural characterization of advanced doped oxide materials.

  7. Contact doping of silicon wafers and nanostructures with phosphine oxide monolayers.

    PubMed

    Hazut, Ori; Agarwala, Arunava; Amit, Iddo; Subramani, Thangavel; Zaidiner, Seva; Rosenwaks, Yossi; Yerushalmi, Roie

    2012-11-27

    Contact doping method for the controlled surface doping of silicon wafers and nanometer scale structures is presented. The method, monolayer contact doping (MLCD), utilizes the formation of a dopant-containing monolayer on a donor substrate that is brought to contact and annealed with the interface or structure intended for doping. A unique feature of the MLCD method is that the monolayer used for doping is formed on a separate substrate (termed donor substrate), which is distinct from the interface intended for doping (termed acceptor substrate). The doping process is controlled by anneal conditions, details of the interface, and molecular precursor used for the formation of the dopant-containing monolayer. The MLCD process does not involve formation and removal of SiO(2) capping layer, allowing utilization of surface chemistry details for tuning and simplifying the doping process. Surface contact doping of intrinsic Si wafers (i-Si) and intrinsic silicon nanowires (i-SiNWs) is demonstrated and characterized. Nanowire devices were formed using the i-SiNW channel and contact doped using the MLCD process, yielding highly doped SiNWs. Kelvin probe force microscopy (KPFM) was used to measure the longitudinal dopant distribution of the SiNWs and demonstrated highly uniform distribution in comparison with in situ doped wires. The MLCD process was studied for i-Si substrates with native oxide and H-terminated surface for three types of phosphorus-containing molecules. Sheet resistance measurements reveal the dependency of the doping process on the details of the surface chemistry used and relation to the different chemical environments of the P═O group. Characterization of the thermal decomposition of several monolayer types formed on SiO(2) nanoparticles (NPs) using TGA and XPS provides insight regarding the role of phosphorus surface chemistry at the SiO(2) interface in the overall MLCD process. The new MLCD process presented here for controlled surface doping

  8. One - Step synthesis of nitrogen doped reduced graphene oxide with NiCo nanoparticles for ethanol oxidation in alkaline media.

    PubMed

    Kakaei, Karim; Marzang, Kamaran

    2016-01-15

    Development of anode catalysts and catalyst supporting carbonaceous material containing non-precious metal have attracted tremendous attention in the field of direct ethanol fuel cells (DEFCs). Herein, we report the synthesis and electrochemical properties of nitrogen-doped reduced graphene oxide (NRGO) supported Co, Ni and NiCo nanocomposites. The metal NRGO nanocomposites, in which metal nanoparticles are embedded in the highly porous nitrogen-doped graphene matrix, have been synthesized by simply and one-pot method at a mild temperature using GO, urea choline chloride and urea as reducing and doping agent. The fabricated NiCo/NRGO exhibit remarkable electrocatalytic activity (with Tafel slope of 159.1mVdec(-1)) and high stability for the ethanol oxidation reaction (EOR). The superior performance of the alloy based NRGO is attributed to high surface area, well uniform distribution of high-density nitrogen, metal active sites and synergistic effect.

  9. Enhanced ceria solid electrolyte fuel cell development. Reduction of electronic conductivity permits use of a solid ceria electrolyte in high efficiency high power density fuel cells at temperatures compatible with metallic cell hardware

    NASA Astrophysics Data System (ADS)

    Maricle, D. L.

    1990-01-01

    The high operating temperature of zirconia based solid oxide fuel cells has been shown in many studies to have advantages for both space and terrestrial applications. The high heat rejection temperature minimizes radiator size and weight for high atmospheric and space applications. Mobile and stationary terrestrial applications take advantage of a cell temperature high enough to directly reform hydro-carbon fuels, achieving high efficiency and energy density. Government funded solid oxide fuel cell (SOFC) efforts are concentrated on the monolithic and tubular cell designs employing zirconia as the oxide ion conduction membrane. Zirconia requires an operating temperature of 1000 C to achieve adequate electrolyte conductivity. All-ceramic cell structures are used in both cases, leading to fragile, failure prone cells, and manufacturing steps which are difficult to scale up and costly. IFC's molten carbonate fuel cell development demonstrates the reliability of ductile sheet metal parts used for gas flow fields, separator plates, and frames in the 650 C temperature range. Ceria doped with gadolinium has ionic conductivity at 700 C comparable to zirconia at 1000 C. At 700 C a variety of stainless steels offer acceptable strength and oxidation resistance for use as cell hardware.

  10. Initial oxidation of pure and K doped NiTi shape memory alloys

    NASA Astrophysics Data System (ADS)

    Tollefsen, H.; Raaen, S.

    2009-06-01

    Initial oxidation of pure and K doped nitinol has been studied by photoelectron spectroscopy. The composition of the TiOx layer that forms on the surface is found to depend on the temperature during oxidation. The oxidation at high temperatures results in enhanced formation of lower oxides, whereas TiO2 predominates for oxidation at lower temperatures, e.g., 70 °C. Submonolayer coverage of K on NiTi enhances the formation of TiO2 on the expense of lower oxides, which is of consequence for formation of a protective oxide layer and biocompatibility. Oxidation in the martensitic phase was found to be independent of temperature for temperatures between -40 and 10 °C, whereas in the austenitic phase the oxide growth is thermally activated.

  11. Electrical and Optical Properties of Hydrogen Doped Aluminum-Doped Zinc Oxide Thin Films for Low Cost Applications.

    PubMed

    Park, Yong Seob; Park, Young; Kwon, Samyoung; Kim, Eung Kwon; Choi, Wonseok; Kim, Donguk; Kim, Minha; Lee, Jaehyeong

    2016-05-01

    Aluminum-doped zinc oxide (AZO) thin films were prepared on glass substrate using a magnetron sputtering system. In this work, a powder target was used as a source material for low cost applications, instead of a conventional sintered ceramic target. The effects of the hydrogen gas ratio on the electrical and optical properties of the AZO films. The hydrogen doped AZO (AZO:H) films had a hexagonal polycrystalline structure. A small amount of hydrogen gas deteriorated the electrical and optical properties of the AZO:H films. However, these properties improved, as the H2/(H2 + Ar) gas ratio increased. The AZO:H films grown at an H2/(H2+Ar) ratio of 10% showed good properties for low cost applications, such as a low resistivity of 1.35 x 10(-3) Ω-cm, high average transmittance of 83.1% in the visible range of light.

  12. Influences of indium doping and annealing on microstructure and optical properties of cadmium oxide thin films

    NASA Astrophysics Data System (ADS)

    Zhu, Yuankun; Lei, Pei; Zhu, Jiaqi; Han, Jiecai

    2016-04-01

    The influences of indium doping and subsequent annealing in nitrogen and air atmospheres on the microstructure and optical properties of cadmium oxide films were studied in detail with the aid of various characterizations. X-ray photoelectronic spectroscopy analysis shows that indium atom forms chemically oxidized bonds in Cd-O matrix. X-ray diffraction results demonstrate that CdO structure remains FCC structure with indium doping, whereas the preferential orientation transforms from (222) into (200) orientation. Indium doping prevents the large crystalline growth, and this role still works under both nitrogen and air annealing processes. Similarly, CdO films show rough surface under annealing conditions, but the force has been greatly weakened at high doping level. It is clear that refractive index and extinction coefficient are closely correlated with crystalline size for undoped films, whereas it turns to the doping level for doped films, which can be performed by the mechanism of indium atom substitution. This work provides a very useful guild for design and application of optical-electronic devices.

  13. Zirconium doped nano-dispersed oxides of Fe, Al and Zn for destruction of warfare agents

    SciTech Connect

    Stengl, Vaclav; Houskova, Vendula; Bakardjieva, Snejana; Murafa, Nataliya; Marikova, Monika; Oplustil, Frantisek; Nemec, Tomas

    2010-11-15

    Zirconium doped nano dispersive oxides of Fe, Al and Zn were prepared by a homogeneous hydrolysis of the respective sulfate salts with urea in aqueous solutions. Synthesized metal oxide hydroxides were characterized using Brunauer-Emmett-Teller (BET) surface area and Barrett-Joiner-Halenda porosity (BJH), X-ray diffraction (XRD), infrared spectroscopy (IR), scanning electron microscopy (SEM) and energy-dispersive X-ray microanalysis (EDX). These oxides were taken for an experimental evaluation of their reactivity with sulfur mustard (HD or bis(2-chloroethyl)sulfide), soman (GD or (3,3'-Dimethylbutan-2-yl)-methylphosphonofluoridate) and VX agent (S-[2-(diisopropylamino)ethyl]-O-ethyl-methylphosphonothionate). The presence of Zr{sup 4+} dopant can increase both the surface area and the surface hydroxylation of the resulting doped oxides, decreases their crystallites' sizes thereby it may contribute in enabling the substrate adsorption at the oxide surface thus it can accelerate the rate of degradation of warfare agents. Addition of Zr{sup 4+} converts the product of the reaction of ferric sulphate with urea from ferrihydrite to goethite. We found out that doped oxo-hydroxides Zr-FeO(OH) - being prepared by a homogeneous hydrolysis of ferric and zirconium oxo-sulfates mixture in aqueous solutions - exhibit a comparatively higher degradation activity towards chemical warfare agents (CWAs). Degradation of soman or VX agent on Zr-doped FeO(OH) containing ca. 8.3 wt.% of zirconium proceeded to completion within 30 min.

  14. Surface Charge Transfer Doping via Transition Metal Oxides for Efficient p-Type Doping of II-VI Nanostructures.

    PubMed

    Xia, Feifei; Shao, Zhibin; He, Yuanyuan; Wang, Rongbin; Wu, Xiaofeng; Jiang, Tianhao; Duhm, Steffen; Zhao, Jianwei; Lee, Shuit-Tong; Jie, Jiansheng

    2016-11-22

    Wide band gap II-VI nanostructures are important building blocks for new-generation electronic and optoelectronic devices. However, the difficulty of realizing p-type conductivity in these materials via conventional doping methods has severely handicapped the fabrication of p-n homojunctions and complementary circuits, which are the fundamental components for high-performance devices. Herein, by using first-principles density functional theory calculations, we demonstrated a simple yet efficient way to achieve controlled p-type doping on II-VI nanostructures via surface charge transfer doping (SCTD) using high work function transition metal oxides such as MoO3, WO3, CrO3, and V2O5 as dopants. Our calculations revealed that these oxides were capable of drawing electrons from II-VI nanostructures, leading to accumulation of positive charges (holes injection) in the II-VI nanostructures. As a result, Fermi levels of the II-VI nanostructures were shifted toward the valence band regions after surface modifications, along with the large enhancement of work functions. In situ ultraviolet photoelectron spectroscopy and X-ray photoelectron spectroscopy characterizations verified the significant interfacial charge transfer between II-VI nanostructures and surface dopants. Both theoretical calculations and electrical transfer measurements on the II-VI nanostructure-based field-effect transistors clearly showed the p-type conductivity of the nanostructures after surface modifications. Strikingly, II-VI nanowires could undergo semiconductor-to-metal transition by further increasing the SCTD level. SCTD offers the possibility to create a variety of electronic and optoelectronic devices from the II-VI nanostructures via realization of complementary doping.

  15. Nitrogen and carbon doped titanium oxide as an alternative and durable electrocatalyst support in polymer electrolyte fuel cells

    NASA Astrophysics Data System (ADS)

    Dhanasekaran, P.; Vinod Selvaganesh, S.; Bhat, Santoshkumar D.

    2016-02-01

    Nitrogen and carbon doped titanium oxide as an alternative and ultra-stable support to platinum catalysts is prepared and its efficiency is determined by polymer electrolyte fuel cell. Nitrogen and carbon doped titanium oxide is prepared by varying the melamine ratio followed by calcination at 900 °C. Platinum nanoparticles are deposited onto doped and undoped titanium oxide by colloidal method. The doping effect, surface morphology, chemical oxidation state and metal/metal oxide interfacial contact are studied by X-ray diffraction, Raman spectroscopy, high resolution transmission electron microscopy and X-ray photo electron spectroscopy. The nitrogen and carbon doping changes both electronic and structural properties of titanium oxide resulting in enhanced oxygen reduction reaction activity. The platinum deposited on optimum level of nitrogen and carbon doped titanium oxide exhibits improved cell performance in relation to platinum on titanium oxide electrocatalysts. The effect of metal loading on cathode electrocatalyst is investigated by steady-state cell polarization. Accelerated durability test over 50,000 cycles for these electrocatalysts suggested the improved interaction between platinum and nitrogen and carbon doped titanium oxide, retaining the electrochemical surface area and oxygen reduction performance as comparable to platinum on carbon support.

  16. Doping-induced spectral shifts in two-dimensional metal oxides

    NASA Astrophysics Data System (ADS)

    Ylvisaker, E. R.; Pickett, W. E.

    2013-03-01

    Doping of strongly layered ionic oxides is an established paradigm for creating novel electronic behavior. This is nowhere more apparent than in superconductivity, where doping gives rise to high-temperature superconductivity in cuprates (hole doped) and to surprisingly high Tc in HfNCl (Tc = 25.5 K, electron doped). First-principles calculations of hole doping of the layered delafossite CuAlO2 reveal unexpectedly large doping-induced shifts in spectral density, strongly in opposition to the rigid-band picture that is widely used as an accepted guideline. These spectral shifts, of similar origin as the charge transfer used to produce negative electron affinity surfaces and adjust Schottky barrier heights, drastically alter the character of the Fermi level carriers, leading in this material to an O-Cu-O molecule-based carrier (or polaron, at low doping) rather than a nearly pure-Cu hole as in a rigid-band picture. First-principles linear response electron-phonon coupling (EPC) calculations reveal, as a consequence, net weak EPC and no superconductivity rather than the high Tc obtained previously using rigid-band expectations. These specifically two-dimensional dipole-layer-driven spectral shifts provide new insights into materials design in layered materials for functionalities besides superconductivity.

  17. Preparation of metal oxide doped ACNFs and their adsorption performance for low concentration SO2

    NASA Astrophysics Data System (ADS)

    Yu, Hong-quan; Wu, Yan-bo; Song, Tie-ben; Li, Yue; Shen, Yu

    2013-11-01

    Metal oxide (TiO2 or Co3O4) doped activated carbon nanofibers (ACNFs) were prepared by electrospinning. These nanofibers were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and Brunner-Emmett-Teller method (BET). The results show that the average diameters of ACNFs were within the range of 200-500 nm, and the lengths were several tens of micrometers. The specific surface areas were 1146.7 m2/g for TiO2-doped ACNFs and 1238.5 m2/g for Co3O4-doped ACNFs, respectively. The electrospun nanofibers were used for adsorption of low concentration sulfur dioxide (SO2). The results showed that the adsorption rates of these ACNFs increased with an increase in SO2 concentration. When the SO2 concentration was 1.0 μg/mL, the adsorption rates of TiO2-doped ACNFs and Co3O4-doped ACNFs were 66.2% and 67.1%, respectively. The adsorption rate also increased as the adsorption time increased. When the adsorption time was 40 min, the adsorption rates were 67.6% and 69.0% for TiO2-doped ACNFs and Co3O4-doped ACNFs, respectively. The adsorption rate decreased as the adsorption temperature increased below 60°C, while it increased as the adsorption temperature increased to more than 60°C.

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

    PubMed

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

    2016-02-10

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

  19. Thermoelectric properties of the yttrium-doped ceramic oxide SrTiO3

    NASA Astrophysics Data System (ADS)

    Khan, Tamal Tahsin; Ur, Soon-Chul

    2017-01-01

    The doping dependence of the thermoelectric figure of merit, ZT, of the ceramic oxide SrTiO3 at high temperature has been studied. In this study, yttrium was used as the doping element. A conventional solid-state reaction method was used for the preparation of Y-doped SrTiO3. The doping level in SrTiO3 was controlled to be in the doping range of 2 - 10 mole%. Almost all the yttrium atoms incorporated into the SrTiO3 provided charge carriers, as was observed by using X-ray diffraction pattern. The relative densities of all the samples varied from 98.53% to 99.45%. The thermoelectric properties, including the electrical conductivity σ, Seebeck coefficient S, thermal conductivity k, and the figure of merit, ZT, were investigated at medium temperatures. The ZT value showed an obvious doping level dependence, in which a value as high as 0.18 is realized at 773 K for a doping of 8 mole%.

  20. The microstructures and electrical properties of Y-doped amorphous vanadium oxide thin films

    NASA Astrophysics Data System (ADS)

    Gu, Deen; Zhou, Xin; Guo, Rui; Wang, Zhihui; Jiang, Yadong

    2017-03-01

    One of promising approaches for further improving the sensitivity of microbolometer arrays with greatly-reduced pixel size is using the thermal-sensitive materials with higher performance. In this paper, Y-doped vanadium oxide (VOx) thin films prepared by a reactively sputtering process exhibit enhanced performance for the microbolometer application compared with frequently-applied VOx thin films. Both undoped and Y-doped VOx thin films are amorphous due to the relatively low deposition temperature. Y-doped VOx thin films exhibit smoother surface morphology than VOx due to the restrained expansion of particles during depositions. Y-doping increases the temperature coefficient of resistivity by over 20% for the doping level of 1.30 at%. The change rate of resistivity, after aging for 72 h, of thin films was reduced from about 15% for undoped VOx to 2% due to the introduction of Y. Moreover, Y-doped VOx thin films have a low 1/f noise level as VOx ones. Y-doping provides an attractive approach for preparing VOx thermal-sensitive materials with enhanced performance for microbolometers.

  1. Synthesis and electrical properties of Cu-doped tin oxide nanowires

    SciTech Connect

    Johari, Anima; Sharma, Manish; Bhatnagar, M. C.

    2013-02-05

    We report on atmospheric pressure growth of Cu-doped Tin oxide nanowires by thermal evaporation method. Scanning-electron-microscopic analysis shows the growth of wire-like SnO{sub 2} nanostructures (diameter Almost-Equal-To 80 nm and length Almost-Equal-To 70 {mu}m) on gold catalyzed silicon substrate. The as-synthesized Cu-doped SnO{sub 2} nanowires show polycrystalline nature with tetragonal rutile structure. EDX analysis confirms that Cu ( Almost-Equal-To 0.7 at%) have been uniformly doped into SnO{sub 2} nanowires. Electrical measurement of Cu-doped SnO{sub 2} nanowires concludes their resistance of about 5 M{Omega} at room temperature.

  2. Reduced ceria nanofilms from structure prediction

    NASA Astrophysics Data System (ADS)

    Kozlov, Sergey M.; Demiroglu, Ilker; Neyman, Konstantin M.; Bromley, Stefan T.

    2015-02-01

    Experimentally, Ce2O3 films are used to study cerium oxide in its fully or partially reduced state, as present in many applications. We have explored the space of low energy Ce2O3 nanofilms using structure prediction and density functional calculations, yielding more than 30 distinct nanofilm structures. First, our results help to rationalize the roles of thermodynamics and kinetics in the preparation of reduced ceria nanofilms with different bulk crystalline structures (e.g. A-type or bixbyite) depending on the support used. Second, we predict a novel, as yet experimentally unresolved, nanofilm which has a structure that does not correspond to any previously reported bulk A2B3 phase and which has an energetic stability between that of A-type and bixbyite. To assist identification and fabrication of this new Ce2O3 nanofilm we calculate some observable properties and propose supports for its epitaxial growth.Experimentally, Ce2O3 films are used to study cerium oxide in its fully or partially reduced state, as present in many applications. We have explored the space of low energy Ce2O3 nanofilms using structure prediction and density functional calculations, yielding more than 30 distinct nanofilm structures. First, our results help to rationalize the roles of thermodynamics and kinetics in the preparation of reduced ceria nanofilms with different bulk crystalline structures (e.g. A-type or bixbyite) depending on the support used. Second, we predict a novel, as yet experimentally unresolved, nanofilm which has a structure that does not correspond to any previously reported bulk A2B3 phase and which has an energetic stability between that of A-type and bixbyite. To assist identification and fabrication of this new Ce2O3 nanofilm we calculate some observable properties and propose supports for its epitaxial growth. Electronic supplementary information (ESI) available: Graph of IP versus DFT relative energies for nanofilms, GGA + U calculated lattice parameters and

  3. Influence of the metal precursor on the catalytic behavior of Pt/ceria catalysts in the preferential oxidation of CO in the presence of H₂ (PROX).

    PubMed

    Jardim, Erika O; Rico-Francés, Soledad; Coloma, Fernando; Anderson, James A; Silvestre-Albero, Joaquín; Sepúlveda-Escribano, Antonio

    2015-04-01

    The effect of the metal precursor (presence or absence of chlorine) on the preferential oxidation of CO in the presence of H2 over Pt/CeO2 catalysts has been studied. The catalysts are prepared using (Pt(NH3)4)(NO3)2 and H2PtCl6, as precursors, in order to ascertain the effect of the chlorine species on the chemical properties of the support and on the catalytic behavior of these systems in the PROX reaction. The results show that chloride species exert an important effect on the redox properties of the oxide support due to surface chlorination. Consequently, the chlorinated catalyst exhibits a poorer catalytic activity at low temperatures compared with the chlorine-free catalyst, and this is accompanied by a higher selectivity to CO2 even at high reaction temperatures. It is proposed that the CO oxidation mechanism follows different pathways on each catalyst.

  4. Sulfur-doped graphene via thermal exfoliation of graphite oxide in H2S, SO2, or CS2 gas.

    PubMed

    Poh, Hwee Ling; Šimek, Petr; Sofer, Zdeněk; Pumera, Martin

    2013-06-25

    Doping of graphene with heteroatoms is an effective way to tailor its properties. Here we describe a simple and scalable method of doping graphene lattice with sulfur atoms during the thermal exfoliation process of graphite oxides. The graphite oxides were first prepared by Staudenmaier, Hofmann, and Hummers methods followed by treatments in hydrogen sulfide, sulfur dioxide, or carbon disulfide. The doped materials were characterized by scanning electron microscopy, high-resolution X-ray photoelectron spectroscopy, combustible elemental analysis, and Raman spectroscopy. The ζ-potential and conductivity of sulfur-doped graphenes were also investigated in this paper. It was found that the level of doping is more dramatically influenced by the type of graphite oxide used rather than the type of sulfur-containing gas used during exfoliation. Resulting sulfur-doped graphenes act as metal-free electrocatalysts for an oxygen reduction reaction.

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

    SciTech Connect

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

    2016-03-22

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

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

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

    PubMed

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

    2015-01-21

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

  8. Microstructure, toughness and flexural strength of self-reinforced silicon nitride ceramics doped with yttrium oxide and ytterbium oxide.

    PubMed

    Zheng, Y. S.; Knowles, K. M.; Vieira, J. M.; Lopes, A. B.; Oliveira, F. J.

    2001-02-01

    Self-reinforced silicon nitride ceramics with additions of either yttrium oxide or ytterbium oxide have been investigated at room temperature after various processing heat treatments. Devitrification of the intergranular phase in these materials is very sensitive to the heat treatment used during processing and does not necessarily improve their strength and toughness. Hot-pressed ceramics without a subsequent devitrification heat treatment were the strongest. The ytterbium oxide-doped silicon nitride ceramics were consistently tougher, but less strong, than the yttrium oxide-doped silicon nitride ceramics. In all the ceramics examined, the fracture toughness showed evidence for R-curve behaviour. This was most significant in pressureless sintered ytterbium oxide-doped silicon nitride ceramics. A number of toughening mechanisms, including crack deflection, bridging, and fibre-like grain pull-out, were observed during microstructural analysis of the ceramics. In common with other silicon nitride-based ceramics, thin amorphous films were found at the grain boundaries in each of the ceramics examined. Arrays of dislocations left in the elongated silicon nitride grains after processing were found to belong to the {101;0}<0001> primary slip system.

  9. Reduced graphene oxide decorated with Fe doped SnO2 nanoparticles for humidity sensor

    NASA Astrophysics Data System (ADS)

    Toloman, D.; Popa, A.; Stan, M.; Socaci, C.; Biris, A. R.; Katona, G.; Tudorache, F.; Petrila, I.; Iacomi, F.

    2017-04-01

    Reduced graphene oxide (rGO) decorated with Fe doped SnO2 nanoparticles were fabricated via the electrostatic interaction between positively charged modified Fe-doped SnO2 oxide and negatively charged graphene oxide (GO) in the presence of poly(allylamine) hydrochloride (PAH). The decoration of rGO layers with SnO2:Fe nanoparticles was highlited by TEM microsopy. For composite sample the diffraction patterns coincide well with those of SnO2:Fe nanoparticles. The reduction of graphene oxide was evidenced using XRD and FT-IR spectroscopy. The formation of SnO2:Fe-PAH-graphene composites was confirmed by FT-IR, Raman and EPR spectroscopy. Sensitivity tests for relative humidity (RH) measurements were carried out at five different concentrations of humid air at room temperature. The prepared composite sensor exhibited a higher sensing response as compared with Fe:SnO2 nanoparticles.

  10. Effect of Gadolinium Doping on the Air Oxidation of Uranium Dioxide

    SciTech Connect

    Scheele, Randall D.; Hanson, Brady D.; Cumblidge, Stephen E.; Jenson, Evan D.; Kozelisky, Anne E.; Sell, Rachel L.; MacFarlan, Paul J.; Snow, Lanee A.

    2004-12-04

    Researchers at the Pacific Northwest National Laboratory (PNNL) investigated the effects of gadolinia concentration on the air oxidization of gadolinia-doped uranium dioxide using thermogravimetry and differential scanning calorimetry to determine if such doping could improve uranium dioxide's stability as a nuclear fuel during potential accident scenarios in a nuclear reactor or during long-term disposal. We undertook this study to determine whether the resistance of the uranium dioxide to oxidation to the orthorhombic U3O8 with its attendant crystal expansion could be prevented by addition of gadolinia. Our studies found that gadolinium has little effect on the thermal initiation of the first step of the reported two-step air oxidation of UO2; however, increasing gadolinia content does stabilize the initial tetragonal or cubic product allowing significant oxidation before the second expansive step to U3O8 begins.

  11. 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.

  12. Nonaqueous synthesis of metal oxide nanoparticles: Short review and doped titanium dioxide as case study for the preparation of transition metal-doped oxide nanoparticles

    SciTech Connect

    Djerdj, Igor Arcon, Denis; Jaglicic, Zvonko; Niederberger, Markus

    2008-07-15

    The liquid-phase synthesis of metal oxide nanoparticles in organic solvents under exclusion of water is nowadays a well-established alternative to aqueous sol-gel chemistry. In this article, we highlight some of the advantages of these routes based on selected examples. The first part reviews some recent developments in the synthesis of ternary metal oxide nanoparticles by surfactant-free nonaqueous sol-gel routes, followed by the discussion of the morphology-controlled synthesis of lanthanum hydroxide nanoparticles, and the presentation of structural peculiarities of manganese oxide nanoparticles with an ordered Mn vacancy superstructure. These examples show that nonaqueous systems, on the one hand, allow the preparation of compositionally complex oxides, and, on the other hand, make use of the organic components (initially present or formed in situ) in the reaction mixture to tailor the morphology. Furthermore, obviously even the crystal structure can differ from the corresponding bulk material like in the case of MnO nanoparticles. In the second part of the paper we present original results regarding the synthesis of dilute magnetic semiconductor TiO{sub 2} nanoparticles doped with cobalt and iron. The structural characterization as well as the magnetic properties with special attention to the doping efficiency is discussed. - Graphical abstract: In the first part of this article, nonaqueous sol-gel routes to ternary metal oxide nanoparticles are briefly reviewed, followed by the discussion of the morphology-controlled synthesis of lanthanum hydroxide nanoparticles, and the appearance of an unprecedented superstructure in MnO nanoparticles. In the second part, doping experiments of TiO{sub 2} with Fe and Co are presented, along with their characterization including magnetic measurements.

  13. Structural studies of lead lithium borate glasses doped with silver oxide.

    PubMed

    Coelho, João; Freire, Cristina; Hussain, N Sooraj

    2012-02-01

    Silver oxide doped lead lithium borate (LLB) glasses have been prepared and characterized. Structural and composition characterization were accessed by XRD, FTIR, Raman, SEM and EDS. Results from FTIR and Raman spectra indicate that Ag(2)O acts as a network modifier even at small quantities by converting three coordinated to four coordinated boron atoms. Other physical properties, such as density, molar volume and optical basicity are also evaluated. Furthermore, they are also affected by the silver oxide composition.

  14. Atomic Layer-Deposited Titanium-Doped Vanadium Oxide Thin Films and Their Thermistor Applications

    NASA Astrophysics Data System (ADS)

    Wang, Shuyu; Yu, Shifeng; Lu, Ming; Liu, Mingzhao; Zuo, Lei

    2017-04-01

    Here we report the enhancement in the temperature coefficient of resistance (TCR) of atomic layer-deposited vanadium oxide thin films through the doping of titanium oxide. The Hall effect measurement provides a potential explanation for the phenomenon. The composition and morphology of the thin films are investigated by x-ray diffraction and scanning electron microscopy techniques. The high TCR, good uniformity, and low processing temperature of the material make it a good candidate for thermistor application.

  15. Effect of preparation conditions on physic-chemical properties of tin-doped nanocrystalline indium oxide

    NASA Astrophysics Data System (ADS)

    Malinovskaya, T. D.; Sachkov, V. I.; Zhek, V. V.; Nefedov, R. A.

    2016-01-01

    In this paper the results of investigation of phase formation and change of concentration of free electrons (Ne) in indium tin oxide system during heat treatment of coprecipitated hydroxides of indium and tin from nitric and hydrochloric solutions and also, for comparison melts of salts nitrates by an alkaline reactant (NH4OH) are considered.The performed investigation allowed to set the optimal condition of preparation of polycrystalline tin-doped indium oxide with maximal electron concentration.

  16. Effects of Doping on Thermal Conductivity of Pyrochlore Oxides for Advanced Thermal Barrier Coatings

    NASA Technical Reports Server (NTRS)

    Bansal, Narottam P.; Zhu, Dongming; Eslamloo-Grami, Maryam

    2006-01-01

    Pyrochlore oxides of general composition, A2B2O7, where A is a 3(+) cation (La to Lu) and B is a 4(+) cation (Zr, Hf, Ti, etc.) have high melting point, relatively high coefficient of thermal expansion, and low thermal conductivity which make them suitable for applications as high-temperature thermal barrier coatings. The effect of doping at the A site on the thermal conductivity of a pyrochlore oxide La2Zr2O7, has been investigated. Oxide powders of various compositions La2Zr2O7, La(1.7)Gd(0.3)Zr2O7, La(1.7)Yb(0.3)Zr2O7 and La(1.7)Gd(0.15)Yb(0.15)Zr2O7 were synthesized by the citric acid sol-gel method. These powders were hot pressed into discs and used for thermal conductivity measurements using a steady-state laser heat flux test technique. The rare earth oxide doped pyrochlores La(1.7)Gd(0.3)Zr2O7, La(1.7)Yb(0.3)Zr2O7 and La(1.7)Gd(0.15)Yb(0.15)Zr2O7 had lower thermal conductivity than the un-doped La2Zr2O7. The Gd2O3 and Yb2O3 co-doped composition showed the lowest thermal conductivity.

  17. Transfer hydrogenation over sodium-modified ceria: Enrichment of redox sites active for alcohol dehydrogenation

    DOE PAGES

    Nelson, Nicholas C.; Boote, Brett W.; Naik, Pranjali; ...

    2017-01-17

    Ceria (CeO2) and sodium-modified ceria (Ce-Na) were prepared through combustion synthesis. Palladium was deposited onto the supports (Pd/CeO2 and Pd/Ce-Na) and their activity for the aqueous-phase transfer hydrogenation of phenol using 2-propanol under liquid flow conditions was studied. Pd/Ce-Na showed a marked increase (6×) in transfer hydrogenation activity over Pd/CeO2. Material characterization indicated that water-stable sodium species were not doped into the ceria lattice, but rather existed as subsurface carbonates. Modification of ceria by sodium provided more adsorption and redox active sites (i.e. defects) for 2-propanol dehydrogenation. This effect was an intrinsic property of the Ce-Na support and independent ofmore » Pd. The redox sites active for 2-propanol dehydrogenation were thermodynamically equivalent on both supports/catalysts. At high phenol concentrations, the reaction was limited by 2-propanol adsorption. Furthermore, the difference in catalytic activity was attributed to the different numbers of 2-propanol adsorption and redox active sites on each catalyst.« less

  18. Effect of W and WC on the oxidation resistance of yttria-doped silicon nitride

    NASA Technical Reports Server (NTRS)

    Schuon, S.

    1980-01-01

    The effect of tungsten and tungsten carbide contamination on the oxidation and cracking in air of yttria-doped silicon nitride ceramics is investigated. Silicon nitride powder containing 8 wt % Y2O3 was doped with 2 wt % W, 4 wt % W, 2 wt % WC or left undoped, and sintered in order to simulate contamination during milling, and specimens were exposed in air to 500, 750 and 1350 C for various lengths of time. Scanning electron and optical microscopy and X-ray diffraction of the specimens in the as-sintered state reveals that the addition of W or WC does not affect the phase relationships in the system, composed of alpha and beta Si3N4, melilite and an amorphous phase. Catastrophic oxidation is observed at 750 C in specimens containing 2 and 4 wt % W, accompanied by the disappearance of alpha Si3N4 and melilite from the structure. At 1350 C, the formation of a protective glassy oxide layer was observed on all specimens without catastrophic oxidation, and it is found that pre-oxidation at 1350 C also improved the oxidation resistance at 750 C of bars doped with 4 wt % W. It is suggested that tungsten contamination from WC grinding balls may be the major cause of the intermediate-temperature cracking and instability frequently observed in Si3N4-8Y2O3.

  19. Subwavelength structure for sound absorption from graphene oxide-doped polyvinylpyrrolidone nanofibers

    NASA Astrophysics Data System (ADS)

    Qamoshi, Khadijeh; Rasuli, Reza

    2016-09-01

    We study the sound absorption of the reinforced polyvinylpyrrolidone nanofibers with graphene oxide. It is shown that reinforced nanofibers can acquire impedance-matched surface to airborne sound at special frequencies. To obtain such surface, nanofibers were spun with polyvinylpyrrolidone polymer that was doped by graphene oxide with concentrations of 0, 6 and 12 wt%. It was found that fibers without graphene oxide were spun continuously and randomly, whereas by doping with graphene oxide, the mode of fibers is changed and some nodes form on the fibers coating. The sound absorption coefficient was measured by an impedance tube based on 105341-1 ISO standard. Measurements in the frequency range from 700 to 1600 Hz show that use of graphene oxide as a reinforcing phase increases sound absorption coefficient of the samples at a frequency ~1500 Hz up to ~40 %. Angular eigenfrequency and dissipation coefficient of the samples were obtained by impedance measurement for the prepared samples. Results show that doping the polymer with graphene oxide causes an increase in the angular eigenfrequency and the dissipation coefficient.

  20. Magnesium-doped zinc oxide nanorod-nanotube semiconductor/p-silicon heterojunction diodes

    NASA Astrophysics Data System (ADS)

    Caglar, Yasemin; Görgün, Kamuran; Ilican, Saliha; Caglar, Mujdat; Yakuphanoğlu, Fahrettin

    2016-08-01

    Nanostructured zinc oxide material is usable in electronic device applications such as light-emitting diodes, heterojunction diode, sensors, solar cell due to its interesting electrical conductivity and optical properties. Magnesium-doped zinc oxide nanorod (NR)-nanotube (NT) films were grown by microwave-assisted chemical bath deposition to fabricate ZnO-based heterojunction diode. It is found that ZnO hexagonal nanorods turn into hexagonal nanotubes when the Mg doping ratio is increased from 1 to 10 %. The values of the optical band gap for 1 % Mg-doped ZnO NR and 10 % Mg-doped ZnO NT films are found to be 3.14 and 3.22 eV, respectively. The n-ZnO:Mg/p-Si heterojunction diodes were fabricated. The diodes exhibited a rectification behavior with ideality factor higher than unity due to the presence of surface states in the junction and series resistance. The obtained results indicate that Mg doping improves the electrical and optical properties of ZnO.

  1. Ceria-based nanocomposites for the enrichment and identification of phosphopeptides.

    PubMed

    Fatima, Batool; Najam-ul-Haq, Muhammad; Jabeen, Fahmida; Majeed, Saadat; Ashiq, Muhammad N; Musharraf, S Ghulam; Shad, Muhammad A; Xu, Guobao

    2013-09-07

    Nanocomposites are given preference over the individual materials due to the combined properties of the components involved. Ceria has a high efficiency in phosphopeptide enrichment as well as in dephosphorylation. Iron oxide and tin oxide are chosen as counter metal oxides to synthesize the ceria nanocomposites using a co-precipitation method. The nanocomposites are characterized by Fourier-transform infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM). Tryptic β-casein digest shows the feasibility of phosphopeptide enrichment by the two nanocomposites. Selectivity studies show their performance in comparison to ceria. Being more selective in the extended mass range, both nanocomposites are applied to spiked human serum and non-fat milk digest. The ceria nanocomposites are also capable of being used as material-enhanced laser desorption/ionization (MELDI) carrier/affinity materials for real biological samples with varying degrees of complexity. The enriched content is analyzed by MALDI-TOF MS. All the phosphopeptides in all variants of casein are identified. The sequence coverage of caseins is also interpreted. Nanocomposites thus offer a high selectivity and sensitivity, which make them promising materials for biomarker discoveries and the identification of phosphorylation pathways for new post translational modifications (PTMs).

  2. Effects of Mn Doping on Zinc Oxide Films Prepared by Spray Pyrolysis Technique

    NASA Astrophysics Data System (ADS)

    Singh, Bhavana; Shrivastava, S. B.; Ganesan, V.

    The work deals with the preparation of Zinc Oxide (ZnO) thin films on microscopic glass substrate by spray pyrolysis technique. The systematic study on the influence of Mn doping up to 15% has been performed. The structural studies revealed that pure and doped film has hexagonal structure. In order to reduce the internal strain due to Mn doping, the crystallite size decreases. The atomic force microscopy (AFM) measurement shows the decrease in grain size and roughness with doping. The resistivity curve shows a clear hump corresponding to smaller Mn doping (x=0.5-4%) around T˜340-365 K. This hump was found to reduce with the increase in Mn concentration and for x≥7.5, beyond which it vanishes completely. This is attributed to critical behavior of resistivity and may be due to the scattering of carriers by magnetic spin fluctuation via exchange interaction. The optical measurement shows the shift in absorption edge of Mn doped ZnO films toward the longer wavelength side. This correlates the reduction in grain size as a function of Mn concentration. The optical bandgap goes down, whereas refractive index increases with dopant concentration.

  3. Facile synthesis of antimony-doped tin oxide nanoparticles by a polymer-pyrolysis method

    SciTech Connect

    Li, Yuan-Qing; Wang, Jian-Lei; Fu, Shao-Yun; Mei, Shi-Gang; Zhang, Jian-Min; Yong, Kang

    2010-06-15

    In this article, antimony-doped tin oxide (ATO) nanoparticles was synthesized by a facile polymer-pyrolysis method. The pyrolysis behaviors of the polymer precursors prepared via in situ polymerization of metal salts and acrylic acid were analyzed by simultaneous thermogravimetric and differential scanning calorimetry (TG-DSC). The structural and morphological characteristics of the products were studied by powder X-ray diffraction (XRD) and transmission electron microscope (TEM). The results reveal that the ATO nanoparticles calcined at 600 {sup o}C show good crystallinity with the cassiterite structure and cubic-spherical like morphology. The average particle size of ATO decreases from 200 to 15 nm as the Sb doping content increases from 5 mol% to 15 mol%. Electrical resistivity measurement shows that the resistivity for the 10-13 mol% Sb-doped SnO{sub 2} nanoparticles is reduced by more than three orders compared with the pure SnO{sub 2} nanoparticles. In addition, due to its versatility this polymer-pyrolysis method can be extended to facile synthesis of other doped n-type semiconductor, such as In, Ga, Al doped ZnO, Sn doped In{sub 2}O{sub 3}.

  4. Low-temperature photochromic response of phosphorus-doped bismuth silicon oxide

    NASA Astrophysics Data System (ADS)

    McCullough, J. S.; Harmon, Angela; Martin, J. J.; Martin, J. J.; Harris, M. T.; Larkin, J. J.

    1995-08-01

    Phosphorus is one of several dopants that electronically compensate the native deep donor responsible for the yellow coloration observed in bismuth silicon oxide (BSO). Low-temperature optical absorption measurements of a series of Czochralski-grown P-doped BSO crystals show that ˜0.1-0.15 at. % P is needed in the sample to fully remove the yellow coloration. The absorption cutoff in the fully compensated P-doped sample was at 3.2 eV while compensated Al- and Ga-doped samples cutoff at 3.35 eV. Excitation at 10-15 K with near band-edge light produces photochromic absorption bands. In the lightly-doped (partially bleached) samples these bands were identical to those observed in undoped BSO. In the fully bleached sample a new spectrum was observed. Its major contribution was a band centered near 1.8 eV with a weaker absorption in the blue-green. By comparison with the spectra observed in undoped and in Al-doped material before and after photoexcitation it is believed that the 1.8 eV band is due to the [PO4]- center and that the broad 2.45 eV band observed in Al- and Ga-doped BSO is due to the [BiO4]0 center.

  5. Chromium and Ruthenium-Doped Zinc Oxide Thin Films for Propane Sensing Applications

    PubMed Central

    Gómez-Pozos, Heberto; González-Vidal, José Luis; Torres, Gonzalo Alberto; Rodríguez-Baez, Jorge; Maldonado, Arturo; de la Luz Olvera, María; Acosta, Dwight Roberto; Avendaño-Alejo, Maximino; Castañeda, Luis

    2013-01-01

    Chromium and ruthenium-doped zinc oxide (ZnO:Cr) and (ZnO:Ru) thin solid films were deposited on soda-lime glass substrates by the sol-gel dip-coating method. A 0.6 M solution of zinc acetate dihydrate dissolved in 2-methoxyethanol and monoethanolamine was used as basic solution. Chromium (III) acetylacetonate and Ruthenium (III) trichloride were used as doping sources. The Ru incorporation and its distribution profile into the films were proved by the SIMS technique. The morphology and structure of the films were studied by SEM microscopy and X-ray diffraction measurements, respectively. The SEM images show porous surfaces covered by small grains with different grain size, depending on the doping element, and the immersions number into the doping solutions. The sensing properties of ZnO:Cr and ZnO:Ru films in a propane (C3H8) atmosphere, as a function of the immersions number in the doping solution, have been studied in the present work. The highest sensitivity values were obtained for films doped from five immersions, 5.8 and 900, for ZnO:Cr and ZnO:Ru films, respectively. In order to evidence the catalytic effect of the chromium (Cr) and ruthenium (Ru), the sensing characteristics of undoped ZnO films are reported as well. PMID:23482091

  6. In-situ loading ultrafine AuPd particles on ceria: highly active catalyst for solvent-free selective oxidation of benzyl alcohol.

    PubMed

    Zhang, Hongye; Xie, Yun; Sun, Zhenyu; Tao, Ranting; Huang, Changliang; Zhao, Yanfei; Liu, Zhimin

    2011-02-01

    Ce(III) oxide was synthesized under the protection of nitrogen gas, which had strong ability to reduce noble metal ions (e.g., Au, Pd ions) into metallic forms under oxygen-free conditions. On the basis of the surface redox reaction between the Ce(III) oxide support and noble metal ions, an effective and novel approach was presented to prepare noble metal/CeO(2) nanocatalysts, and a series of AuPd/CeO(2) nanocomposites with different Au:Pd molar ratios and metal loadings were obtained in the absence of any extra reducing and protective agents. The resultant composites were characterized by different techniques including X-ray diffraction, transmission electron microspectroscopy, X-ray photoelectron microspectroscopy, and ICP-AES analysis. It was demonstrated that in the AuPd/CeO(2) composites the content of Ce(III) reached about 30%, and the AuPd bimetallic particles with average size of 2.6 or 3.3 nm and narrow size distribution were uniformly distributed on the CeO(2) nanorods. The AuPd/CeO(2) composites were found to be excellent heterogeneous nanocatalysts for the selective oxidation of benzyl alcohol under solvent-free conditions. It was shown that all the AuPd/CeO(2) catalysts exhibited good selectivity toward benzaldehyde; especially, the catalyst with Au:Pd = 1:5 and metal loading of 1.2 wt % displayed extremely high activity with a TOF = 30.1 s(-1) at 160 °C.

  7. Boron-doped cadmium oxide composite structures and their electrochemical measurements

    SciTech Connect

    Lokhande, B.J.; Ambare, R.C.; Mane, R.S.; Bharadwaj, S.R.

    2013-08-01

    Graphical abstract: Conducting nano-fibrous 3% boron doped cadmium oxide thin films were prepared by SILAR and its super capacitive properties were studied. - Highlights: • Samples are of nanofibrous nature. • All samples shows pseudocapacitive behavior. • 3% B doped CdO shows good specific capacitance. • 3% B doped CdO shows maximum 74.93% efficiency at 14 mA/cm{sup 2}. • 3% B doped CdO shows 0.8 Ω internal resistance. - Abstract: Boron-doped and undoped cadmium oxide composite nanostructures in thin film form were prepared onto stainless steel substrates by a successive ionic layer adsorption and reaction method using aqueous solutions of cadmium nitrate, boric acid and 1% H{sub 2}O{sub 2}. As-deposited films were annealed at 623 K for 1 h. The X-ray diffraction study shows crystalline behavior for both doped and undoped films with a porous topography and nano-wires type architecture, as observed in SEM image. Wettability test confirms the hydrophilic surface with 58° contact angle value. Estimated band gap energy is around 1.9 eV. Electrochemical behavior of the deposited films is attempted in 1 M KOH electrolyte using cyclic voltammetry (CV), electrochemical impedance spectroscopy and galvanostatic charge–discharge tests. Maximum values of the specific capacitance, specific energy and specific power obtained for 3% B doped CdO film at 2 mV/s scan rate are 20.05 F/g, 1.22 Wh/kg and 3.25 kW/kg, respectively.

  8. Method of forming supported doped palladium containing oxidation catalysts

    SciTech Connect

    Mohajeri, Nahid

    2014-04-22

    A method of forming a supported oxidation catalyst includes providing a support comprising a metal oxide or a metal salt, and depositing first palladium compound particles and second precious metal group (PMG) metal particles on the support while in a liquid phase including at least one solvent to form mixed metal comprising particles on the support. The PMG metal is not palladium. The mixed metal particles on the support are separated from the liquid phase to provide the supported oxidation catalyst.

  9. Detection of Aeromonas hydrophila DNA oligonucleotide sequence using a biosensor design based on Ceria nanoparticles decorated reduced graphene oxide and Fast Fourier transform square wave voltammetry.

    PubMed

    Jafari, Safiye; Faridbod, Farnoush; Norouzi, Parviz; Dezfuli, Amin Shiralizadeh; Ajloo, Davood; Mohammadipanah, Fatemeh; Ganjali, Mohammad Reza

    2015-10-01

    A new strategy was introduced for ssDNA immobilization on a modified glassy carbon electrode. The electrode surface was modified using polyaniline and chemically reduced graphene oxide decorated cerium oxide nanoparticles (CeO2NPs-RGO). A single-stranded DNA (ssDNA) probe was immobilized on the modified electrode surface. Fast Fourier transform square wave voltammetry (FFT-SWV) was applied as detection technique and [Ru(bpy)3](2+/3+) redox signal was used as electrochemical marker. The hybridization of ssDNA with its complementary target caused a dramatic decrease in [Ru(bpy)3](2+/3+) FFT-SW signal. The proposed electrochemical biosensor was able to detect Aeromonas hydrophila DNA oligonucleotide sequence encoding aerolysin protein. Under optimal conditions, the biosensor showed excellent selectivity toward complementary sequence in comparison with noncomplementary and two-base mismatch sequences. The dynamic linear range of this electrochemical DNA biosensor for detecting 20-mer oligonucleotide sequence of A. hydrophila was from 1 × 10(-15) to 1 × 10(-8) mol L(-1). The proposed biosensor was successfully applied for the detection of DNA extracted from A. hydrophila in fish pond water up to 0.01 μg mL(-1) with RSD of 5%. Besides, molecular docking was applied to consider the [Ru(bpy)3](2+/3+) interaction with ssDNA before and after hybridization.

  10. Phosphorus-Doped Graphene Oxide Layer as a Highly Efficient Flame Retardant.

    PubMed

    Some, Surajit; Shackery, Iman; Kim, Sun Jun; Jun, Seong Chan

    2015-10-26

    A simple and easy process has been developed to efficiently dope phosphorus into a graphene oxide surface. Phosphorus-doped graphene oxide (PGO) is prepared by the treatment of polyphosphoric acid with phosphoric acid followed by addition of a graphene oxide solution while maintaining a pH of around 5 by addition of NaOH solution. The resulting materials are characterized by X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), Raman spectroscopy, thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). The as-made PGO solution-coated cloth exhibits excellent flame retardation properties. The PGO-coated cloth emits some smoke at the beginning without catching fire for more than 120 s and maintains its initial shape with little shrinkage. In contrast, the pristine cloth catches fire within 5 s and is completely burned within 25 s, leaving trace amounts of black residue. The simple technique of direct introduction of phosphorus into the graphene oxide surface to produce phosphorus-doped oxidized carbon nanoplatelets may be a general approach towards the low-cost mass production of PGO for many practical applications, including flame retardation.

  11. Cu4 Cluster Doped Monolayer MoS2 for CO Oxidation

    PubMed Central

    Chen, Z. W.; Yan, J. M.; Zheng, W. T.; Jiang, Q.

    2015-01-01

    The catalytic oxidation of CO molecule on a thermodynamically stable Cu4 cluster doped MoS2 monolayer is investigated by density functional theory (DFT) where the reaction proceeds in a new formation order of COOOCO* (O2* + 2CO* → COOOCO*), OCO* (COOOCO* → CO2 + OCO*), and CO2 (OCO* → CO2) desorption with the corresponding reaction barrier values of 0.220 eV, 0.370 eV and 0.119 eV, respectively. Therein, the rate-determining step is the second one. This low barrier indicates high activity of this system where CO oxidation could be realized at room temperature (even lower). As a result, the Cu4 doped MoS2 could be a candidate for CO oxidation with lower cost and higher activity without poisoning and corrosion problems. PMID:26052674

  12. Cu4 Cluster Doped Monolayer MoS2 for CO Oxidation

    NASA Astrophysics Data System (ADS)

    Chen, Z. W.; Yan, J. M.; Zheng, W. T.; Jiang, Q.

    2015-06-01

    The catalytic oxidation of CO molecule on a thermodynamically stable Cu4 cluster doped MoS2 monolayer is investigated by density functional theory (DFT) where the reaction proceeds in a new formation order of COOOCO* (O2* + 2CO* → COOOCO*), OCO* (COOOCO* → CO2 + OCO*), and CO2 (OCO* → CO2) desorption with the corresponding reaction barrier values of 0.220 eV, 0.370 eV and 0.119 eV, respectively. Therein, the rate-determining step is the second one. This low barrier indicates high activity of this system where CO oxidation could be realized at room temperature (even lower). As a result, the Cu4 doped MoS2 could be a candidate for CO oxidation with lower cost and higher activity without poisoning and corrosion problems.

  13. Oxidative Recession, Sulfur Release, and Al203 Spallation for Y-Doped Alloys

    NASA Technical Reports Server (NTRS)

    Smialek, James L.

    2001-01-01

    Second-order spallation phenomena have been noted for Y-doped Rene'N5 after long term oxidation at 1150 degrees C. The reason for this behavior has not been conclusively identified. A mass equivalence analysis has shown that the surface recession resulting from oxidation has the potential of releasing about 0.15 monolayer of sulfur for every 1 mg/sq cm of oxygen reacted for an alloy containing 5 ppmw of sulfur. This amount is significant in comparison to levels that have been shown to result in first-order spallation behavior for undoped alloys. Oxidative recession is therefore speculated to be a contributing source of sulfur and second-order spallation for Y-doped alloys.

  14. Alkaline earth metal doped tin oxide as a novel oxygen storage material

    SciTech Connect

    Dong, Qiang; Yin, Shu; Yoshida, Mizuki; Wu, Xiaoyong; Liu, Bin; Miura, Akira; Takei, Takahiro; Kumada, Nobuhiro; Sato, Tsugio

    2015-09-15

    Alkaline earth metal doped tin oxide (SnO{sub 2}) hollow nanospheres with a diameter of 50 nm have been synthesized successfully via a facial solvothermal route in a very simple system composed of only ethanol, acetic acid, SnCl{sub 4}·5H{sub 2}O and A(NO{sub 3}){sub 2}·xH{sub 2}O (A = Mg, Ca, Sr, Ba). The synthesized undoped SnO{sub 2} and A-doped SnO{sub 2} hollow nanospheres were characterized by the oxygen storage capacity (OSC), X-ray diffraction, transmission electron microscopy and the Brunauer–Emmet–Teller (BET) technique. The OSC values of all samples were measured using thermogravimetric-differential thermal analysis. The incorporation of alkaline earth metal ion into tin oxide greatly enhanced the thermal stability and OSC. Especially, Ba-doped SnO{sub 2} hollow nanospheres calcined at 1000 °C for 20 h with a BET surface area of 61 m{sup 2} g{sup −1} exhibited the considerably high OSC of 457 μmol-O g{sup −1} and good thermal stability. Alkaline earth metal doped tin oxide has the potential to be a novel oxygen storage material.

  15. Preparation of Cu-doped nickel oxide thin films and their properties

    SciTech Connect

    Gowthami, V.; Meenakshi, M.; Anandhan, N.; Sanjeeviraja, C.

    2014-04-24

    Copper doped Nickel oxide film was preferred on glass substrate by simple nebulizer technique keeping the substrate temperature at 350°C and characterized by X-ray diffraction (XRD), Photoluminescence (PL) and Four probe resistivity measurements. XRD studies indicated cubic structure and the crystallites are preferentially oriented along the [111] direction. Interesting results have been obtained from the study of PL spectra. A peak corresponding to 376nm in the emission spectra for 0%, 5% and 10% copper doped samples. The samples show sharp and strong UV emission corresponding to the near band edge emission under excitation of 275nm.

  16. Structural and optical properties of Nd{sup 3+} doped gadolinium oxide 1D nanorods

    SciTech Connect

    Boopathi, G. Mohan, R.; Raj, S. Gokul; Kumar, G. Ramesh

    2014-04-24

    Neodymium doped gadolinium hydroxide [Nd:Gd(OH)3] nanorods were successfully synthesized at 60 °C through co-precipitation method. The dopant percentage was maintained at 5% and calcination was done at 750 °C temperature for 1 hour to form the respective neodymium doped gadolinium oxide [Nd:Gd{sub 2}O{sub 3}] nanorods. The as-formed and annealed products were investigated in detail by using powder X-ray diffraction (XRD) pattern, scanning electron microscopy (SEM) with an energy dispersive X-ray spectrum (EDX), high-resolution transmission electron microscopy (HRTEM) and photoluminescence (PL) spectrophotometry.

  17. Structural, morphological and optical investigations on Sm{sup 3+} doped gadolinium oxide nanorods

    SciTech Connect

    Boopathi, G.; Mohan, R.; Raj, S. Gokul; Kumar, G. Ramesh

    2014-04-24

    One dimensional uniform Sm{sup 3+} doped gadolinium hydroxide nanorods have been prepared via simple co– precipitation technique at 60 °C temperature for 1 hour. The samples were calcinated at 750 °C to obtain Sm{sup 3+} doped gadolinium oxide nanorods. The 1D nanorods were then subjected to different characterization techniques to ascertain its structural stability and its morphology were investigated using high–resolution transmission electron microscopy. Photoluminescence (PL) spectrophotometry was investigated and the obtained results were discussed in detail.

  18. Surfactant Assisted Sonochemical Synthesis and Characterization of Gadolinium Doped Zinc Oxide Nanoparticles.

    PubMed

    Khajuria, Heena; Ladol, Jigmet; Singh, Rajinder; Khajuria, Sonika; Khajuria, Haq N

    2015-01-01

    Pure and Gd doped Zinc Oxide (ZnO) nanoparticles were synthesized by sonochemical method using different surfactants (PVP/CTAB). The nanoparticles were characterized by powder X-ray diffraction (PXRD), fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), particle size analysis by DLS technique and UV-Visible spectroscopy. The effect of Gd doping and nature of surfactants on crystallite size, morphology and band gap of ZnO nanoparticles have been investigated. In addition to this, the effect of nature of surfactant on amount of dopant inserted in the ZnO lattice was also studied.

  19. Oxidation studies on small atom doped TI*5*SI*3*

    SciTech Connect

    Thom, Andrew

    1995-09-26

    This report described the oxidation and oxidation resistance of Ti5Si3, along with a discussion on general material properties. Single crystal studies of Ti5Si3Zx are included.

  20. Phosphorus Doping Effect in a Zinc Oxide Channel Layer to Improve the Performance of Oxide Thin-Film Transistors

    NASA Astrophysics Data System (ADS)

    Han, Dong-Suk; Moon, Yeon-Keon; Lee, Sih; Kim, Kyung-Taek; Moon, Dae-Yong; Lee, Sang-Ho; Kim, Woong-Sun; Park, Jong-Wan

    2012-09-01

    In this study, we fabricated phosphorus-doped zinc oxide-based thin-film transistors (TFTs) using direct current (DC) magnetron sputtering at a relatively low temperature of 100°C. To improve the TFT device performance, including field-effect mobility and bias stress stability, phosphorus dopants were employed to suppress the generation of intrinsic defects in the ZnO-based semiconductor. The positive and negative bias stress stabilities were dramatically improved by introducing the phosphorus dopants, which could prevent turn-on voltage ( V ON) shift in the TFTs caused by charge trapping within the active channel layer. The study showed that phosphorus doping in ZnO was an effective method to control the electrical properties of the active channel layers and improve the bias stress stability of oxide-based TFTs.

  1. Synthesis and characterization of lanthanum doped zinc oxide nanoparticles

    NASA Astrophysics Data System (ADS)

    Kumar, Vinod; Sonia, Suman, Kumar, Sacheen; Kumar, Dinesh

    2016-05-01

    La doped ZnO (Zn1-xLaxO, x = 0, 3, 6 and 9) were prepared via chemical co-precipitation method using Zinc Acetate, Lanthanum Acetate and Sodium Hydroxide at 50°C. Hydrate nanoparticles were annealed in air at 300°C for 3 hours. The synthesized samples have been characterized by powder X-ray diffraction and UV-Visiblespectrophotometer. The XRD measurement revealsthat the prepared nanoparticles have different microstructure without changing a hexagonal wurtzite structure. The result shows the change in nanoparticles size with the increment of lanthanum concentration for lower concentration for x = 0 to 6 and decreases at x = 9.

  2. Doped, porous iron oxide films and their optical functions and anodic photocurrents for solar water splitting

    SciTech Connect

    Kronawitter, Coleman X.; Mao, Samuel S.; Antoun, Bonnie R.

    2011-02-28

    The fabrication and morphological, optical, and photoelectrochemical characterization of doped iron oxide films is presented. The complex index of refraction and absorption coefficient of polycrystalline films are determined through measurement and modeling of spectral transmission and reflection data using appropriate dispersion relations. Photoelectrochemical characterization for water photo-oxidation reveals that the conversion efficiencies of electrodes are strongly influenced by substrate temperature during their oblique-angle physical vapor deposition. These results are discussed in terms of the films' morphological features and the known optoelectronic limitations of iron oxide films for application in solar water splitting devices.

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

    SciTech Connect

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

    2013-01-15

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

  4. Dielectric Properties of Rare-Earth-Oxide-Doped BaTiO3 Ceramics Fired in Reducing Atmosphere

    NASA Astrophysics Data System (ADS)

    Okino, Yoshikazu; Shizuno, Hisamitsu; Kusumi, Shinya; Kishi, Hiroshi

    1994-09-01

    In order to gain an understanding of highly reliable electrical characteristics for the Ho-doped multilayer ceramic capacitors with Ni electrodes, dielectric properties of various rare-earth-oxide-doped BaTiO3 ceramics were studied. The smaller ionic radius rare-earth-oxide (Dy, Ho, Er)-doped samples showed lower resistivity in reducing atmosphere, but higher resistivity in oxidizing atmosphere at the cooling stage, compared with the larger-ion (La, Sm, Gd)-doped samples. Multilayer ceramic capacitors with Ni electrodes using the smaller-ion-doped materials showed smaller aging rate and longer lifetime. We developed Ni-electrode MLCs with X7R specification as 1 µ F in the 2125 type.

  5. Rational design of mixed ionic and electronic conducting perovskite oxides for solid oxide fuel cell anode materials: A case study for doped SrTiO3

    SciTech Connect

    Suthirakun, Suwit; Xiao, Guoliang; Ammal, Salai Cheettu; Chen, Fanglin; zur Loye, Hans-Conrad; Heyden, Andreas

    2014-01-01

    The effect of p- and n-type dopants on ionic and electronic conductivity of SrTiO3 based perovskites were investigated both computationally and experimentally. Specifically, we performed density functional theory (DFT) calculations of Na- and La-doped SrTiO3 and Na- and Nb-doped SrTiO3 systems. Constrained ab initio thermodynamic calculations were used to evaluate the phase stability and reducibility of doped SrTiO3 under both oxidizing and reducing synthesis conditions, as well as under anodic solid oxide fuel cell (SOFC) conditions. The density of states (DOS) of these materials was analyzed to study the effects of p- and n-doping on the electronic conductivity. Furthermore, Na- and La-doped SrTiO3 and Na- and Nb-doped SrTiO3 samples were experimentally prepared and the conductivity was measured to confirm our computational predictions. The experimental observations are in very good agreement with the theoretical predictions that doping n-doped SrTiO3 with small amounts of p-type dopants promotes both the ionic and electronic conductivity of the material. This doping strategy is valid independent of p- and n-doping site and permits the synthesis of perovskite based mixed ionic/electronic conductors.

  6. Cross-beam pulsed laser fabrication of Free-Standing Nanostructured Carbon Nanotubes-Pt-Ceria Anode with unprecedented electroactivity and durability for ethanol oxidation

    NASA Astrophysics Data System (ADS)

    Wang, Youling; Tabet-Aoul, Amel; Gougis, Maxime; Mohamedi, Mohamed

    2015-01-01

    Owing to its inherent properties such as great capacity to store and release oxygen, lattice oxygen that has a key role in removing the CO poisoning effect, non-toxicity, abundance, low cost and low temperature processing, CeO2 is emerging as a unique class of electrode material for low temperature polymer electrolyte fuel cells such as direct ethanol fuel cells (DEFCs). However, the maximal exploitation of its functional properties is strictly reliant on the availability of optimized synthesis routes that allow tailor-designing, architecturing and manipulation of CeO2 in a precise manner when it is combined with other functional materials. Here we use the cross-beam pulsed laser deposition (CBPLD) technique to synthesize free-standing (binderless) Pt-CeO2 nanostructured thin films onto carbon nanotubes as anodes for ethanol oxidation reaction. Further significance of this work is that it establishes the importance in the design of the catalyst layer architecture. Indeed, we demonstrate here that when CeO2 material is beneath or when it is mixed with Pt, the interactions between Pt with CeO2 are not similar leading inevitably to different electrocatalytic performances. Given proper tailoring synthesis conditions, CBPLD-developed Pt-CeO2 thin films are remarkably stable and provide electrochemical performance much greater than the layer onto layer CeO2/Pt architecture.

  7. Effect of nitrogen doping of graphene oxide on hydrogen and hydroxyl adsorption

    NASA Astrophysics Data System (ADS)

    Min, Byeong June; Jeong, Hae Kyung

    2014-05-01

    We investigate how nitrogen-doping affects the hydrogen (H) and the hydroxyl (OH) adsorption on graphene oxide (GO) and on nitrogen-doped GO (NGO) via pseudopotential plane wave density functional calculations within the local spin density approximation. We find that the nitrogendoping brings about drastic changes in the hydrogen and the hydroxyl adsorption energetics, but its effects depend sensitively on the nitrogen configuration in NGO. The H and the OH adsorption energies are comparable only for pyrrolic NGO. In GO and quarternary NGO, the H adsorption energy is greater than the OH adsorption energy while the trend is reversed in pyridinic NGO. Also, the OH adsorption process is less affected by nitrogen-doping than the H adsorption is.

  8. Effect of W and WC on the oxidation resistance of yttria-doped silicon nitride

    NASA Technical Reports Server (NTRS)

    Schuon, S.

    1980-01-01

    The effect of W and WC contamination on the oxidation and cracking in air of sintered Si3N4 - 8 w/o Y2O3 ceramics at 500, 750, and 1350 C is examined. A mixture of Si3N4 - 8Y2O3, milled with alumina balls, was divided into four portions. Three portions were doped with 2 w/o WC W, and 4 w/o W respectively, in order to simulate contamination during milling. The fourth portion was undoped and used on a control. The addition of W or WC did not affect the phase relationships in the system, as all bars with or without additions contained melilite as the major Si-Y-O-N phase after sintering. At 750 C, instability (rapid oxidation and cracking) of W-doped bars appears to have occurred as a result of oxidation of the tungsten containing melilite phase. No intermediate temperature instability was observed in bars containing 2 w/o WC or in bars with no additive. Specimens exposed at 1350 C had good oxidation resistance due to the formation of a protective siliceous oxide layer. A specimen containing 4 w/o W which was preoxidized at 1350 C had improved oxidation resistance at 750 C. The tendency towards oxidation and cracking of Si3N4 - 8 Y2O3 at 750 C is concluded to be related to tungsten content of the sintered bars.

  9. Catalytically Active and Spectator Ce(3+) in Ceria-Supported Metal Catalysts.

    PubMed

    Kopelent, René; van Bokhoven, Jeroen A; Szlachetko, Jakub; Edebeli, Jacinta; Paun, Cristina; Nachtegaal, Maarten; Safonova, Olga V

    2015-07-20

    Identification of active species and the rate-determining reaction steps are crucial for optimizing the performance of oxygen-storage materials, which play an important role in catalysts lowering automotive emissions, as electrode materials for fuel cells, and as antioxidants in biomedicine. We demonstrated that active Ce(3+) species in a ceria-supported platinum catalyst during CO oxidation are short-lived and therefore cannot be observed under steady-state conditions. Using time-resolved resonant X-ray emission spectroscopy, we quantitatively correlated the initial rate of Ce(3+) formation under transient conditions to the overall rate of CO oxidation under steady-state conditions and showed that ceria reduction is a kinetically relevant step in CO oxidation, whereas a fraction of Ce(3+) was present as spectators. This approach can be applied to various catalytic processes involving oxygen-storage materials and reducible oxides to distinguish between redox and nonredox catalytic mechanisms.

  10. Fully transparent thin film transistors based on zinc oxide channel layer and molybdenum doped indium oxide electrodes

    NASA Astrophysics Data System (ADS)

    MÄ dzik, Mateusz; Elamurugu, Elangovan; Viegas, Jaime

    2016-03-01

    In this work we report the fabrication of thin film transistors (TFT) with zinc oxide channel and molybdenum doped indium oxide (IMO) electrodes, achieved by room temperature sputtering. A set of devices was fabricated, with varying channel width and length from 5μm to 300μm. Output and transfer characteristics were then extracted to study the performance of thin film transistors, namely threshold voltage and saturation current, enabling to determine optimal fabrication process parameters. Optical transmission in the UV-VIS-IR are also reported.

  11. Pd doped reduced graphene oxide for hydrogen storage

    SciTech Connect

    Das, Tapas; Banerjee, Seemita; Sudarsan, V.

    2015-06-24

    Pd nanoparticles dispersed reduced graphene oxide sample has been prepared by a simple chemical method using hydrazine as the reducing agent. Based on XRD and {sup 13}C MAS NMR studies it is confirmed that, Pd nanoparticles are effectively mixed with the reduced graphene oxide sample. Maximum hydrogen storage capacity has been estimated to be ∼1.36 wt % at 123K. Improved hydrogen storage capacity of Pd incorporated sample can be explained based on the phenomenon of spillover of atomic hydrogen.

  12. Pd doped reduced graphene oxide for hydrogen storage

    NASA Astrophysics Data System (ADS)

    Das, Tapas; Banerjee, Seemita; Sudarsan, V.

    2015-06-01

    Pd nanoparticles dispersed reduced graphene oxide sample has been prepared by a simple chemical method using hydrazine as the reducing agent. Based on XRD and 13C MAS NMR studies it is confirmed that, Pd nanoparticles are effectively mixed with the reduced graphene oxide sample. Maximum hydrogen storage capacity has been estimated to be ˜1.36 wt % at 123K. Improved hydrogen storage capacity of Pd incorporated sample can be explained based on the phenomenon of spillover of atomic hydrogen.

  13. High-rate Li4Ti5O12/N-doped reduced graphene oxide composite using cyanamide both as nanospacer and a nitrogen doping source

    NASA Astrophysics Data System (ADS)

    Jeong, Jun Hui; Kim, Myeong-Seong; Kim, Young-Hwan; Roh, Kwang Chul; Kim, Kwang-Bum

    2016-12-01

    A Li4Ti5O12(LTO)/N-doped reduced graphene oxide (RGO) composite is proposed using dual functional nitrogen doping source to prevent RGO restacking and achieve uniform nitrogen doping on RGO sheets to increase the rate performance of high-rate lithium ion batteries. The pore structure (both meso- and macro pores) is developed when RGO restacking is prevented, facilitating electrolyte ion diffusion to active sites with lower resistance. Uniform nitrogen doping on RGO sheets with high nitrogen contents provides additional free electrons to the sheets, resulting in increased electronic conductivity. Cyanamide is used as the nitrogen doping source for the N-doped RGO as well as a nanospacer between the RGO sheets. In the composite, the nitrogen content of the RGO sheets is 2.3 wt%, which increases the electronic conductivity of the composite to 1.60 S cm-1. The specific surface area of the composite is increased to 35.8 m2 g-1. Thus, the composite structure with the N-doped RGO sheets and porous secondary particles has high electrical conductivity and high ion accessibility. The LTO/N-doped RGO composite demonstrates excellent electrochemical performance with a low resistance of 48.4 Ω, a high specific capacity of 117.8 mAh g-1 at 30 C, and good cycle stability.

  14. The effect of material composition of 3-dimensional graphene oxide and self-doped polyaniline nanocomposites on DNA analytical sensitivity.

    PubMed

    Yang, Tao; Chen, Huaiyin; Yang, Ruirui; Wang, Xinxing; Nan, Fuxin; Jiao, Kui

    2015-09-01

    Until now, morphology effects of 2-dimensional or 3-dimensional graphene nanocomposites and the effect of material composition on the biosensors have been rarely reported. In this paper, the various nanocomposites based on graphene oxide and self-doped polyaniline nanofibres for studying the effect of morphology and material composition on DNA sensitivity were directly reported. The isolation and dispersion of graphene oxide were realized via intercalated self-doped polyaniline and ultrasonication, where the ultrasonication prompts the aggregates of graphite oxide to break up and self-doped polyaniline to diffuse into the stacked graphene oxide. Significant electrochemical enhancement has been observed due to the existence of self-doped polyaniline, which bridges the defects for electron transfer and, in the mean time, increases the basal spacing between graphene oxide sheets. Different morphologies can result in different ssDNA surface density, which can further influence the hybridization efficiency. Compared with 2-dimensional graphene oxide, self-doped polyaniline and other morphologies of nanocomposites, 3-dimensional graphene oxide-self-doped polyaniline nanowalls exhibited the highest surface density and hybridization efficiency. Furthermore, the fabricated biosensors presented the broad detection range with the low detection limit due to the specific surface area, a large number of electroactive species, and open accessible space supported by nanowalls.

  15. Converting graphene oxide monolayers into boron carbonitride nanosheets by substitutional doping.

    PubMed

    Lin, Tsung-Wu; Su, Ching-Yuan; Zhang, Xin-Quan; Zhang, Wenjing; Lee, Yi-Hsien; Chu, Chih-Wei; Lin, Hsin-Yu; Chang, Mu-Tung; Chen, Fu-Rong; Li, Lain-Jong

    2012-05-07

    To realize graphene-based electronics, bandgap opening of graphene has become one of the most important issues that urgently need to be addressed. Recent theoretical and experimental studies show that intentional doping of graphene with boron and nitrogen atoms is a promising route to open the bandgap, and the doped graphene might exhibit properties complementary to those of graphene and hexagonal boron nitride (h-BN), largely extending the applications of these materials in the areas of electronics and optics. This work demonstrates the conversion of graphene oxide nanosheets into boron carbonitride (BCN) nanosheets by reacting them with B(2) O(3) and ammonia at 900 to 1100 °C, by which the boron and nitrogen atoms are incorporated into the graphene lattice in randomly distributed BN nanodomains. The content of BN in BN-doped graphene nanosheets can be tuned by changing the reaction temperature, which in turn affects the optical bandgap of these nanosheets. Electrical measurements show that the BN-doped graphene nanosheet exhibits an ambipolar semiconductor behavior and the electrical bandgap is estimated to be ≈25.8 meV. This study provides a novel and simple route to synthesize BN-doped graphene nanosheets that may be useful for various optoelectronic applications.

  16. Synergistic effect of graphene-oxide-doping and microwave-curing on mechanical strength of cement

    NASA Astrophysics Data System (ADS)

    Qin, Hao; Wei, Wei; Hang Hu, Yun

    2017-04-01

    In this communication, efficient reinforcement of cement matrix was obtained by graphene-oxide (GO) doping and curing treatments. The compressive strength of plain cement is 14.3±0.2 MPa. When the cement contained 0.5 wt% GO, its strength reached 19.4±0.9 MPa. The strength can be further enhanced by curing, which follows the sequence: Microwave-cured GO-cement > Microwave and water-cured GO-cement > Water-cured GO-cement > GO-cement without curing. The highest compressive strength (32.4±0.7 MPa), which was achieved by combining GO-doping and microwave curing, is 126.6±8.1% higher than that without GO-doping and microwave curing. This demonstrates a synergistic effect of GO doping and microwave-curing on the strength of cement composite materials. Furthermore, X-ray diffraction (XRD), Fourier transform Infrared Spectroscopy (FTIR), and field emission scanning electron microscope (FESEM) characterizations revealed that the combination of GO doping and microwave-curing remarkably accelerated cement hydration, leading to the regular and compact structure and thus a high compressive strength. This work provides a new way to improve the mechanical properties of cement composites.

  17. Microporous Ni-doped TiO2 film photocatalyst by plasma electrolytic oxidation.

    PubMed

    Yao, Zhongping; Jia, Fangzhou; Tian, Shujun; Li, ChunXiang; Jiang, Zhaohua; Bai, Xuefeng

    2010-09-01

    Ni-doped TiO2 film catalysts were prepared by a plasma electrolytic oxidation (PEO) method and were mainly characterized by means of SEM, EDS, XRD, XPS, and DRS, respectively. The effects of Ni doping on the structure, composition and optical absorption property of the film catalysts were investigated along with their inherent relationships. The results show that the film catalyst is composed of anatase and rutile TiO2 with microporous structure. Doping Ni changes the phase composition and the lattice parameters (interplanar crystal spacing and cell volume) of the films. The optical absorption range of TiO2 film gradually expands and shifts to the red with increasing dosages. Both direct and indirect transition band gaps of the TiO2 films are deduced consequently. Moreover, the photocatalytic activity of the film catalysts for splitting Na2S+Na2SO3 solution into H2 is enhanced by doping with an appropriate amount of Ni. The as-prepared TiO2 film catalyst doping with 10 g/L of Ni(Ac)2 presents the highest photocatalytic reducing activity.

  18. Nitrogen-doped reduced graphene oxide as electrode material for high rate supercapacitors

    NASA Astrophysics Data System (ADS)

    Śliwak, Agata; Grzyb, Bartosz; Díez, Noel; Gryglewicz, Grażyna

    2017-03-01

    Nitrogen-doped reduced graphene oxides (N-rGOs) have been synthesized at various temperatures by a facile hydrothermal route involving the doping of an aqueous graphene oxide dispersion with amitrole. The N-rGOs had a nitrogen content ranging from 10.9 to 13.4 at%, which is among the highest reported for this type of material. The predominant nitrogen species were pyridinic followed by amide/amine, pyrrolic, and quaternary nitrogen. Cyclic voltammetry and impedance spectroscopy measurements performed on the N-doped and nitrogen-free samples revealed that nitrogen fixation provided the material with pseudocapacitive behaviour and improved ion diffusion and charge propagation. A high specific capacitance of 244 F g-1 was obtained at a high scan rate of 100 mV s-1 for the N-rGO with the highest nitrogen content. An outstanding rate capability for the N-rGO, with increasing scan rates, of 98% was obtained, while only 70% was obtained for the non-doped rGO. 92% of the initial capacitance was maintained over 5000 charge/discharge cycles due to the high stability of the electrochemically active nitrogen moieties. Hydrothermal synthesis using amitrole as a nitrogen dopant represents a simple route for the synthesis of graphene with very high nitrogen content and exceptional behaviour for use as electrode material in high-power supercapacitors.

  19. Influence of neodymium concentration on excitation and emission properties of Nd doped gallium oxide nanocrystalline films

    SciTech Connect

    Podhorodecki, A.; Banski, M.; Misiewicz, J.; Lecerf, C.; Marie, P.; Cardin, J.; Portier, X.

    2010-09-15

    Gallium oxide and more particularly {beta}-Ga{sub 2}O{sub 3} matrix is an excellent material for new generation of devices electrically or optically driven as it is known as the widest band gap transparent conductive oxide. In this paper, the optical properties of neodymium doped gallium oxide films grown by magnetron sputtering have been analyzed. The influence of the Nd ions concentration on the excitation/emission mechanisms of Nd ions and the role of gallium oxide matrix have been investigated. The grain size reduction into gallium oxide films have been observed when concentration of Nd increases. It has been found for all samples that the charge transfer is the main excitation mechanism for Nd ions where defect states play an important role as intermediate states. As a consequence Nd emission efficiency increases with temperature giving rise to most intensive emission at 1087 nm at room temperature.

  20. Influence of neodymium concentration on excitation and emission properties of Nd doped gallium oxide nanocrystalline films

    NASA Astrophysics Data System (ADS)

    Podhorodecki, A.; Banski, M.; Misiewicz, J.; Lecerf, C.; Marie, P.; Cardin, J.; Portier, X.

    2010-09-01

    Gallium oxide and more particularly β-Ga2O3 matrix is an excellent material for new generation of devices electrically or optically driven as it is known as the widest band gap transparent conductive oxide. In this paper, the optical properties of neodymium doped gallium oxide films grown by magnetron sputtering have been analyzed. The influence of the Nd ions concentration on the excitation/emission mechanisms of Nd ions and the role of gallium oxide matrix have been investigated. The grain size reduction into gallium oxide films have been observed when concentration of Nd increases. It has been found for all samples that the charge transfer is the main excitation mechanism for Nd ions where defect states play an important role as intermediate states. As a consequence Nd emission efficiency increases with temperature giving rise to most intensive emission at 1087 nm at room temperature.

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

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

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

  2. Reactivity enhancement of oxide skins in reversible Ti-doped NaAlH{sub 4}

    SciTech Connect

    Delmelle, Renaud; Borgschulte, Andreas; Gehrig, Jeffrey C.; Züttel, Andreas

    2014-12-15

    The reversibility of hydrogen sorption in complex hydrides has only been shown unambiguously for NaAlH{sub 4} doped with transition metal compounds. Despite a multitude of investigations of the effect of the added catalyst on the hydrogen sorption kinetics of NaAlH{sub 4}, the mechanism of catalysis remains elusive so far. Following the decomposition of TiCl{sub 3}-doped NaAlH{sub 4} by in-situ X-ray photoelectron spectroscopy (XPS), we link the chemical state of the dopant with those of the hydride and decomposition products. Titanium and aluminium change their oxidation states during cycling. The change of the formal oxidation state of Al from III to zero is partly due to the chemical reaction from NaAlH{sub 4} to Al. Furthermore, aluminium oxide is formed (Al{sub 2}O{sub 3}), which coexists with titanium oxide (Ti{sub 2}O{sub 3}). The interplay of metallic and oxidized Ti with the oxide skin might explain the effectiveness of Ti and similar dopants (Ce, Zr…)

  3. Acetone Sensing Properties of a Gas Sensor Composed of Carbon Nanotubes Doped With Iron Oxide Nanopowder

    PubMed Central

    Tan, Qiulin; Fang, Jiahua; Liu, Wenyi; Xiong, Jijun; Zhang, Wendong

    2015-01-01

    Iron oxide (Fe2O3) nanopowder was prepared by a precipitation method and then mixed with different proportions of carbon nanotubes. The composite materials were characterized by X-ray powder diffraction, Fourier transform infrared spectroscopy and scanning electron microscopy. A fabricated heater-type gas sensor was compared with a pure Fe2O3 gas sensor under the influence of acetone. The effects of the amount of doping, the sintering temperature, and the operating temperature on the response of the sensor and the response recovery time were analyzed. Experiments show that doping of carbon nanotubes with iron oxide effectively improves the response of the resulting gas sensors to acetone gas. It also reduces the operating temperature and shortens the response recovery time of the sensor. The response of the sensor in an acetone gas concentration of 80 ppm was enhanced, with good repeatability. PMID:26569253

  4. Chlorine sensing properties of zinc oxide resistive gas sensor doped with platinum

    NASA Astrophysics Data System (ADS)

    Fiedot, M.; Suchorska-Woźniak, P.; Rac, O.; Nawrot, W.; Teterycz, H.

    2016-11-01

    In presented studies resistive chlorine gas sensor with gas sensitive layer in the form of zinc oxide microrods doped with platinum was developed. The growth of active layer was carried out in water solution containing zinc nitrate (V), hexamethylenetetramine and chloroplatinic acid using the chemical bath deposition method. The structure and morphology of obtained sensors was characterized by scanning electron microscope (SEM) and energy-dispersive X-ray spectroscopy (EDX). To determine the chlorine gas sensing properties Temperature-Stimulated Conductance method (TSC) was used. During the measurements sensor was tested in a reference atmosphere and an atmosphere with 2, 5 or 8 ppm of chlorine. Obtained results have shown that zinc oxide microrods doped with platinum were obtained. TSC measurements showed that developed sensor allows to detect chlorine with very good sensitivity.

  5. Interfacial control of oxygen vacancy doping and electrical conduction in thin film oxide heterostructures.

    PubMed

    Veal, Boyd W; Kim, Seong Keun; Zapol, Peter; Iddir, Hakim; Baldo, Peter M; Eastman, Jeffrey A

    2016-06-10

    Oxygen vacancies in proximity to surfaces and heterointerfaces in oxide thin film heterostructures have major effects on properties, resulting, for example, in emergent conduction behaviour, large changes in metal-insulator transition temperatures or enhanced catalytic activity. Here we report the discovery of a means of reversibly controlling the oxygen vacancy concentration and distribution in oxide heterostructures consisting of electronically conducting In2O3 films grown on ionically conducting Y2O3-stabilized ZrO2 substrates. Oxygen ion redistribution across the heterointerface is induced using an applied electric field oriented in the plane of the interface, resulting in controlled oxygen vacancy (and hence electron) doping of the film and possible orders-of-magnitude enhancement of the film's electrical conduction. The reversible modified behaviour is dependent on interface properties and is attained without cation doping or changes in the gas environment.

  6. Interfacial control of oxygen vacancy doping and electrical conduction in thin film oxide heterostructures

    PubMed Central

    Veal, Boyd W.; Kim, Seong Keun; Zapol, Peter; Iddir, Hakim; Baldo, Peter M.; Eastman, Jeffrey A.

    2016-01-01

    Oxygen vacancies in proximity to surfaces and heterointerfaces in oxide thin film heterostructures have major effects on properties, resulting, for example, in emergent conduction behaviour, large changes in metal-insulator transition temperatures or enhanced catalytic activity. Here we report the discovery of a means of reversibly controlling the oxygen vacancy concentration and distribution in oxide heterostructures consisting of electronically conducting In2O3 films grown on ionically conducting Y2O3-stabilized ZrO2 substrates. Oxygen ion redistribution across the heterointerface is induced using an applied electric field oriented in the plane of the interface, resulting in controlled oxygen vacancy (and hence electron) doping of the film and possible orders-of-magnitude enhancement of the film's electrical conduction. The reversible modified behaviour is dependent on interface properties and is attained without cation doping or changes in the gas environment. PMID:27283250

  7. Co-doped titanium oxide foam and water disinfection device

    SciTech Connect

    Shang, Jian-Ku; Wu, Pinggui; Xie, Rong-Cai

    2016-01-26

    A quaternary oxide foam, comprises an open-cell foam containing (a) a dopant metal, (b) a dopant nonmetal, (c) titanium, and (d) oxygen. The foam has the advantages of a high surface area and a low back pressure during dynamic flow applications. The inactivation of Escherichia coli (E. coli) was demonstrated in a simple photoreactor.

  8. Highly conducting and crystalline doubly doped tin oxide films fabricated using a low-cost and simplified spray technique

    NASA Astrophysics Data System (ADS)

    Ravichandran, K.; Muruganantham, G.; Sakthivel, B.

    2009-11-01

    Doubly doped (simultaneous doping of antimony and fluorine) tin oxide films (SnO 2:Sb:F) have been fabricated by employing an inexpensive and simplified spray technique using perfume atomizer from aqueous solution of SnCl 2 precursor. The structural studies revealed that the films are highly crystalline in nature with preferential orientation along the (2 0 0) plane. It is found that the size of the crystallites of the doubly doped tin oxide films is larger (69 nm) than that (27 nm) of their undoped counterparts. The dislocation density of the doubly doped film is lesser (2.08×10 14 lines/m 2) when compared with that of the undoped film (13.2×10 14 lines/m 2), indicating the higher degree of crystallinity of the doubly doped films. The SEM images depict that the films are homogeneous and uniform. The optical transmittance in the visible range and the optical band gap of the doubly doped films are 71% and 3.56 eV respectively. The sheet resistance (4.13 Ω/□) attained for the doubly doped film in this study is lower than the values reported for spray deposited fluorine or antimony doped tin oxide films prepared from aqueous solution of SnCl 2 precursor (without using methanol or ethanol).

  9. Nitrogen Doping in Oxygen-Deficient Ca2Fe2O5: A Strategy for Efficient Oxygen Reduction Oxide Catalysts.

    PubMed

    Jijil, Chamundi P; Lokanathan, Moorthi; Chithiravel, Sundaresan; Nayak, Chandrani; Bhattacharyya, Dibyendu; Jha, Shambhu Nath; Babu, P D; Kakade, Bhalchandra; Devi, R Nandini

    2016-12-21

    Oxygen reduction reaction (ORR) is increasingly being studied in oxide systems due to advantages ranging from cost effectiveness to desirable kinetics. Oxygen-deficient oxides like brownmillerites are known to enhance ORR activity by providing oxygen adsorption sites. In parallel, nitrogen and iron doping in carbon materials, and consequent presence of catalytically active complex species like C-Fe-N, is also suggested to be good strategies for designing ORR-active catalysts. A combination of these features in N-doped Fe containing brownmillerite can be envisaged to present synergistic effects to improve the activity. This is conceptualized in this report through enhanced activity of N-doped Ca2Fe2O5 brownmillerite when compared to its oxide parents. N doping is demonstrated by neutron diffraction, UV-vis spectroscopy, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy. Electrical conductivity is also found to be enhanced by N doping, which influences the activity. Electrochemical characterization by cyclic voltammetry, rotating disc electrode, and rotating ring disk electrode (RRDE) indicates an improved oxygen reduction activity in N-doped brownmillerite, with a 10 mV positive shift in the onset potential. RRDE measurements show that the compound exhibits 4-electron reduction pathways with lower H2O2 production in the N-doped system; also, the N-doped sample exhibited better stability. The observations will enable better design of ORR catalysts that are stable and cost-effective.

  10. The single cell of low temperature solid oxide fuel cell with sodium carbonate-SDC (samarium-doped ceria) as electrolyte and biodiesel as fuel

    NASA Astrophysics Data System (ADS)

    Rahmawati, F.; Nuryanto, A.; Nugrahaningtyas, K. D.

    2016-02-01

    In this research NSDC (composite of Na2CO3-SDC) was prepared by the sol-gel method to produce NSDC1 and also by the ceramic method to produce NSDC2. The prepared NSDC then were analyzed by XRD embedded with Le Bail refinement to study the change of characteristic peaks, their crystal structure, and their cell parameters. Meanwhile, the measurement of impedance was conducted to study the electrical conductivity of the prepared materials. A single cell was prepared by coating NSDC-L (a composite of NSDC with Li0.2Ni0.7Cu0.1O2) on both surfaces of NSDC. The NSDC-L was used as anode and cathode. The ionic conductivity of NSDC1 and NSDC2 at 400 oC are 4.1109 x 10-2 S.cm-1 and 1.6231 x 10-2 S.cm-1, respectively. Both electrolytes have ionic conductivity higher than 1 x 10-4 S.cm-1, therefore, can be categorized as good electrolyte [1]. However, the NSDC1 shows electrodeelectrolyte conduction. It indicates the existence of electronic migration from electrolyte- electrode or vice versa. Those may cause a short circuit during fuel cell operation and will reduce the fuel cell performance fastly. The single cell tests were conducted at 300, 400, 500 and 600 °C. The single fuel cell with NSDC1 and NSDC2 as electrolyte show maximum power density at 400 °C with the power density of 3.736 x 10-2 mW.cm-2 and 2.245 x 10-2 mW.cm-2, respectively.

  11. Nickel supported on nitrogen-doped carbon nanotubes as hydrogen oxidation reaction catalyst in alkaline electrolyte

    SciTech Connect

    Zhuang, Zhongbin; Giles, Stephen A.; Zheng, Jie; Jenness, Glen R.; Caratzoulas, Stavros; Vlachos, Dionisios G.; Yan, Yushan

    2016-01-14

    The development of a low-cost, high-performance platinum-group-metal-free hydroxide exchange membrane fuel cell is hindered by the lack of a hydrogen oxidation reaction catalyst at the anode. Here we report that a composite catalyst, nickel nanoparticles supported on nitrogen-doped carbon nanotubes, has hydrogen oxidation activity similar to platinum-group metals in alkaline electrolyte. Although nitrogen-doped carbon nanotubes are a very poor hydrogen oxidation catalyst, as a support, it increases the catalytic performance of nickel nanoparticles by a factor of 33 (mass activity) or 21 (exchange current density) relative to unsupported nickel nanoparticles. Density functional theory calculations indicate that the nitrogen-doped support stabilizes the nanoparticle against reconstruction, while nitrogen located at the edge of the nanoparticle tunes local adsorption sites by affecting the d-orbitals of nickel. Here, owing to its high activity and low cost, our catalyst shows significant potential for use in low-cost, high-performance fuel cells.

  12. Nickel supported on nitrogen-doped carbon nanotubes as hydrogen oxidation reaction catalyst in alkaline electrolyte

    DOE PAGES

    Zhuang, Zhongbin; Giles, Stephen A.; Zheng, Jie; ...

    2016-01-14

    The development of a low-cost, high-performance platinum-group-metal-free hydroxide exchange membrane fuel cell is hindered by the lack of a hydrogen oxidation reaction catalyst at the anode. Here we report that a composite catalyst, nickel nanoparticles supported on nitrogen-doped carbon nanotubes, has hydrogen oxidation activity similar to platinum-group metals in alkaline electrolyte. Although nitrogen-doped carbon nanotubes are a very poor hydrogen oxidation catalyst, as a support, it increases the catalytic performance of nickel nanoparticles by a factor of 33 (mass activity) or 21 (exchange current density) relative to unsupported nickel nanoparticles. Density functional theory calculations indicate that the nitrogen-doped support stabilizesmore » the nanoparticle against reconstruction, while nitrogen located at the edge of the nanoparticle tunes local adsorption sites by affecting the d-orbitals of nickel. Here, owing to its high activity and low cost, our catalyst shows significant potential for use in low-cost, high-performance fuel cells.« less

  13. Nickel supported on nitrogen-doped carbon nanotubes as hydrogen oxidation reaction catalyst in alkaline electrolyte.

    PubMed

    Zhuang, Zhongbin; Giles, Stephen A; Zheng, Jie; Jenness, Glen R; Caratzoulas, Stavros; Vlachos, Dionisios G; Yan, Yushan

    2016-01-14

    The development of a low-cost, high-performance platinum-group-metal-free hydroxide exchange membrane fuel cell is hindered by the lack of a hydrogen oxidation reaction catalyst at the anode. Here we report that a composite catalyst, nickel nanoparticles supported on nitrogen-doped carbon nanotubes, has hydrogen oxidation activity similar to platinum-group metals in alkaline electrolyte. Although nitrogen-doped carbon nanotubes are a very poor hydrogen oxidation catalyst, as a support, it increases the catalytic performance of nickel nanoparticles by a factor of 33 (mass activity) or 21 (exchange current density) relative to unsupported nickel nanoparticles. Density functional theory calculations indicate that the nitrogen-doped support stabilizes the nanoparticle against reconstruction, while nitrogen located at the edge of the nanoparticle tunes local adsorption sites by affecting the d-orbitals of nickel. Owing to its high activity and low cost, our catalyst shows significant potential for use in low-cost, high-performance fuel cells.

  14. Nickel supported on nitrogen-doped carbon nanotubes as hydrogen oxidation reaction catalyst in alkaline electrolyte

    PubMed Central

    Zhuang, Zhongbin; Giles, Stephen A.; Zheng, Jie; Jenness, Glen R.; Caratzoulas, Stavros; Vlachos, Dionisios G.; Yan, Yushan

    2016-01-01

    The development of a low-cost, high-performance platinum-group-metal-free hydroxide exchange membrane fuel cell is hindered by the lack of a hydrogen oxidation reaction catalyst at the anode. Here we report that a composite catalyst, nickel nanoparticles supported on nitrogen-doped carbon nanotubes, has hydrogen oxidation activity similar to platinum-group metals in alkaline electrolyte. Although nitrogen-doped carbon nanotubes are a very poor hydrogen oxidation catalyst, as a support, it increases the catalytic performance of nickel nanoparticles by a factor of 33 (mass activity) or 21 (exchange current density) relative to unsupported nickel nanoparticles. Density functional theory calculations indicate that the nitrogen-doped support stabilizes the nanoparticle against reconstruction, while nitrogen located at the edge of the nanoparticle tunes local adsorption sites by affecting the d-orbitals of nickel. Owing to its high activity and low cost, our catalyst shows significant potential for use in low-cost, high-performance fuel cells. PMID:26762466

  15. Structural, optical, photocatalytic and antibacterial activity of zinc oxide and manganese doped zinc oxide nanoparticles

    NASA Astrophysics Data System (ADS)

    Rekha, K.; Nirmala, M.; Nair, Manjula G.; Anukaliani, A.

    2010-08-01

    Polycrystalline ZnO doped with Mn (5 and 10 at%) was prepared by the co-precipitation method. The effect of Mn doping on the photocatalytic, antibacterial activities and the influence of doping concentration on structural, optical properties of nanoparticles were studied. Structural and optical properties of the particles elucidated that the Mn 2+ ions have substituted the Zn 2+ ions without changing the Wurtzite structure of ZnO. The optical spectra showed a blue shift in the absorbance spectrum with increasing dopant concentration. The photocatalytic activities of ZnO powders were evaluated by measuring the degradation of methylene blue (MB) in water under the UV region. It was found that undoped ZnO bleaches MB much faster than manganese doped ZnO upon its exposure to the UV light. The potential toxicity of nanosized ZnO and Mn doped ZnO were investigated using both Gram positive and Gram negative bacteria as test organisms. The results showed that Mn doped ZnO nanoparticles enhanced the antibacterial activity than ZnO nanoparticles.

  16. Oxidative degradation of acid orange 7 using Ag-doped zinc oxide thin films.

    PubMed

    Shinde, S S; Bhosale, C H; Rajpure, K Y

    2012-12-05

    Ag-doped ZnO thin films with preferred c-axis orientation along (002) have been prepared by spray pyrolysis technique in aqueous medium on to the corning glass substrates. The effect of Ag-doping on to the photoelectrochemical, structural, morphological, optical, luminescence, electrical and thermal properties has been investigated. XRD and Raman study indicates that the films have hexagonal (wurtzite) crystal structure. The effect of Ag loading on the photocatalytic activity of Ag-doped ZnO in the degradation of azo dye is studied and results are compared with pure ZnO. The results show that the rate of degradation of azo dye over Ag-doped ZnO is much higher as compared to pure ZnO. Ag doping in ZnO is highly effective and can significantly enhance the photocatalytic degradation and mineralization of azo dye. The enhancement of photocatalytic activity of Ag-doped ZnO thin films is mainly due to their smaller crystallite size and capability for reducing the electron-hole pair recombination. Kinetic parameters have been investigated in terms of a first order rate equation. The rate constant (-k) for this heterogeneous photocatalysis is evaluated as a function of the initial concentration of original species. Substantial reduction in azo dye is achieved as analyzed from COD and TOC studies.

  17. Comparison of beryllium oxide and pyrolytic graphite crucibles for boron doped silicon epitaxy

    SciTech Connect

    Ali, Dyan; Richardson, Christopher J. K.

    2012-11-15

    This article reports on the comparison of beryllium oxide and pyrolytic graphite as crucible liners in a high-temperature effusion cell used for boron doping in silicon grown by molecular beam epitaxy. Secondary ion mass spectroscopy analysis indicates decomposition of the beryllium oxide liner, leading to significant incorporation of beryllium and oxygen in the grown films. The resulting films are of poor crystal quality with rough surfaces and broad x-ray diffraction peaks. Alternatively, the use of pyrolytic graphite crucible liners results in higher quality films.

  18. Ta-doped Anatase TiO2 Epitaxial Film as Transparent Conducting Oxide

    NASA Astrophysics Data System (ADS)

    Hitosugi, Taro; Furubayashi, Yutaka; Ueda, Atsuki; Itabashi, Kinnosuke; Inaba, Kazuhisa; Hirose, Yasushi; Kinoda, Go; Yamamoto, Yukio; Shimada, Toshihiro; Hasegawa, Tetsuya

    2005-08-01

    We present electrical transport and optical properties of Ta-doped TiO2 epitaxial thin films with varying Ta concentration grown by the pulsed laser deposition method. The Ti0.95Ta0.05O2 film exhibited a resistivity of 2.5× 10-4 Ω cm at room temperature, and an internal transmittance of 95% in the visible light region. These values are comparable to those of a widely used transparent conducting oxide (TCO), indium tin oxide. Furthermore, this new material falls into a new category of TCOs that utilizes d electrons.

  19. Determination of active doping in highly resistive boron doped silicon nanocrystals embedded in SiO2 by capacitance voltage measurement on inverted metal oxide semiconductor structure

    NASA Astrophysics Data System (ADS)

    Zhang, Tian; Puthen-Veettil, Binesh; Wu, Lingfeng; Jia, Xuguang; Lin, Ziyun; Yang, Terry Chien-Jen; Conibeer, Gavin; Perez-Wurfl, Ivan

    2015-10-01

    We investigate the Capacitance-Voltage (CV) measurement to study the electrically active boron doping in Si nanocrystals (ncSi) embedded in SiO2. The ncSi thin films with high resistivity (200-400 Ω cm) can be measured by using an inverted metal oxide semiconductor (MOS) structure (Al/ncSi (B)/SiO2/Si). This device structure eliminates the complications from the effects of lateral current flow and the high sheet resistance in standard lateral MOS structures. The characteristic MOS CV curves observed are consistent with the effective p-type doping. The CV modeling method is presented and used to evaluate the electrically active doping concentration. We find that the highly boron doped ncSi films have electrically active doping of 1018-1019 cm-3 despite their high resistivity. The saturation of doping at about 1.4 × 1019 cm-3 and the low doping efficiency less than 5% are observed and discussed. The calculated effective mobility is in the order of 10-3 cm2/V s, indicating strong impurity/defect scattering effect that hinders carriers transport.

  20. Determination of active doping in highly resistive boron doped silicon nanocrystals embedded in SiO{sub 2} by capacitance voltage measurement on inverted metal oxide semiconductor structure

    SciTech Connect

    Zhang, Tian Puthen-Veettil, Binesh; Wu, Lingfeng; Jia, Xuguang; Lin, Ziyun; Yang, Terry Chien-Jen; Conibeer, Gavin; Perez-Wurfl, Ivan

    2015-10-21

    We investigate the Capacitance-Voltage (CV) measurement to study the electrically active boron doping in Si nanocrystals (ncSi) embedded in SiO{sub 2}. The ncSi thin films with high resistivity (200–400 Ω cm) can be measured by using an inverted metal oxide semiconductor (MOS) structure (Al/ncSi (B)/SiO{sub 2}/Si). This device structure eliminates the complications from the effects of lateral current flow and the high sheet resistance in standard lateral MOS structures. The characteristic MOS CV curves observed are consistent with the effective p-type doping. The CV modeling method is presented and used to evaluate the electrically active doping concentration. We find that the highly boron doped ncSi films have electrically active doping of 10{sup 18}–10{sup 19 }cm{sup −3} despite their high resistivity. The saturation of doping at about 1.4 × 10{sup 19 }cm{sup −3} and the low doping efficiency less than 5% are observed and discussed. The calculated effective mobility is in the order of 10{sup −3} cm{sup 2}/V s, indicating strong impurity/defect scattering effect that hinders carriers transport.

  1. Identification of the native defect doping mechanism in amorphous indium zinc oxide thin films studied using ultra high pressure oxidation

    NASA Astrophysics Data System (ADS)

    Lee, Sunghwan; Paine, David C.

    2013-02-01

    The mechanism of native defect doping in amorphous In-Zn-O (a-IZO) has not previously been established but is likely associated with native oxygen defect doping. We have used high pressure oxidation and defect equilibrium analysis to show a -1/6 power dependence of carrier density on oxygen fugacity in a-IZO. This dependency is predicted for oxygen vacancy-like donor defects. Extrapolation of equilibrium constants established at high pressures to atmospheric pressure reveals that the equilibrium carrier density in a-IZO at 200 °C is higher (>1020/cm3) than typical as-deposited channel carrier densities (<1017/cm3). This is consistent with observed increases in channel carrier density and negative threshold voltage shift in annealed a-IZO thin film transistor devices.

  2. Surface functionalization of fluorine-doped tin oxide samples through electrochemical grafting.

    PubMed

    Lamberti, F; Agnoli, S; Brigo, L; Granozzi, G; Giomo, M; Elvassore, N

    2013-12-26

    Transparent conductive oxides are emerging materials in several fields, such as photovoltaics, photoelectrochemistry, and optical biosensing. Their high chemical inertia, which ensured long-term stability on one side, makes challenging the surface modification of transparent conductive oxides; long-term robust modification, high yields, and selective surface modifications are essential prerequisite for any further developments. In this work, we aim at inducing chemical functionality on fluorine-doped tin oxide surfaces (one of the most inexpensive transparent conductive oxide) by means of electrochemical grafting of aryl diazonium cations. The grafted layers are fully characterized by photoemission spectroscopy, cyclic voltammetry, and atomic force microscopy showing linear correlation between surface coverage and degree of modification. The electrochemical barrier effect of modified surfaces was studied at different pH to characterize the chemical nature of the coating. We showed immuno recognition of biotin complex built onto grafted fluorine-doped tin oxides, which opens the perspective of integrating FTO samples with biological-based devices.

  3. Global and local reactivity indexes applied to understand the chemistry of graphene oxide and doped graphene.

    PubMed

    Cortés Arriagada, Diego

    2013-02-01

    At the density functional theory level, the electronic reactivity of oxidized and doped (with N, B, and P) graphene (G) has been analyzed. Molecular hardness and electrophilicity were used as global reactivity descriptors, while those at the local level, Fukui functions, Mulliken charges and molecular electrostatic potential were used in the order to characterize the intramolecular and intermolecular reactivity. These descriptors show that in GO, the global and local reactivity of the basal plane is improved mainly by hydroxyl groups, which improve besides the physisorption of small molecules, while, the active carbon atoms around the functional group would allow enhancement of the consecutively chemisorption. Furthermore, epoxide, carbonyl and carboxyl groups allow mainly enhancement of intermolecular non-covalent interactions. On the other hand, doping with N and B atoms increases the electrophilic character and the reactivity in the bulk. Specifically, in N-doped G, N and around carbon atoms would be able to serve as active sites of detection by frontier-controlled processes, explaining the improvement in electrochemical sensing; in addition, electron-deficient carbon atoms around N enhance the physisorption. Respecting the B-doped G, dopant and carbon atoms adjacent to B act as donor sites, suggesting that adsorption of cations on B-doped G is a frontier-controlled process; moreover, positively-charged B atoms enhance charge-controlled interactions with polarized molecules, and consecutively, in a frontier-controlled step, chemisorption is possible. Finally, P-doping increases the electrophilic reactivity in the bulk; also, P atoms enhance the physisorption of chemical species with negatively-charged centers or lone-pair electrons, and consecutively, chemisorption on P is possible.

  4. Electrical properties of zinc-oxide-based thin-film transistors using strontium-oxide-doped semiconductors

    NASA Astrophysics Data System (ADS)

    Wu, Shao-Hang; Zhang, Nan; Hu, Yong-Sheng; Chen, Hong; Jiang, Da-Peng; Liu, Xing-Yuan

    2015-10-01

    Strontium-zinc-oxide (SrZnO) films forming the semiconductor layers of thin-film transistors (TFTs) are deposited by using ion-assisted electron beam evaporation. Using strontium-oxide-doped semiconductors, the off-state current can be dramatically reduced by three orders of magnitude. This dramatic improvement is attributed to the incorporation of strontium, which suppresses carrier generation, thereby improving the TFT. Additionally, the presence of strontium inhibits the formation of zinc oxide (ZnO) with the hexagonal wurtzite phase and permits the formation of an unusual phase of ZnO, thus significantly changing the surface morphology of ZnO and effectively reducing the trap density of the channel. Project supported by the National Natural Science Foundation of China (Grant No. 6140031454) and the Innovation Program of Chinese Academy of Sciences and State Key Laboratory of Luminescence and Applications.

  5. Ultra-low contact resistance at an epitaxial metal/oxide heterojunction through interstitial site doping

    SciTech Connect

    Chambers, Scott A.; Gu, Meng; Sushko, Petr V.; Yang, Hao; Wang, Chong M.; Browning, Nigel D.

    2013-08-07

    The ability to form reliable, low-resistance Ohmic contacts is of critical importance to the ongoing development of oxide electronics. Most metals form Schottky barriers when deposited on oxide surfaces. Ohmic contacts rarely occur, and the associated contact resistances are not particularly low. Little is known at an atomistic level about what leads to a good Ohmic contact on a wide-gap oxide. Here we describe the structure of a simple, yet exceptionally low-contact resistance Ohmic metal on an important oxide semiconductor -- epitaxial Cr on Nb-doped SrTiO3(001). Heteroepitaxial growth is accompanied by Cr diffusion into the STO and occupation of interstitial sites within the first few atomic planes. Interstitial Cr is ionized and the resulting electrons occupy the STO conduction band, resulting in effective metallization near the interface.

  6. Fluorescent Nanocomposite of Embedded Ceria Nanoparticles in Crosslinked PVA Electrospun Nanofibers

    PubMed Central

    Shehata, Nader; Gaballah, Soha; Samir, Effat; Hamed, Aya; Saad, Marwa

    2016-01-01

    This paper introduces a new fluorescent nanocomposite of electrospun biodegradable nanofibers embedded with optical nanoparticles. In detail, this work introduces the fluorescence properties of PVA nanofibers generated by the electrospinning technique with embedded cerium oxide (ceria) nanoparticles. Under near-ultra violet excitation, the synthesized nanocomposite generates a visible fluorescent emission at 520 nm, varying its intensity peak according to the concentration of in situ embedded ceria nanoparticles. This is due to the fact that the embedded ceria nanoparticles have optical tri-valiant cerium ions, associated with formed oxygen vacancies, with a direct allowed bandgap around 3.5 eV. In addition, the impact of chemical crosslinking of the PVA on the fluorescence emission is studied in both cases of adding ceria nanoparticles in situ or of a post-synthesis addition via a spin-coating mechanism. Other optical and structural characteristics such as absorbance dispersion, direct bandgap, FTIR spectroscopy, and SEM analysis are presented. The synthesized optical nanocomposite could be helpful in different applications such as environmental monitoring and bioimaging.

  7. Fluorescent Nanocomposite of Embedded Ceria Nanoparticles in Crosslinked PVA Electrospun Nanofibers.

    PubMed

    Shehata, Nader; Gaballah, Soha; Samir, Effat; Hamed, Aya; Saad, Marwa

    2016-06-01

    This paper introduces a new fluorescent nanocomposite of electrospun biodegradable nanofibers embedded with optical nanoparticles. In detail, this work introduces the fluorescence properties of PVA nanofibers generated by the electrospinning technique with embedded cerium oxide (ceria) nanoparticles. Under near-ultra violet excitation, the synthesized nanocomposite generates a visible fluorescent emission at 520 nm, varying its intensity peak according to the concentration of in situ embedded ceria nanoparticles. This is due to the fact that the embedded ceria nanoparticles have optical tri-valiant cerium ions, associated with formed oxygen vacancies, with a direct allowed bandgap around 3.5 eV. In addition, the impact of chemical crosslinking of the PVA on the fluorescence emission is studied in both cases of adding ceria nanoparticles in situ or of a post-synthesis addition via a spin-coating mechanism. Other optical and structural characteristics such as absorbance dispersion, direct bandgap, FTIR spectroscopy, and SEM analysis are presented. The synthesized optical nanocomposite could be helpful in different applications such as environmental monitoring and bioimaging.

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

    PubMed

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

    2016-08-26

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

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

    PubMed Central

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

    2016-01-01

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

  10. Ceria nanoparticles stabilized by organic surface coatings activate the lysosome-autophagy system and enhance autophagic clearance.

    PubMed

    Song, Wensi; Soo Lee, Seung; Savini, Marzia; Popp, Lauren; Colvin, Vicki L; Segatori, Laura

    2014-10-28

    Cerium oxide nanoparticles (nanoceria) are widely used in a variety of industrial applications including UV filters and catalysts. The expanding commercial scale production and use of ceria nanoparticles have inevitably increased the risk of release of nanoceria into the environment as well as the risk of human exposure. The use of nanoceria in biomedical applications is also being currently investigated because of its recently characterized antioxidative properties. In this study, we investigated the impact of ceria nanoparticles on the lysosome-autophagy system, the main catabolic pathway that is activated in mammalian cells upon internalization of exogenous material. We tested a battery of ceria nanoparticles functionalized with different types of biocompatible coatings (N-acetylglucosamine, polyethylene glycol and polyvinylpyrrolidone) expected to have minimal effect on lysosomal integrity and function. We found that ceria nanoparticles promote activation of the transcription factor EB, a master regulator of lysosomal function and autophagy, and induce upregulation of genes of the lysosome-autophagy system. We further show that the array of differently functionalized ceria nanoparticles tested in this study enhance autophagic clearance of proteolipid aggregates that accumulate as a result of inefficient function of the lysosome-autophagy system. This study provides a mechanistic understanding of the interaction of ceria nanoparticles with the lysosome-autophagy system and demonstrates that ceria nanoparticles are activators of autophagy and promote clearance of autophagic cargo. These results provide insights for the use of nanoceria in biomedical applications, including drug delivery. These findings will also inform the design of engineered nanoparticles with safe and precisely controlled impact on the environment and the design of nanotherapeutics for the treatment of diseases with defective autophagic function and accumulation of lysosomal storage material.

  11. Morphological Control and Characterization of Monodispersed Ceria Particles

    SciTech Connect

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

    2010-11-24

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

  12. Direct oxidation of hydrocarbons in a solid-oxide fuel cell

    NASA Astrophysics Data System (ADS)

    Park, Seungdoo; Vohs, John M.; Gorte, Raymond J.

    2000-03-01

    The direct electrochemical oxidation of dry hydrocarbon fuels to generate electrical power has the potential to accelerate substantially the use of fuel cells in transportation and distributed-power applications. Most fuel-cell research has involved the use of hydrogen as the fuel, although the practical generation and storage of hydrogen remains an important technological hurdle. Methane has been successfully oxidized electrochemically, but the susceptibility to carbon formation from other hydrocarbons that may be present or poor power densities have prevented the application of this simple fuel in practical applications. Here we report the direct, electrochemical oxidation of various hydrocarbons (methane, ethane, 1-butene, n-butane and toluene) using a solid-oxide fuel cell at 973 and 1,073 K with a composite anode of copper and ceria (or samaria-doped ceria). We demonstrate that the final products of the oxidation are CO2 and water, and that reasonable power densities can be achieved. The observation that a solid-oxide fuel cell can be operated on dry hydrocarbons, including liquid fuels, without reforming, suggests that this type of fuel cell could provide an alternative to hydrogen-based fuel-cell technologies.

  13. Direct oxidation of hydrocarbons in a solid-oxide fuel cell

    PubMed

    Park; Vohs; Gorte

    2000-03-16

    The direct electrochemical oxidation of dry hydrocarbon fuels to generate electrical power has the potential to accelerate substantially the use of fuel cells in transportation and distributed-power applications. Most fuel-cell research has involved the use of hydrogen as the fuel, although the practical generation and storage of hydrogen remains an important technological hurdle. Methane has been successfully oxidized electrochemically, but the susceptibility to carbon formation from other hydrocarbons that may be present or poor power densities have prevented the application of this simple fuel in practical applications. Here we report the direct, electrochemical oxidation of various hydrocarbons (methane, ethane, 1-butene, n-butane and toluene) using a solid-oxide fuel cell at 973 and 1,073 K with a composite anode of copper and ceria (or samaria-doped ceria). We demonstrate that the final products of the oxidation are CO2 and water, and that reasonable power densities can be achieved. The observation that a solid-oxide fuel cell can be operated on dry hydrocarbons, including liquid fuels, without reforming, suggests that this type of fuel cell could provide an alternative to hydrogen-based fuel-cell technologies.

  14. Spectroscopic properties of doped and defective semiconducting oxides from hybrid density functional calculations.

    PubMed

    Di Valentin, Cristiana; Pacchioni, Gianfranco

    2014-11-18

    CONSPECTUS: Very rarely do researchers use metal oxides in their pure and fully stoichiometric form. In most of the countless applications of these compounds, ranging from catalysis to electronic devices, metal oxides are either doped or defective because the most interesting chemical, electronic, optical, and magnetic properties arise when foreign components or defects are introduced in the lattice. Similarly, many metal oxides are diamagnetic materials and do not show a response to specific spectroscopies such as electron paramagnetic resonance (EPR) spectroscopy. However, doped or defective oxides may exhibit an interesting and informative paramagnetic behavior. Doped and defective metal oxides offer an expanding range of applications in contemporary condensed matter science; therefore researchers have devoted enormous effort to the understanding their physical and chemical properties. The interplay between experiment and computation is particularly useful in this field, and contemporary simulation techniques have achieved high accuracies with these materials. In this Account, we show how the direct comparison between spectroscopic experimental and computational data for some selected and relevant materials provides ways to understand and control these complex systems. We focus on the EPR properties and electronic transitions that arise from the presence of dopants and defects in bulk metal oxide materials. We analyze and compare the effect of nitrogen doping in TiO2 and ZnO (two semiconducting oxides) and MgO (a wide gap insulator) and examine the effect of oxygen deficiency in the semiconducting properties of TiO2-x, ZnO1-x, and WO3-x materials. We chose these systems because of their relevance in applications including photocatalysis, touch screens, electrodes in magnetic random access memories, and smart glasses. Density functional theory (DFT) provides the general computational framework used to illustrate the electronic structure of these systems. However

  15. Oxygen ion conduction in barium doped LaInO3 perovskite oxides

    NASA Astrophysics Data System (ADS)

    Kim, Hye-Lim; Kim, Shin; Lee, Kyu-Hyung; Lee, Hong-Lim; Lee, Ki-Tae

    2014-12-01

    Oxygen ion conduction behaviors of the 0-5 mol% excess Ba-doped La0.6Ba0.4InO3-δ cubic perovskite oxides have been investigated to elucidate their potential as electrolyte materials. The highest conductivity, 5.6 × 10-2 S cm-1 at 800 °C, is obtained at the 3 mol% excess Ba-doped composition benefiting from a supplementation of Ba2+ ions on the vacant A-site generated by the volatilization during the heat-treatment processes. Interestingly, all the samples except the undoped composition show curved electrical conductivity behavior in the Arrhenius plot. The activation energy is 0.50-0.52 eV in the high-temperature region above 900 °C, which is slightly lower than that of the doped LaGaO3 system. Moreover, all the samples show significantly lower activation energy values of both the high- and low-temperature regions compared with yttria-stabilized zirconia. The 3 mol% excess Ba-doped La1-xBaxInO3-δ (0.4 ≤ x ≤ 0.8) sample has also been studied. All of the compositions show a cubic perovskite structure and a nearly pure oxygen ion conduction behavior in a dry atmosphere even when p(O2) = 1atm. The composition of x = 0.4 exhibits the highest oxygen ion conductivities.

  16. Aluminum-doped lithium nickel cobalt oxide electrodes for high-power lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Chen, C. H.; Liu, J.; Stoll, M. E.; Henriksen, G.; Vissers, D. R.; Amine, K.

    Non-doped and aluminum-doped LiNi 0.8Co 0.2O 2 cathodes from three industrial developers coupled with graphite anodes were made into lithium-ion cells for high-power applications. The powder morphology of the active cathode materials was examined by a scanning electron microscope. The electrochemical performance of these cells was investigated by hybrid pulse power characterization (HPPC) testing, accelerated aging, and AC impedance measurement of symmetric cells. Although all of the fresh cells are found to meet and exceed the power requirements set by PNGV, the power capability of those cells with non-doped LiNi 0.8Co 0.2O 2 cathodes fades rapidly due to the rise of the cell impedance. Al-doping is found very effective to suppress the cell impedance rise by stabilizing the charge-transfer impedance on the cathode side. The stabilization mechanism may be related to the low average oxidation state of nickel ions in the cathode. The powder morphology also plays a secondary role in determining the impedance stabilization.

  17. Impact of hole doping on spin transition in perovskite-type cobalt oxides.

    PubMed

    Che, Xiangli; Li, Liping; Hu, Wanbiao; Li, Guangshe

    2016-06-28

    Series of perovskite PrCo1-xNixO3-δ (x = 0-0.4) were prepared and carefully investigated to understand the spin state transition driven by hole doping and further to reveal the effect of spin state transition on electronic conduction. It is shown that with increasing doping level, the transition temperature Ts for Co(3+) ions from low-spin (LS) to intermediate-spin (IS) reduces from 211.9 K for x = 0 to 190.5 K for x = 0.4. XPS and FT-IR spectra demonstrate that hole doping promoted this transition due to a larger Jahn-Teller distortion. Moreover, a thermal activation of spin disorder caused by thermal population of the spin states for Co ions has a great impact on the electrical transport of these perovskite samples. This work may shed light on the comprehension of spin transition in cobalt oxides through hole doping, which is promising for finding new strategies of enhancing electronic conduction, especially for energy and catalysis applications.

  18. Structural and photoluminescence properties of terbium-doped zinc oxide nanoparticles

    NASA Astrophysics Data System (ADS)

    Ningthoujam Surajkumar, Singh; Shougaijam Dorendrajit, Singh; Sanoujam Dhiren, Meetei

    2014-05-01

    We present in this paper a study of the structural and photoluminescence (PL) properties of terbium (Tb) doped zinc oxide (ZnO) nanoparticles synthesized by a simple low temperature chemical precipitation method, using zinc acetate and terbium nitrate in an isopropanol medium with diethanolamine (DEA) as the capping agent at 60 °C. The as-prepared samples were heat treated and the PL of the annealed samples were studied. The prepared nanoparticles were characterized with X-ray diffraction (XRD). The XRD patterns show the pattern of typical ZnO nanoparticles and correspond with the standard XRD pattern given by JCPDS card No. 36-1451, showing the hexagonal phase structure. The PL intensity was enhanced due to Tb3+ doping, and it decreased at higher concentrations of Tb3+ doping after reaching a certain optimum concentration. The PL spectra of Tb3+ doped samples exhibited blue, bluish green, and green emissions at 460 nm (5D3 - 7F3), 484 nm (5D4 - 7F6), and 530 nm (5D4 - 7F5), respectively, which were more intense than the emissions for the undoped ZnO sample. Based on the results, an energy level schematic diagram was proposed to explain the possible electron transition processes.

  19. Distribution, elimination, and biopersistence to 90 days of a systemically introduced 30 nm ceria-engineered nanomaterial in rats.

    PubMed

    Yokel, Robert A; Au, Tu C; MacPhail, Robert; Hardas, Sarita S; Butterfield, D Allan; Sultana, Rukhsana; Goodman, Michael; Tseng, Michael T; Dan, Mo; Haghnazar, Hamed; Unrine, Jason M; Graham, Uschi M; Wu, Peng; Grulke, Eric A

    2012-05-01

    Nanoceria is used as a catalyst in diesel fuel, as an abrasive in printed circuit manufacture, and is being pursued as an antioxidant therapeutic. Our objective is to extend previous findings showing that there were no reductions of cerium in organs of the mononuclear phagocyte (reticuloendothelial) system up to 30 days after a single nanoscale ceria administration. An ~5% aqueous dispersion of citrate-stabilized 30 nm ceria, synthesized and characterized in-house, or vehicle, was iv infused into rats terminated 1, 7, 30, or 90 days later. Cageside observations were obtained daily, body weight weekly. Daily urinary and fecal cerium outputs were quantified for 2 weeks. Nine organs were weighed and samples collected from 14 tissues/organs/systems, blood and cerebrospinal fluid for cerium determination. Histology and oxidative stress were assessed. Less than 1% of the nanoceria was excreted in the first 2 weeks, 98% in feces. Body weight gain was initially impaired. Spleen weight was significantly increased in some ceria-treated groups, associated with abnormalities. Ceria was primarily retained in the spleen, liver, and bone marrow. There was little decrease of ceria in any tissue over the 90 days. Granulomas were observed in the liver. Time-dependent oxidative stress changes were seen in the liver and spleen. Nanoscale ceria was persistently retained by organs of the mononuclear phagocyte system, associated with adverse changes. The results support concern about the long-term fate and adverse effects of inert nanoscale metal oxides that distribute throughout the body, are persistently retained, and produce adverse changes.

  20. Reconsidering the possibility of room temperature ferromagnetism in Mn-doped zirconium oxide

    NASA Astrophysics Data System (ADS)

    Chakraborty, Akash; Bouzerar, Georges

    2013-12-01

    The possibility to induce long-range ferromagnetic order by doping oxides with transition metal ions has become a very exciting challenge in the last decade. Theoretically, it has been claimed that Mn-doped ZrO2 could be a very promising spintronic candidate and that high critical temperatures could be already achieved even for a low Mn concentration. Some experiments have reported room temperature ferromagnetism (RT-FM) whilst some others only paramagnetism. When observed, the nature of RT-FM appears to be controversial and not clearly understood. In this study, we propose to clarify and shed light on some of theses existing issues. A detailed study of the critical temperatures and low-energy magnetic excitations in Mn-doped ZrO2 is performed. We show that the Curie temperatures were largely overestimated previously, due to the inadequate treatment of both thermal and transverse fluctuations, and disorder. It appears that the Mn-Mn couplings cannot explain the observed RT-FM. We argue, that this can be attributed to the interaction between large moments induced in the vicinity of the manganese. This is similar to the non-magnetic defect-induced ferromagnetism reported in oxides, semiconductors and graphene/graphite.

  1. Antimony-Doped Tin Oxide Thin Films Grown by Home Made Spray Pyrolysis Technique

    NASA Astrophysics Data System (ADS)

    Yusuf, Gbadebo; Babatola, Babatunde Keji; Ishola, Abdulahi Dimeji; Awodugba, Ayodeji O.; Solar cell Collaboration

    2016-03-01

    Transparent conducting antimony-doped tin oxide (ATO) films have been deposited on glass substrates by home made spray pyrolysis technique. The structural, electrical and optical properties of the ATO films have been investigated as a function of Sb-doping level and annealing temperature. The optimum target composition for high conductivity and low resistivity was found to be 20 wt. % SnSb2 + 90 wt. ATO. Under optimized deposition conditions of 450oC annealing temperature, electrical resistivity of 5.2×10-4 Ω -cm, sheet resistance of 16.4 Ω/sq, average optical transmittance of 86% in the visible range, and average optical band-gap of 3.34eV were obtained. The film deposited at lower annealing temperature shows a relatively rough, loosely bound slightly porous surface morphology while the film deposited at higher annealing temperature shows uniformly distributed grains of greater size. Keywords: Annealing, Doping, Homemade spray pyrolysis, Tin oxide, Resistivity

  2. Dysprosium-doped cadmium oxide as a gateway material for mid-infrared plasmonics.

    PubMed

    Sachet, Edward; Shelton, Christopher T; Harris, Joshua S; Gaddy, Benjamin E; Irving, Douglas L; Curtarolo, Stefano; Donovan, Brian F; Hopkins, Patrick E; Sharma, Peter A; Sharma, Ana Lima; Ihlefeld, Jon; Franzen, Stefan; Maria, Jon-Paul

    2015-04-01

    The interest in plasmonic technologies surrounds many emergent optoelectronic applications, such as plasmon lasers, transistors, sensors and information storage. Although plasmonic materials for ultraviolet-visible and near-infrared wavelengths have been found, the mid-infrared range remains a challenge to address: few known systems can achieve subwavelength optical confinement with low loss in this range. With a combination of experiments and ab initio modelling, here we demonstrate an extreme peak of electron mobility in Dy-doped CdO that is achieved through accurate 'defect equilibrium engineering'. In so doing, we create a tunable plasmon host that satisfies the criteria for mid-infrared spectrum plasmonics, and overcomes the losses seen in conventional plasmonic materials. In particular, extrinsic doping pins the CdO Fermi level above the conduction band minimum and it increases the formation energy of native oxygen vacancies, thus reducing their populations by several orders of magnitude. The substitutional lattice strain induced by Dy doping is sufficiently small, allowing mobility values around 500 cm(2) V(-1) s(-1) for carrier densities above 10(20) cm(-3). Our work shows that CdO:Dy is a model system for intrinsic and extrinsic manipulation of defects affecting electrical, optical and thermal properties, that oxide conductors are ideal candidates for plasmonic devices and that the defect engineering approach for property optimization is generally applicable to other conducting metal oxides.

  3. Dysprosium-doped cadmium oxide as a gateway material for mid-infrared plasmonics

    DOE PAGES

    Sachet, Edward; Shelton, Christopher T.; Harris, Joshua S.; ...

    2015-02-16

    The interest in plasmonic technologies surrounds many emergent optoelectronic applications, such as plasmon lasers, transistors, sensors and information storage. Although plasmonic materials for ultraviolet–visible and near-infrared wavelengths have been found, the mid-infrared range remains a challenge to address: few known systems can achieve subwavelength optical confinement with low loss in this range. With a combination of experiments and ab initio modelling, here we demonstrate an extreme peak of electron mobility in Dy-doped CdO that is achieved through accurate ‘defect equilibrium engineering’. In so doing, we create a tunable plasmon host that satisfies the criteria for mid-infrared spectrum plasmonics, and overcomesmore » the losses seen in conventional plasmonic materials. In particular, extrinsic doping pins the CdO Fermi level above the conduction band minimum and it increases the formation energy of native oxygen vacancies, thus reducing their populations by several orders of magnitude. The substitutional lattice strain induced by Dy doping is sufficiently small, allowing mobility values around 500 cm2 V–1 s–1 for carrier densities above 1020 cm–3. As a result, our work shows that CdO:Dy is a model system for intrinsic and extrinsic manipulation of defects affecting electrical, optical and thermal properties, that oxide conductors are ideal candidates for plasmonic devices and that the defect engineering approach for property optimization is generally applicable to other conducting metal oxides.« less

  4. Morphological and substrate effects on the electrochemical behaviour of doped tin oxide anodes

    NASA Astrophysics Data System (ADS)

    Miljkovic, Bojan

    Films of Sb-doped SnO2 were successfully fabricated on a Ti substrate through precursor application by spin coating followed by a thermal decomposition process. The dependence of film characteristics on fabrication temperature was studied in the range of 500 to 800°C. An optimum electrocatalytic response was found for a firing temperature of 600°C. This was attributed to a balance between Sb-doping effects, titanium substrate oxidation, and film morphological development. This was determined through observation of the morphology, crystallographic texture, and electrochemical characteristics, such as the oxygen evolution potential (OEP), ferri/ferrocyanide electron transfer reaction, and phenol oxidation. Polymerization of phenol and the subsequent deactivation of the anode surface was related to the active surface area of the SnO2 film. Preliminary studies on the effect of Ni-Sb and Zn-Sb co-doping of SnO2 were conducted. The addition of Ni was shown to decrease the film conductivity while maintaining the OEP. Inclusion of Zn resulted in the formation of a second phase, Zn2SnO4 , which effectively inhibited oxygen evolution causing an increase in the OEP.

  5. Energy transfer mechanisms in heavy metal oxide glasses doped with lanthanide ions

    NASA Astrophysics Data System (ADS)

    Ragin, Tomasz; Zmojda, Jacek; Kochanowicz, Marcin; Miluski, Piotr; Dorosz, Dominik

    2016-09-01

    In this paper, glasses based on bismuth, germanium, gallium and sodium oxides have been synthesized in terms of low phonon energy (724 cm-1) and high thermal stability (ΔT = 127°C). Synthesis process have been optimized using low vacuum conditions (approx. 60 mBar) to improve the transmittance in the mid-infrared region and decrease the content of hydroxide groups in the material structure. Glass doped with erbium ions has been pumped with high power diode (λexc = 980 nm) to obtain luminescence in the band of 2.7 μm as a result of Er3+: 4I11/2 -> 4I13/2 radiative transition. For analysis of emission properties and energy transfer mechanisms, glasses co-doped with Er3+/Ho3+, Er3+/Pr3+, Er3+/Nd3+ ions have been synthesized. Obtained results indicated energy transfer phenomenon between lanthanide ions and elements forming the glass matrix. This demonstrates that developed heavy metal oxide glass doped with optimal rare earth elements system is an attractive material for mid-infrared applications.

  6. Seeded growth of metal-doped plasmonic oxide heterodimer nanocrystals and their chemical transformation.

    PubMed

    Ye, Xingchen; Reifsnyder Hickey, Danielle; Fei, Jiayang; Diroll, Benjamin T; Paik, Taejong; Chen, Jun; Murray, Christopher B

    2014-04-02

    We have developed a generalized seeded-growth methodology for the synthesis of monodisperse metal-doped plasmonic oxide heterodimer nanocrystals (NCs) with a near-unity morphological yield. Using indium-doped cadmium oxide (ICO) as an example, we show that a wide variety of preformed metal NCs (Au, Pt, Pd, FePt, etc.) can serve as the seeds for the tailored synthesis of metal-ICO heterodimers with exquisite size, shape, and composition control, facilitated by the delayed nucleation mechanism of the CdO phase. The metal-ICO heterodimers exhibit broadly tunable near-infrared localized surface plasmon resonances, and dual plasmonic bands are observed for Au-ICO heterodimers. We further demonstrate that the oxide domain of the Au-ICO heterodimers can be selectively and controllably transformed into a series of partially and completely hollow cadmium chalcogenide nanoarchitectures with unprecedented structural complexity, leaving the metal domain intact. Our work not only represents an exciting addition to the rapidly expanding library of chemical reactions that produce colloidal hybrid NCs, but it also provides a general route for the bottom-up chemical design of multicomponent metal-oxide-semiconductor NCs in a rational and sequential manner.

  7. Aqueous Co-precipitation of Pd-doped Cerium Oxide Nanoparticles: Chemistry Structure and Particle Growth

    SciTech Connect

    Liang H.; Zhang L.; Raitano J.M.; He G.; Akey A.J.; Herman I.P.; Chan S.-W.

    2012-01-01

    Nanoparticles of palladium-doped cerium oxide (Pd-CeO{sub 2}) have been prepared by aqueous co-precipitation resulting in a single phase cubic structure after calcination according to X-ray diffraction (XRD). Inhomogeneous strain, calculated using the Williamson-Hall method, was found to increase with palladium content, and the lattice contracts slightly, relative to nano-cerium oxide, as palladium content is increased. Moreover, high resolution transmission electron microscopy reveals some instances of defective microstructure. These factors combined imply that palladium is in solid solution with CeO{sub 2} in these nanoparticles, but palladium (II) oxide (PdO) peaks in the Raman spectra indicate that solid solution formation is partial and that highly dispersed PdO is present as well as the solid solution. Nevertheless, the addition of palladium to the CeO{sub 2} lattice inhibits the growth of the 6% Pd-CeO{sub 2} particles compared to pure CeO{sub 2} between 600 and 850 C. Activation energies for grain growth of 54 {+-} 7 and 79 {+-} 8 kJ/mol were determined for 6% Pd-CeO{sub 2} and pure CeO{sub 2}, respectively, along with pre-exponential Arrhenius factors of 10 for the doped sample and 600 for pure cerium oxide.

  8. On the structure of vanadia supported on ceria nanoshapes

    SciTech Connect

    Wu, Zili; Li, Meijun; Overbury, Steven {Steve} H

    2012-01-01

    Vanadia supported on ceria nanocrystals with defined surface planes, i.e., ceria nanoshapes including rods, cubes and octahedra were successfully synthesized. The effect of surface structure of these ceria nanoshapes on the structure of surface vanadia species as well as the formation of CeVO4 was investigated in details via in situ visible and UV Raman spectroscopy. The surface vanadia species on ceria nanoshapes evolve from monomeric vanadia to dimeric, trimeric, polymeric vanadia, and eventually crystalline V2O5 and CeVO4 as a function of vanadia loading. As expected, the nanoshaped ceria provides a rather homogeneous platform for anchoring vanadia, especially at low vanadia loading leading to only monomeric species, in contrast to the co-existence of different vanadia species on polycrystalline ceria even at extremely low vanadia loading. The formation of CeVO4 from the reaction between surface vanadia species and ceria was compared on the three ceria nanoshapes with similar surface vanadia density. It was found that both the surface structure and amount of defect sites of the ceria nanoshapes play major roles in the production of CeVO4. The easiest formation of CeVO4 on ceria rods is attributed to the lowest surface oxygen vacancy formation energy and the largest amount of defect sites available on the rods surface.

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

    DOE PAGES

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

    2016-11-21

    The stability of palladium supported on ceria (Pd/CeO2) was studied during liquid flow transfer hydrogenation using primary and secondary alcohols as hydrogen donors. For primary alcohols, the ceria support was reduced to cerium hydroxy carbonate within 14 h and was a contributing factor toward catalyst deactivation. For secondary alcohols, cerium hydroxy carbonate was not observed during the same time period and the catalyst was stable upon prolonged reaction. Regeneration through oxidation/reduction does not restore initial activity likely due to irreversible catalyst restructuring. Lastly, a deactivation mechanism involving C–C scission of acyl and carboxylate intermediates is proposed.

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

    SciTech Connect

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

    2016-11-21

    The stability of palladium supported on ceria (Pd/CeO2) was studied during liquid flow transfer hydrogenation using primary and secondary alcohols as hydrogen donors. For primary alcohols, the ceria support was reduced to cerium hydroxy carbonate within 14 h and was a contributing factor toward catalyst deactivation. For secondary alcohols, cerium hydroxy carbonate was not observed during the same time period and the catalyst was stable upon prolonged reaction. Regeneration through oxidation/reduction does not restore initial activity likely due to irreversible catalyst restructuring. Lastly, a deactivation mechanism involving C–C scission of acyl and carboxylate intermediates is proposed.

  11. Nitrogen-doped and simultaneously reduced graphene oxide with superior dispersion as electrocatalysts for oxygen reduction reaction

    SciTech Connect

    Lee, Cheol-Ho; Yun, Jin-Mun; Lee, Sungho; Jo, Seong Mu; Yoo, Sung Jong; Cho, Eun Ae; Khil, Myung-Seob; Joh, Han-Ik

    2014-11-15

    Nitrogen doped graphene oxide (Nr-GO) with properties suitable for electrocatalysts is easily synthesized using phenylhydrazine as a reductant at relatively low temperature. The reducing agent removes various oxygen functional groups bonded to graphene oxide and simultaneously dope the nitrogen atoms bonded with phenyl group all over the basal planes and edge sites of the graphene. The Nr-GO exhibits remarkable electrocatalytic activities for oxygen reduction reaction compared to the commercial carbon black and graphene oxide due to the electronic modification of the graphene structure. In addition, Nr-GO shows excellent dispersibility in various solvent due to the dopant molecules.

  12. Raman and Photoluminescence Spectroscopy of Er(3+) Doped Heavy Metal Oxide Glasses

    NASA Technical Reports Server (NTRS)

    Dyer, Keith; Pan, Zheng-Da; Morgan, Steve

    1997-01-01

    The potential applications of rare-earth ion doped materials include fiber lasers which can be pumped conveniently by infrared semiconductor laser diodes. The host material systems most widely studied are fluoride crystals and glasses because fluorides have low nonradiative relaxation rates due to their lower phonon energies. However, the mechanical strength, chemical durability and temperature stability of the oxide glasses are generally much better than fluoride glasses. The objective of this research was to investigate the optical and spectroscopic properties of Er(3+)-doped lead-germanate and lead-tellurium-germanate glasses. The maximum vibrational energy of lead-tellurium-germanate glasses are in the range of 740-820/cm, intermediate between those of silicate (1150/cm) and fluoride (530/cm) glasses.

  13. Flame-made niobium doped zinc oxide nanoparticles in bulk heterojunction solar cells

    NASA Astrophysics Data System (ADS)

    Kruefu, Viruntachar; Peterson, Eric; Khantha, Chanitpa; Siriwong, Chawarat; Phanichphant, Sukon; Carroll, David L.

    2010-08-01

    We report fabrication and measurement of bulk heterojunction solar cells utilizing a poly(3-hexylthiophene) (P3HT), phenyl-C61-butyric acid methyl ester (PCBM) composite loaded with different concentrations of niobium doped zinc oxide (Nb/ZnO) nanoparticles produced by flame spray pyrolysis. Nanoparticles with different niobium concentrations were compared, along with devices without Nb/ZnO nanoparticles and with undoped ZnO nanoparticles. It was found that niobium doping leads to a slight increase in open circuit voltage and an increase in short circuit current that scales with niobium concentration. Additional comparison was made between the nanoparticles with 3% niobium by weight to unloaded devices. These also showed a similar open circuit voltage increase and an increase in current that scales with Nb/ZnO nanoparticle concentration to 30% by volume and drops off at 33% Nb/ZnO by volume. Possible mechanisms for these improvements are discussed.

  14. Photocatalysts of Cr Doped TiO2 Film Prepared by Micro Arc Oxidation

    NASA Astrophysics Data System (ADS)

    Wan, Li; Li, Jian-feng; Feng, Jia-you; Sun, Wei; Mao, Zong-qiang

    2008-10-01

    A series of Cr doped TiO2 films were prepared by micro arc oxidation (MAO) using an electrolyte of Na3PO4+K2Cr2O7. X-ray diffraction and scanning electron microscopy revealed that the films mainly consisted of anatase phase with a porous surface morphology. The films have an excellent photocatalytic effect for degradation of methylene blue and decomposition of water under visible light illumination. This arises from the formation of Cr3+/Cr4+ and oxygen vacancy energy levels owing to Cr doping. The former reduces the electron-hole recombination chance, while the latter generates a new gap between the conduction band (CB) and valence band (VB) of TiO2, which lowers the photo energy of the excited electron in the VB to the oxygen vacancy states. The mechanisms for film synthesis during the MAO process are also presented.

  15. Permanent optical doping of amorphous metal oxide semiconductors by deep ultraviolet irradiation at room temperature

    SciTech Connect

    Seo, Hyungtak; Cho, Young-Je; Bobade, Santosh M.; Park, Kyoung-Youn; Choi, Duck-Kyun; Kim, Jinwoo; Lee, Jaegab

    2010-05-31

    We report an investigation of two photon ultraviolet (UV) irradiation induced permanent n-type doping of amorphous InGaZnO (a-IGZO) at room temperature. The photoinduced excess electrons were donated to change the Fermi-level to a conduction band edge under the UV irradiation, owing to the hole scavenging process at the oxide interface. The use of optically n-doped a-IGZO channel increased the carrier density to approx10{sup 18} cm{sup -3} from the background level of 10{sup 16} cm{sup -3}, as well as the comprehensive enhancement upon UV irradiation of a-IGZO thin film transistor parameters, such as an on-off current ratio at approx10{sup 8} and field-effect mobility at 22.7 cm{sup 2}/V s.

  16. Microstructure evolution of Al-doped zinc oxide and Sn-doped indium oxide deposited by radio-frequency magnetron sputtering: A comparison

    SciTech Connect

    Nie, Man; Bikowski, Andre; Ellmer, Klaus

    2015-04-21

    The microstructure and morphology evolution of Al-doped zinc oxide (AZO) and Sn-doped indium oxide (ITO) thin films on borosilicate glass substrates deposited by radio-frequency magnetron sputtering at room temperature (RT) and 300 °C were investigated by X-ray diffraction and atomic force microscopy (AFM). One-dimensional power spectral density (1DPSD) functions derived from the AFM profiles, which can be used to distinguish different growth mechanisms, were used to compare the microstructure scaling behavior of the thin films. The rms roughness R{sub q} evolves with film thickness as a power law, R{sub q} ∼ d{sub f}{sup β}, and different growth exponents β were found for AZO and ITO films. For AZO films, β of 1.47 and 0.56 are obtained for RT and 300 °C depositions, respectively, which are caused by the high compressive stress in the film at RT and relaxation of the stress at 300 °C. While for ITO films, β{sub 1} = 0.14 and β{sub 2} = 0.64 for RT, and β{sub 1} = 0.89 and β{sub 2} = 0.3 for 300 °C deposition are obtained, respectively, which is related to the strong competition between the surface diffusion and shadowing effect and/or grain growth. Electrical properties of both materials as a function of film thickness were also compared. By the modified Fuchs-Sondheimer model fitting of the electrical transport in both materials, different nucleation states are pointed out for both types of films.

  17. Al-doped zinc oxide nanocomposites with enhanced thermoelectric properties.

    PubMed

    Jood, Priyanka; Mehta, Rutvik J; Zhang, Yanliang; Peleckis, Germanas; Wang, Xiaolin; Siegel, Richard W; Borca-Tasciuc, Theo; Dou, Shi Xue; Ramanath, Ganpati

    2011-10-12

    ZnO is a promising high figure-of-merit (ZT) thermoelectric material for power harvesting from heat due to its high melting point, high electrical conductivity σ, and Seebeck coefficient α, but its practical use is limited by a high lattice thermal conductivity κ(L). Here, we report Al-containing ZnO nanocomposites with up to a factor of 20 lower κ(L) than non-nanostructured ZnO, while retaining bulklike α and σ. We show that enhanced phonon scattering promoted by Al-induced grain refinement and ZnAl(2)O(4) nanoprecipitates presages ultralow κ ∼ 2 Wm( -1) K(-1) at 1000 K. The high α∼ -300 μV K(-1) and high σ ∼ 1-10(4) Ω(-1 )m(-1) result from an offsetting of the nanostructuring-induced mobility decrease by high, and nondegenerate, carrier concentrations obtained via excitation from shallow Al donor states. The resultant ZT ∼ 0.44 at 1000 K is 50% higher than that for the best non-nanostructured counterpart material at the same temperature and holds promise for engineering advanced oxide-based high-ZT thermoelectrics for applications.

  18. DC electrical conductivity measurements for pure and titanium oxide doped KDP Crystals grown by gel medium

    NASA Astrophysics Data System (ADS)

    Mareeswaran, S.; Asaithambi, T.

    2016-10-01

    Now a day's crystals are the pillars of current technology. Crystals are applied in various fields like fiber optic communications, electronic industry, photonic industry, etc. Crystal growth is an interesting and innovative field in the subject of physics, chemistry, material science, metallurgy, chemical engineering, mineralogy and crystallography. In recent decades optically good quality of pure and metal doped KDP crystals have been grown by gel growth method in room temperature and its characterizations were studied. Gel method is a very simple and one of the easiest methods among the various crystal growth methods. Potassium dihydrogen phosphate KH2PO4 (KDP) continues to be an interesting material both academically and technologically. KDP is a delegate of hydrogen bonded materials which possess very good electrical and nonlinear optical properties in addition to interesting electro-optic properties. We made an attempt to grow pure and titanium oxide doped KDP crystals with various doping concentrations (0.002, 0.004, 0.006, 0.008 and 0.010) using gel method. The grown crystals were collected after 20 days. We get crystals with good quality and shaped crystals. The dc electrical conductivity (resistance, capacitance and dielectric constant) values of the above grown crystals were measured at two different frequencies (1KHz and 100 Hz) with a temperature range of 500C to 1200C using simple two probe setup with Q band digital LCR meter present in our lab. The electrical conductivity increases with the increase of temperature. Dielectric constants value of titanium oxide doped KDP crystal was slightly decreased compared with pure KDP crystals. Results were discussed in details.

  19. Tc enhancement of excess Sr-doped Bi-2223 oxides by control of oxygen content

    NASA Astrophysics Data System (ADS)

    Miura, N.; Sakata, F.; Shimizu, Y.; Deshimaru, Y.; Yamazoe, N.

    1994-12-01

    The superconducting properties of excess Sr-doped 2223 phase samples, Bi 1.84Pb 0.34Sr 1.91+xCa 2.03Cu 3.06O y ( x=0.1, 0.3, 0.5, 1.0, 1.5), were examined. All the oxides as-prepared showed almost the same Tc of 109∼110 K, After heat-treatment in He at 600 °C for 3h, however, Tc increased up to 114∼115 K for the oxides with x=0.3∼, and decreased down to 102∼106 K for x=0∼0.1. The oxygen contents of the oxides as determined by iodometry increased with increasing x and slightly decreased with the heat-treatment in He. The heat treatment also brough about small increases in lattice constant of c-axis.

  20. Effects of process parameters on sheet resistance uniformity of fluorine-doped tin oxide thin films.

    PubMed

    Hudaya, Chairul; Park, Ji Hun; Lee, Joong Kee

    2012-01-05

    An alternative indium-free material for transparent conducting oxides of fluorine-doped tin oxide [FTO] thin films deposited on polyethylene terephthalate [PET] was prepared by electron cyclotron resonance - metal organic chemical vapor deposition [ECR-MOCVD]. One of the essential issues regarding metal oxide film deposition is the sheet resistance uniformity of the film. Variations in process parameters, in this case, working and bubbler pressures of ECR-MOCVD, can lead to a change in resistance uniformity. Both the optical transmittance and electrical resistance uniformity of FTO film-coated PET were investigated. The result shows that sheet resistance uniformity and the transmittance of the film are affected significantly by the changes in bubbler pressure but are less influenced by the working pressure of the ECR-MOCVD system.

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

    PubMed Central

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

    2014-01-01

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

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

    PubMed

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

    2013-11-19

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

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

    PubMed Central

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

    2014-01-01

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

  4. A room temperature nitric oxide gas sensor based on a copper-ion-doped polyaniline/tungsten oxide nanocomposite.

    PubMed

    Wang, Shih-Han; Shen, Chi-Yen; Su, Jian-Ming; Chang, Shiang-Wen

    2015-03-24

    The parts-per-billion-level nitric oxide (NO) gas sensing capability of a copper-ion-doped polyaniline/tungsten oxide nanocomposite (Cu(2+)/PANI/WO3) film coated on a Rayleigh surface acoustic wave device was investigated. The sensor developed in this study was sensitive to NO gas at room temperature in dry nitrogen. The surface morphology, dopant distribution, and electric properties were characterized using scanning electron microscopy, energy-dispersive X-ray spectroscopy mapping, and Hall effect measurements, respectively. The Cu(2+)/PANI/WO3 film exhibited high NO gas sensitivity and selectivity as well as long-term stability. At 1 ppb of NO, a signal with a frequency shift of 4.3 ppm and a signal-to-noise ratio of 17 was observed. The sensor exhibited distinct selectivity toward NO gas with no substantial response to O2, NH3 and CO2 gases.

  5. Microscopic annealing process and its impact on superconductivity in T'-structure electron-doped copper oxides.

    PubMed

    Kang, Hye Jung; Dai, Pengcheng; Campbell, Branton J; Chupas, Peter J; Rosenkranz, Stephan; Lee, Peter L; Huang, Qingzhen; Li, Shiliang; Komiya, Seiki; Ando, Yoichi

    2007-03-01

    High-transition-temperature superconductivity arises in copper oxides when holes or electrons are doped into the CuO(2) planes of their insulating parent compounds. Whereas hole doping quickly induces metallic behaviour and superconductivity in many cuprates, electron doping alone is insufficient in materials such as R(2)CuO(4) (R is Nd, Pr, La, Ce and so on), where it is necessary to anneal an as-grown sample in a low-oxygen environment to remove a tiny amount of oxygen in order to induce superconductivity. Here we show that the microscopic process of oxygen reduction repairs Cu deficiencies in the as-grown materials and creates oxygen vacancies in the stoichiometric CuO(2) planes, effectively reducing disorder and providing itinerant carriers for superconductivity. The resolution of this long-standing materials issue suggests that the fundamental mechanism for superconductivity is the same for electron- and hole-doped copper oxides.

  6. Influence of low concentration V and Co oxide doping on the dissolution behaviors of simplified nuclear waste glasses

    SciTech Connect

    Lu, Xiaonan; Neeway, James J.; Ryan, Joseph V.; Du, Jincheng

    2016-11-01

    Transition metal oxides are commonly present in nuclear waste and they can alter the structure, property and especially dissolution behaviors of the glasses used for waste immobilization. In this paper, we investigated vanadium and cobalt oxide induced structural and properties changes, especially dissolution behaviors, of International Simple Glass (ISG), a model nuclear waste glass system. Static chemical durability tests were performed at 90 °C with a pH value of 7 and a surface-area-to-solution-volume of 200 m-1 for 112 days on three glasses: ISG, ISG doped with 0.5 mol% Co2O3, and ISG doped with 2.0 mol% V2O5. ICP-MS was used to analyze the dissolved ion concentrations. It was found that doping with vanadium and cobalt oxide, even at the low doping concentration, significantly reduced the extent of the ISG glass dissolution. Differential Scanning Calorimetry (DSC) analysis showed that vanadium oxide doping reduced the glass transition temperature (Tg) while cobalt oxide did not significantly change the Tg of ISG. X-ray diffraction (XRD), Raman spectrometry and scanning electron microscopy (SEM) were used to analyze the glass samples before and after corrosion to understand the phase and microstructure changes.

  7. Charge transfer and formation of reduced Ce3+ upon adsorption of metal atoms at the ceria (110) surface.

    PubMed

    Nolan, Michael

    2012-04-07

    The modification of cerium dioxide with nanoscale metal clusters is intensely researched for catalysis applications, with gold, silver, and copper having been particularly well studied. The interaction of the metal cluster with ceria is driven principally by a localised interaction between a small number of metal atoms (as small as one) and the surface and understanding the fundamentals of the interaction of metal atoms with ceria surfaces is therefore of great interest. Much attention has been focused on the interaction of metals with the (111) surface of ceria, since this is the most stable surface and can be grown as films, which are probed experimentally. However, nanostructures exposing other surfaces such as (110) show high activity for reactions including CO oxidation and require further study; these nanostructures could be modified by deposition of metal atoms or small clusters, but there is no information to date on the atomic level details of metal-ceria interactions involving the (110) surface. This paper presents the results of density functional theory (DFT) corrected for on-site Coulomb interactions (DFT+U) calculations of the adsorption of a number of different metal atoms at an extended ceria (110) surface; the metals are Au, Ag, Cu, Al, Ga, In, La, Ce, V, Cr, and Fe. Upon adsorption all metals are oxidised, transferring electron(s) to the surface, resulting in localised surface distortions. The precise details depend on the identity of the metal atom. Au, Ag, Cu each transfer one electron to the surface, reducing one Ce ion to Ce(3+), while of the trivalent metals, Al and La are fully oxidised, but Ga and In are only partially oxidised. Ce and the transition metals are also partially oxidised, with the number of reduced Ce ions possible in this surface no more than three per adsorbed metal atom. The predicted oxidation states of the adsorbed metal atoms should be testable in experiments on ceria nanostructures modified with metal atoms.

  8. Charge transfer and formation of reduced Ce{sup 3+} upon adsorption of metal atoms at the ceria (110) surface

    SciTech Connect

    Nolan, Michael

    2012-04-07

    The modification of cerium dioxide with nanoscale metal clusters is intensely researched for catalysis applications, with gold, silver, and copper having been particularly well studied. The interaction of the metal cluster with ceria is driven principally by a localised interaction between a small number of metal atoms (as small as one) and the surface and understanding the fundamentals of the interaction of metal atoms with ceria surfaces is therefore of great interest. Much attention has been focused on the interaction of metals with the (111) surface of ceria, since this is the most stable surface and can be grown as films, which are probed experimentally. However, nanostructures exposing other surfaces such as (110) show high activity for reactions including CO oxidation and require further study; these nanostructures could be modified by deposition of metal atoms or small clusters, but there is no information to date on the atomic level details of metal-ceria interactions involving the (110) surface. This paper presents the results of density functional theory (DFT) corrected for on-site Coulomb interactions (DFT+U) calculations of the adsorption of a number of different metal atoms at an extended ceria (110) surface; the metals are Au, Ag, Cu, Al, Ga, In, La, Ce, V, Cr, and Fe. Upon adsorption all metals are oxidised, transferring electron(s) to the surface, resulting in localised surface distortions. The precise details depend on the identity of the metal atom. Au, Ag, Cu each transfer one electron to the surface, reducing one Ce ion to Ce{sup 3+}, while of the trivalent metals, Al and La are fully oxidised, but Ga and In are only partially oxidised. Ce and the transition metals are also partially oxidised, with the number of reduced Ce ions possible in this surface no more than three per adsorbed metal atom. The predicted oxidation states of the adsorbed metal atoms should be testable in experiments on ceria nanostructures modified with metal atoms.

  9. Rare-earth metal oxide doped transparent mesoporous silica plates under non-aqueous condition as a potential UV sensor.

    PubMed

    Lee, Sang-Joon; Park, Sung Soo; Lee, Sang Hyun; Hong, Sang-Hyun; Ha, Chang-Sik

    2013-11-01

    Transparent mesoporous silica plates doped with rare-earth metal oxide were prepared using solvent-evaporation method based on the self-organization between structure-directing agent and silicate in a non-aqueous solvent. A triblock copolymer, Pluronic (F127 or P123), was used as the structure-directing agent, while tetraethyl orthosilicate (TEOS) was used as a silica source. The pore diameter and the surface area of the mesoporous silica plate prepared with the optimized conditions were ca 40 A and 600 m2 g(-1), respectively, for both structure-directing agent. Rare-earth metal oxides (Eu, Tb, Tm oxide) in mesochannel were formed via one-step synthetic route based on the preparation method of a silica plate. Optical properties of rare-earth metal oxide-doped mesoporous silica plates were investigated by UV irradiation and photoluminescence (PL) spectroscopy. Under the exitation wavelength of 254 nm, the doped mesoporous silica plates emitted red, green and blue for Eu, Tb and Tm oxides, respectively. Rare-earth metal oxide-doped mesoporous silica plates showed enhanced PL intensity compared to that of the bulk rare-earth metal oxide.

  10. PEGylated silver doped zinc oxide nanoparticles as novel photosensitizers for photodynamic therapy against Leishmania.

    PubMed

    Nadhman, Akhtar; Nazir, Samina; Khan, Malik Ihsanullah; Arooj, Syeda; Bakhtiar, Muhammad; Shahnaz, Gul; Yasinzai, Masoom

    2014-12-01

    We describe daylight responsive silver (Ag) doped semiconductor nanoparticles of zinc oxide (DSNs) for photodynamic therapy (PDT) against Leishmania. The developed materials were characterized by X-ray diffraction analysis (XRD), Rutherford backscattering (RBS), diffused reflectance spectroscopy (DRS), and band-gap analysis. The Ag doped semiconductor nanoparticles of zinc oxide were PEGylated to enhance their biocompatibility. The DSNs demonstrated effective daylight response in the PDT of Leishmania protozoans, through the generation of reactive oxygen species (ROS) with a quantum yield of 0.13 by nondoped zinc oxide nanoparticles (NDSN) whereas 0.28 by DSNs. None of the nanoparticles have shown any antileishmanial activity in dark, confirming that only ROS produced in the daylight were involved in the killing of leishmanial cells. Furthermore, the synthesized nanoparticles were found biocompatible. Using reactive oxygen species scavengers, cell death was attributable mainly to 77-83% singlet oxygen and 18-27% hydroxyl radical. The nanoparticles caused permeability of the cell membrane, leading to the death of parasites. Further, the uptake of nanoparticles by Leishmania cells was confirmed by inductively coupled plasma atomic emission spectroscopy (ICP-AES). We believe that these DSNs are widely applicable for the PDT of leishmaniasis, cancers, and other infections due to daylight response.

  11. Possible Superconductivity Induced by Strong Spin-Orbit Coupling in Carrier Doped Iridium Oxides Insulators

    NASA Astrophysics Data System (ADS)

    Nishiguchi, Kazutaka; Shirakawa, Tomonori; Watanabe, Hiroshi; Arita, Ryotaro; Yunoki, Seiji

    2014-03-01

    5 d transition metal oxide Sr2IrO4 and its relevant Iridium oxides have attracted much interest because of exotic properties arising from highly entangled spin and orbital degrees of freedom due to strong spin-orbit coupling (SOC). Sr2IrO4 crystalizes in the layered perovskite structure, similar to cuprates. Five 5 d electrons in Ir occupy its t2 g orbitals which are split by strong SOC, locally inducing an effective total angular momentum Jeff = 1 / 2 , analogous to a S = 1 / 2 state in cuprates. Because of the similarities to cuprates, the possibility of superconductivity (SC) in Iridium oxides has been expected theoretically once mobile carriers are introduced into the Jeff = 1 / 2 antiferromagnetic insulator. To study theoretically possible SC in carrier doped Sr2IrO4, we investigate a three-orbital Hubbard model with SOC. By solving the Eliashberg equation in the random phase approximation, we find that Jeff = 1 / 2 antiferromagnetic fluctuations favor dx2 -y2-wave SC with a mixture of singlet and triplet Cooper pairings. We will also discuss the particle-hole asymmetry of the SC induced by electron and hole doping.

  12. High Performance, Low Temperature Solution-Processed Barium and Strontium Doped Oxide Thin Film Transistors

    PubMed Central

    2013-01-01

    Amorphous mixed metal oxides are emerging as high performance semiconductors for thin film transistor (TFT) applications, with indium gallium zinc oxide, InGaZnO (IGZO), being one of the most widely studied and best performing systems. Here, we investigate alkaline earth (barium or strontium) doped InBa(Sr)ZnO as alternative, semiconducting channel layers and compare their performance of the electrical stress stability with IGZO. In films fabricated by solution-processing from metal alkoxide precursors and annealed to 450 °C we achieve high field-effect electron mobility up to 26 cm2 V–1 s–1. We show that it is possible to solution-process these materials at low process temperature (225–200 °C yielding mobilities up to 4.4 cm2 V–1 s–1) and demonstrate a facile “ink-on-demand” process for these materials which utilizes the alcoholysis reaction of alkyl metal precursors to negate the need for complex synthesis and purification protocols. Electrical bias stress measurements which can serve as a figure of merit for performance stability for a TFT device reveal Sr- and Ba-doped semiconductors to exhibit enhanced electrical stability and reduced threshold voltage shift compared to IGZO irrespective of the process temperature and preparation method. This enhancement in stability can be attributed to the higher Gibbs energy of oxidation of barium and strontium compared to gallium. PMID:24511184

  13. Enhanced organic photovoltaic properties via structural modifications in PEDOT:PSS due to graphene oxide doping

    SciTech Connect

    Goutham, Raj P.; Sandhya, Rani V.; Kanwat, Anil; Jang, Jin

    2016-02-15

    Highlights: • Graphene oxide(GO) blended with PEDOT:PSS is used as HTL for PTB7:PCBM BHJ solar cells. • Increase in conductivity due to structural alterations in PEDOT:PSS by GO addition. • The structural alterations are reaveled under Raman spectroscopy, XPS and AFM. • PEDOT:PSS changed to extended coil due to addition of GO to PEDOT:PSS. • Enhanced conductivity after GO addition to PEDOT:PSS resulted in enhanced PCE. - Abstract: Poly(3,4-thylenedioxythiophene):poly(styrene sulfonate), PEDOT:PSS is a well-known conductive polymer for hole transport in organic devices, the properties of which can be enhanced by doping. Common dopants are metal oxides and nanoparticles. In this study, addition of graphene oxide (GO) to PEDOT:PSS as a dopant is addressed in organic photovoltaics (OPVs). With GO doping, electrical conductivity and transport properties of PEDOT:PSS increases due to structural alterations in the presence of −COOH and −OH functional groups in GO. These structural alterations have been revealed under detailed study of Raman spectra, X-ray photoelectron spectroscopy (XPS) analysis, Topographical and conductive Atom force microscopy (AFM/C-AFM) mapping. OPVs fabricated using PEDOT:PSS: GO (5:1) as a hole transport layer (HTL) exhibited a power conversion efficiency (PCE) of 7.68%, which was higher than the 7.01% that was obtained for the OPVs using pristine PEDOT:PSS.

  14. Ultrasonic-assisted degradation of phenazopyridine with a combination of Sm-doped ZnO nanoparticles and inorganic oxidants.

    PubMed

    Eskandarloo, Hamed; Badiei, Alireza; Behnajady, Mohammad A; Ziarani, Ghodsi Mohammadi

    2016-01-01

    Pure and samarium doped ZnO nanoparticles were synthesized by a sonochemical method and characterized by TEM, SEM, EDX, XRD, Pl, and DRS techniques. The average crystallite size of pure and Sm-doped ZnO nanoparticles was about 20 nm. The sonocatalytic activity of pure and Sm-doped ZnO nanoparticles was considered toward degradation of phenazopyridine as a model organic contaminant. The Sm-doped ZnO nanoparticles with Sm concentration of 0.4 mol% indicated a higher sonocatalytic activity (59%) than the pure ZnO (51%) and other Sm-doped ZnO nanoparticles. It was believed that Sm(3+) ion with optimal concentration (0.4 mol%) can act as superficial trapping for electrons in the conduction band of ZnO and delayed the recombination of charge carriers. The influence of the nature and concentration of various oxidants, including periodate, hydrogen peroxide, peroxymonosulfate, and peroxydisulfate on the sonocatalytic activity of Sm-doped ZnO nanoparticles was studied. The influence of the oxidants concentration (0.2-1.4 g L(-1)) on the degradation rate was established by the 3D response surface and the 2D contour plots. The results demonstrated that the utilizing of oxidants in combination with Sm-doped ZnO resulting in rapid removal of contaminant, which can be referable to a dual role of oxidants; (i) scavenging the generated electrons in the conduction band of ZnO and (ii) creating highly reactive radical species under ultrasonic irradiation. It was found that the Sm-doped ZnO and periodate combination is the most efficient catalytic system under ultrasonic irradiation.

  15. Electrical Study of Trapped Charges in Copper-Doped Zinc Oxide Films by Scanning Probe Microscopy for Nonvolatile Memory Applications

    PubMed Central

    Su, Ting; Zhang, Haifeng

    2017-01-01

    Charge trapping properties of electrons and holes in copper-doped zinc oxide (ZnO:Cu) films have been studied by scanning probe microscopy. We investigated the surface potential dependence on the voltage and duration applied to the copper-doped ZnO films by Kelvin probe force microscopy. It is found that the Fermi Level of the 8 at.% Cu-doped ZnO films shifted by 0.53 eV comparing to undoped ZnO films. This shift indicates significant change in the electronic structure and energy balance in Cu-doped ZnO films. The Fermi Level (work function) of zinc oxide films can be tuned by Cu doping, which are important for developing this functional material. In addition, Kelvin probe force microscopy measurements demonstrate that the nature of contact at Pt-coated tip/ZnO:Cu interface is changed from Schottky contact to Ohmic contact by increasing sufficient amount of Cu ions. The charge trapping property of the ZnO films enhance greatly by Cu doping (~10 at.%). The improved stable bipolar charge trapping properties indicate that copper-doped ZnO films are promising for nonvolatile memory applications. PMID:28135335

  16. Polaronic contributions to oxidation and hole conductivity in acceptor-doped BaZrO3

    NASA Astrophysics Data System (ADS)

    Lindman, Anders; Erhart, Paul; Wahnström, Göran

    2016-08-01

    Acceptor-doped perovskite oxides like BaZrO3 are showing great potential as materials for renewable energy technologies where hydrogen acts an energy carrier, such as solid oxide fuel cells and hydrogen separation membranes. While ionic transport in these materials has been investigated intensively, the electronic counterpart has received much less attention and further exploration in this field is required. Here, we use density functional theory (DFT) to study hole polarons and their impact on hole conductivity in Y-doped BaZrO3. Three different approaches have been used to remedy the self-interaction error of local and semilocal exchange-correlation functionals: DFT +U , pSIC-DFT, and hybrid functionals. Self-trapped holes are found to be energetically favorable by about -0.1 eV and the presence of yttrium results in further stabilization. Polaron migration is predicted to occur through intraoctahedral transfer and polaron rotational processes, which are associated with adiabatic barriers of about 0.1 eV. However, the rather small energies associated with polaron formation and migration suggest that the hole becomes delocalized and bandlike at elevated temperatures. These results together with an endothermic oxidation reaction [A. Lindman, P. Erhart, and G. Wahnström, Phys. Rev. B 91, 245114 (2015), 10.1103/PhysRevB.91.245114] yield a picture that is consistent with experimental data for the hole conductivity. The results we present here provide new insight into hole transport in acceptor-doped BaZrO3 and similar materials, which will be of value in the future development of sustainable technologies.

  17. Characterization of mesoporosity in ceria particles using electron microscopy.

    PubMed

    Shih, Shao-Ju; Herrero, Pilar Rodrigo; Li, Guoqiang; Chen, Chin-Yi; Lozano-Perez, Sergio

    2011-02-01

    The geometry and three-dimensional (3D) morphology of the ceria particles synthesized by spray pyrolysis (SP) from two different precursors--cerium acetate hydrate and cerium nitrate hydrate (CeA and CeN ceria particles)--were characterized by transmission electron microscopy and electron tomography. Results were compared with surface area measurements, confirming that the surface area of CeA ceria particles is twice as large as that of CeN ceria particles. This result was supported by 3D microstructural observations, which have revealed that CeA ceria particles contain open pores (connected to surfaces) and closed pores (embedded in particles), while CeN ceria particles only contained closed pores. This experimental result suggests that the type of porosity is controlled by the precursors and could be related to their melting temperature during the heating process in SP.

  18. Cu-doped zinc oxide and its polythiophene composites: preparation and antibacterial properties.

    PubMed

    Ma, Ge; Liang, Xiaoxi; Li, Liangchao; Qiao, Ru; Jiang, Donghua; Ding, Yan; Chen, Haifeng

    2014-04-01

    Cu-doped zinc oxide and its polythiophene nanocomposites were prepared by the Sol-Gel and in situ polymerization methods, respectively. The structures, morphologies and compositions of the samples were characterized. The antibacterial properties of the samples on three kinds of strains were determined by using powder inhibition zones, minimum inhibitory concentrations and minimal bactericidal concentrations. The study confirmed that the antibacterial activities of the composites were better than those of their each component. The antibacterial mechanisms of the samples were discussed further.

  19. Paramagnon excitations' theory for resonant inelastic X-ray scattering in doped plane copper oxide superconductors

    NASA Astrophysics Data System (ADS)

    Larionov, I. A.

    2015-04-01

    A relaxation function theory with paramagnon excitations for doped S = 1 / 2 two-dimensional Heisenberg antiferromagnetic system in the paramagnetic state is given in view of magnetic response of high-Tc copper oxide superconductors as obtained by resonant inelastic X-ray scattering (RIXS). The results of the theory on Nd(La)-Ba(Sr)-Cu-O and Y-Ba-Cu-O family compounds give fair agreement without especially adjusted parameters to RIXS data. It is shown that RIXS data analysis depends on paramagnon damping and thus affected by approximations made for dynamic spin susceptibility.

  20. Insights into electrical characteristics of silicon doped hafnium oxide ferroelectric thin films

    NASA Astrophysics Data System (ADS)

    Zhou, Dayu; Müller, J.; Xu, Jin; Knebel, S.; Bräuhaus, D.; Schröder, U.

    2012-02-01

    Silicon doped hafnium oxide thin films were recently discovered to exhibit ferroelectricity. In the present study, metal-ferroelectric-metal capacitors with Si:HfO2 thin films as ferroelectric material and TiN as electrodes have been characterized with respect to capacitance and current density as functions of temperature and applied voltage. Polarity asymmetry of the frequency dependent coercive field was explained by interfacial effects. No ferroelectric-paraelectric phase transition was observed at temperatures up to 478 K. Clear distinctions between current evolutions with or without polarization switching were correlated to the time competition between the measurement and the response of relaxation mechanisms.

  1. Synthesis and assembly of barium-doped iron oxide nanoparticles and nanomagnets.

    PubMed

    Wu, Liheng; Shen, Bo; Sun, Shouheng

    2015-10-21

    A facile organic-phase synthesis of monodisperse barium-doped iron oxide (Ba-Fe-O) nanoparticles (NPs) is reported. The Ba-Fe-O NPs can be converted into hexagonal barium ferrite NPs at 700 °C, showing strong ferromagnetic properties with H(c) reaching 5260 Oe and M(s) at 54 emu g(-1). Moreover, the Ba-Fe-O NPs can be assembled into densely packed magnetic arrays, providing a unique model system for studying nanomagnetism and for nanomagnetic applications.

  2. CRYSTALLINE CHROMIUM DOPED ALUMINUM OXIDE (RUBY) USE AS A LUMINESCENT SCREEN FOR PROTON BEAMS.

    SciTech Connect

    BROWN,K.A.; GASSNER,D.M.

    1999-03-29

    In our search for a better luminescent screen material, we tested pieces of mono-crystalline chromium doped aluminum oxide (more commonly known as a ruby) using a 24 GeV proton beam. Due to the large variations in beam intensity and species which are run at the Alternating Gradient Synchrotron (AGS), we hope to find a material which can sufficiently luminesce, is compatible in vacuum, and maintain its performance level over extended use. Results from frame grabbed video camera images using a variety of neutral density filters are presented.

  3. Effect of S-doping on structural, optical and electrochemical properties of vanadium oxide thin films prepared by spray pyrolysis

    NASA Astrophysics Data System (ADS)

    Mousavi, M.; Kompany, A.; Shahtahmasebi, N.; Bagheri-Mohagheghi, M.-M.

    2013-12-01

    In this research, S-doped vanadium oxide thin films, with doping levels from 0 to 40 at.%, are prepared by spray pyrolysis technique on glass substrates. For electrochemical measurements, the films were deposited on florin-tin oxide coated glass substrates. The effect of S-doping on structural, electrical, optical and electrochemical properties of vanadium oxide thin films was studied. The x-ray diffractometer analysis indicated that most of the samples have cubic β-V2O5 phase structure with preferred orientation along [200]. With increase in the doping levels, the structure of the samples tends to be amorphous. The scanning electron microscopy images show that the structure of the samples is nanobelt-shaped and the width of the nanobelts decreases from nearly 100 to 40 nm with increase in the S concentration. With increase in the S-doping level, the sheet resistance and the optical band gap increase from 940 to 4015 kΩ/square and 2.41 to 2.7 eV, respectively. The cyclic voltammogram results obtained for different samples show that the undoped sample is expanded and the sample prepared at 20 at.% S-doping level has sharper anodic and cathodic peaks.

  4. Cerium-modified doped strontium titanate compositions for solid oxide fuel cell anodes and electrodes for other electrochemical devices

    DOEpatents

    Marina, Olga A [Richland, WA; Stevenson, Jeffry W [Richland, WA

    2010-11-23

    The present invention provides novel compositions that find advantageous use in making electrodes for electrochemical cells and electrochemical devices such as solid oxide fuel cells, electrolyzers, sensors, pumps and the like, the compositions comprising cerium-modified doped strontium titanate. The invention also provides novel methods for making and using anode material compositions and solid oxide fuel cells and solid oxide fuel cell assemblies having anodes comprising the compositions.

  5. Cerium-modified doped strontium titanate compositions for solid oxide fuel cell anodes and electrodes for other electrochemical devices

    DOEpatents

    Marina, Olga A [Richland, WA; Stevenson, Jeffry W [Richland, WA

    2010-03-02

    The present invention provides novel compositions that find advantageous use in making electrodes for electrochemical cells and electrochemical devices such as solid oxide fuel cells, electrolyzers, sensors, pumps and the like, the compositions comprising cerium-modified doped strontium titanate. The invention also provides novel methods for making and using anode material compositions and solid oxide fuel cells and solid oxide fuel cell assemblies having anodes comprising the compositions.

  6. Solution-processed gadolinium doped indium-oxide thin-film transistors with oxide passivation

    NASA Astrophysics Data System (ADS)

    Lee, Seung-Hun; Kim, Taehun; Lee, Jihun; Avis, Christophe; Jang, Jin

    2017-03-01

    We studied the effect of Gd doping on the structural properties of solution processed, crystalline In2O3 for thin-film transistor (TFT) application. With increasing Gd in In2O3 up to 20%, the material structure changes into amorphous phase, and the oxygen vacancy concentration decreases from 15.4 to 8.4%, and M-OH bonds from 33.5 to 23.7%. The field-effect mobility for the Gd doped In2O3 TFTs decreases and threshold voltage shifts to the positive voltage with increasing Gd concentration. In addition, the stability of the solution processed TFTs can also be improved by increasing Gd concentration. As a result, the optimum Gd concentration is found to be ˜5% in In2O3 and the 5% Gd doped In2O3 TFTs with the Y2O3 passivation layer exhibit the linear mobility of 9.74 cm2/V s, the threshold voltage of -0.27 V, the subthreshold swing of 79 mV/dec., and excellent bias stability.

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

    SciTech Connect

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

    2013-01-01

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

  8. Optical and electrical properties of lithium doped nickel oxide films deposited by spray pyrolysis onto alumina substrates

    NASA Astrophysics Data System (ADS)

    Garduño, I. A.; Alonso, J. C.; Bizarro, M.; Ortega, R.; Rodríguez-Fernández, L.; Ortiz, A.

    2010-11-01

    Non-doped and lithium doped nickel oxide crystalline films have been prepared onto quartz and crystalline alumina substrates at high substrate temperature (600 °C) by the pneumatic spray pyrolysis process using nickel and lithium acetates as source materials. The structure of all the deposited films was the crystalline cubic phase related to NiO, although this crystalline structure was a little bit stressed for the films with higher lithium concentration. The grain size had values between 60 and 70 nm, almost independently of doping concentration. The non-doped and lithium doped films have an energy band gap of the order of 3.6 eV. Hot point probe results show that all deposited films have a p-type semiconductor behavior. From current-voltage measurements it was observed that the electrical resistivity decreases as the lithium concentration increases, indicating that the doping action of lithium is carried out. The electrical resistivity changed from 10 6 Ω cm for the non-doped films up to 10 2 Ω cm for the films prepared with the highest doping concentration.

  9. Mid- to long-wavelength infrared surface plasmon properties in doped zinc oxides

    NASA Astrophysics Data System (ADS)

    Cleary, Justin W.; Snure, Michael; Leedy, Kevin D.; Look, David C.; Eyink, Kurt; Tiwari, Ashutosh

    2012-09-01

    This work investigates properties of surface plasmons on doped metal oxides in the 2-20 μm wavelength regime. By varying the stoichiometry in pulse laser deposited Ga and Al doped ZnO, the plasmonic properties can be controlled via a fluctuating free carrier concentration. This deterministic approach may enable one to develop the most appropriate stoichometry of ZnAlO and ZnGaO in regards to specific plasmonic applications for particular IR wavelengths. Presented are theoretical and experimental investigations pertaining to ZnAlO and ZnGaO as surface plasmon host materials. Samples are fabricated via pulsed laser deposition and characterized by infrared ellipsometry and Hall-effect measurements. Complex permittivity spectra are presented, as well as plasmon properties such as the field propagation lengths and penetration depths, in the infrared range of interest. Drude considerations are utilized to determine how the optical properties may change with doping. Finite element simulations verify these plasmonic properties. These materials not only offer potential use as IR plasmon hosts for sensor applications, but also offer new integrated device possibilities due to stoichiometric control of electrical and optical properties.

  10. Significant Enhancement in the Conductivity of Al-Doped Zinc Oxide thin Films for TCO Application

    NASA Astrophysics Data System (ADS)

    Mohite, R. M.; Ansari, J. N.; Roy, A. S.; Kothawale, R. R.

    2016-03-01

    Nanostructured Al-doped Zinc oxide (ZnO) thin films were deposited on glass substrate by chemical bath deposition (CBD) using aqueous zinc nitrate solution and subjected for different characterizations. Effect of Al3+ substitution on the properties of ZnO annealed at 400∘C was studied by XRD and UV-Vis for structural studies, SEM and TEM for surface morphology and DC four probe resistivity measurements for electrical properties. Al3+ substitution does not influence the morphology and well-known peaks related to wurtzite structure of ZnO. Electron microscopy (SEM and TEM) confirms rod shaped Al-doped ZnO nanocrystals with average width of 50nm. The optical band gap determined by UV-Visible spectroscopy was found to be in the range 3.37eV to 3.44eV. An EPR spectrum of AZO reveals peak at g=1.96 is due to shallow donors Zn interstitial. The DC electrical resistivity measurements of Al-doped ZnO show a minimum resistivity of 3.77×10-2Ω-cm. Therefore, these samples have potential use in n-type window layer in optoelectronic devices, organic solar cells, photonic crystals, photo-detectors, light emitting diodes (LEDs), gas sensors and chemical sensors.

  11. Paramagnetic dysprosium-doped zinc oxide thin films grown by pulsed-laser deposition

    SciTech Connect

    Lo, Fang-Yuh Ting, Yi-Chieh; Chou, Kai-Chieh; Hsieh, Tsung-Chun; Ye, Cin-Wei; Hsu, Yung-Yuan; Liu, Hsiang-Lin; Chern, Ming-Yau

    2015-06-07

    Dysprosium(Dy)-doped zinc oxide (Dy:ZnO) thin films were fabricated on c-oriented sapphire substrate by pulsed-laser deposition with doping concentration ranging from 1 to 10 at. %. X-ray diffraction (XRD), Raman-scattering, optical transmission spectroscopy, and spectroscopic ellipsometry revealed incorporation of Dy into ZnO host matrix without secondary phase. Solubility limit of Dy in ZnO under our deposition condition was between 5 and 10 at. % according to XRD and Raman-scattering characteristics. Optical transmission spectroscopy and spectroscopic ellipsometry also showed increase in both transmittance in ultraviolet regime and band gap of Dy:ZnO with increasing Dy density. Zinc vacancies and zinc interstitials were identified by photoluminescence spectroscopy as the defects accompanied with Dy incorporation. Magnetic investigations with a superconducting quantum interference device showed paramagnetism without long-range order for all Dy:ZnO thin films, and a hint of antiferromagnetic alignment of Dy impurities was observed at highest doping concentration—indicating the overall contribution of zinc vacancies and zinc interstitials to magnetic interaction was either neutral or toward antiferromagnetic. From our investigations, Dy:ZnO thin films could be useful for spin alignment and magneto-optical applications.

  12. Structural studies of lithium boro tellurite glasses doped with praseodymium and samarium oxides

    SciTech Connect

    Damas, Pedro; Coelho, João; Hungerford, Graham; Hussain, N. Sooraj

    2012-11-15

    Graphical abstract: [TeO{sub 4}] trigonal bipyramid structural unit, which is formed by two unequivalent pair of oxygen atoms: two equatorial oxygens (O{sub eq}) and two axial oxygens (O{sub ax}). Highlights: ► Pr{sup 3+} and Sm{sup 3+} doped LBT glasses have been prepared and characterized. ► LBT glasses present normal surfaces without metallic clusters. ► Raman spectra revealed the network modifying behaviour of dopant ions. -- Abstract: This paper reports the preparation and structural studies of praseodymium and samarium (0.5, 2 and 4 mol%) oxide doped lithium boro tellurite glasses. These materials were prepared by the quenching technique in a ceramic crucible at 950 °C. Structural characterization was performed by Raman spectroscopy, Scanning Electron Microscopy and Energy Dispersive X-ray spectroscopy techniques. Results from Raman analysis are in good agreement with those reported in the literature, revealing a normal glass structure for the host material. Understanding on how the glasses internal structure changed when the doping concentration increases was also assessed.

  13. Paramagnetic dysprosium-doped zinc oxide thin films grown by pulsed-laser deposition

    NASA Astrophysics Data System (ADS)

    Lo, Fang-Yuh; Ting, Yi-Chieh; Chou, Kai-Chieh; Hsieh, Tsung-Chun; Ye, Cin-Wei; Hsu, Yung-Yuan; Chern, Ming-Yau; Liu, Hsiang-Lin

    2015-06-01

    Dysprosium(Dy)-doped zinc oxide (Dy:ZnO) thin films were fabricated on c-oriented sapphire substrate by pulsed-laser deposition with doping concentration ranging from 1 to 10 at. %. X-ray diffraction (XRD), Raman-scattering, optical transmission spectroscopy, and spectroscopic ellipsometry revealed incorporation of Dy into ZnO host matrix without secondary phase. Solubility limit of Dy in ZnO under our deposition condition was between 5 and 10 at. % according to XRD and Raman-scattering characteristics. Optical transmission spectroscopy and spectroscopic ellipsometry also showed increase in both transmittance in ultraviolet regime and band gap of Dy:ZnO with increasing Dy density. Zinc vacancies and zinc interstitials were identified by photoluminescence spectroscopy as the defects accompanied with Dy incorporation. Magnetic investigations with a superconducting quantum interference device showed paramagnetism without long-range order for all Dy:ZnO thin films, and a hint of antiferromagnetic alignment of Dy impurities was observed at highest doping concentration—indicating the overall contribution of zinc vacancies and zinc interstitials to magnetic interaction was either neutral or toward antiferromagnetic. From our investigations, Dy:ZnO thin films could be useful for spin alignment and magneto-optical applications.

  14. Emergence of particle-hole symmetry near optimal doping in high-temperature copper oxide superconductors

    NASA Astrophysics Data System (ADS)

    Chakraborty, Shiladitya; Galanakis, Dimitrios; Phillips, Philip

    2010-12-01

    High-temperature copper oxide superconductors (cuprates) display unconventional physics when they are lightly doped whereas the standard theory of metals prevails in the opposite regime. For example, the thermoelectric power, that is the voltage that develops across a sample in response to a temperature gradient, changes sign abruptly near optimal doping in a wide class of cuprates, a stark departure from the standard theory of metals in which the thermopower vanishes only when one electron exists per site. We show that this effect arises from proximity to a state in which particle-hole symmetry is dynamically generated. The operative mechanism is dynamical spectral weight transfer from states that lie at least 2 eV away from the chemical potential. We show that the sign change is reproduced quantitatively within the Hubbard model for moderate values of the on-site repulsion, U . For sufficiently large values of on-site repulsion, for example, U=20t ( t the hopping matrix element), dynamical spectral weight transfer attenuates and our calculated results for the thermopower are in prefect agreement with exact atomic limit. The emergent particle-hole symmetry close to optimal doping points to pairing in the cuprates being driven by high-energy electronic states.

  15. Gallium-doped indium oxide nanoleaves: Structural characterization, growth mechanism and optical properties

    NASA Astrophysics Data System (ADS)

    Liu, Lizhu; Chen, Yiqing; Guo, Linliang; Guo, Taibo; Zhu, Yunqing; Su, Yong; Jia, Chong; Wei, Meiqin; Cheng, Yinfen

    2011-11-01

    The novel two-dimensional (2-D) Ga-doped In2O3 nanoleaves are synthesized by a simple one-step carbonthermal evaporation method using Cu-Sn alloy as the substrates. Two basic parts construct this leaf-like nanostructure: a long central trunk and two tapered nanoribbons in symmetric distribution in relation to the trunk. The Ga-In-O alloy particles are located at or close to the tips of the central trunks and serve as catalysts for the central trunk growth by the self-catalytic vapor-liquid-solid (VLS) mechanism. And the homoepitaxial growth of tapered nanoribbon on the surface of the central trunk can be explained by vapor-solid (VS) mechanism. The room-temperature photoluminescence (PL) measurement of this nanoscaled Ga-doped In2O3 transparent conducting oxide (TCO) detected two blue peaks located at 432 nm and 481 nm, respectively, which can be used by Ru-based dye and indicates potential application in dye-sensitized solar cells (DSSCs). The successful preparation of this novel 2-D Ga-doped In2O3 nanoleaves not only enriches the synthesis of TCO materials, but also provides new blocks in future architecture of functional nano-devices.

  16. Application of N-Doped Three-Dimensional Reduced Graphene Oxide Aerogel to Thin Film Loudspeaker.

    PubMed

    Kim, Choong Sun; Lee, Kyung Eun; Lee, Jung-Min; Kim, Sang Ouk; Cho, Byung Jin; Choi, Jung-Woo

    2016-08-31

    We built a thermoacoustic loudspeaker employing N-doped three-dimensional reduced graphene oxide aerogel (N-rGOA) based on a simple template-free fabrication method. A two-step fabrication process, which includes freeze-drying and reduction/doping, was used to realize a three-dimensional, freestanding, and porous graphene-based loudspeaker, whose macroscopic structure can be easily modulated. The simplified fabrication process also allows the control of structural properties of the N-rGOAs, including density and area. Taking advantage of the facile fabrication process, we fabricated and analyzed thermoacoustic loudspeakers with different structural properties. The anlayses showed that a N-rGOA with lower density and larger area can produce a higher sound pressure level (SPL). Furthermore, the resistance of the proposed loudspeaker can be easily controlled through heteroatom doping, thereby helping to generate higher SPL per unit driving voltage. Our success in constructing an array of optimized N-rGOAs able to withstand input power as high as 40 W demonstrates that a practical thermoacoustic loudspeaker can be fabricated using the proposed mass-producible solution-based process.

  17. FAST TRACK COMMUNICATION: Influence of doping on the properties of vanadium oxide gel films

    NASA Astrophysics Data System (ADS)

    Pergament, A. L.; Velichko, A. A.; Berezina, O. Ya; Kazakova, E. L.; Kuldin, N. A.; Artyukhin, D. V.

    2008-10-01

    The effect of doping with H and W on the properties of V2O5 and VO2 derived from V2O5 gel has been studied. It is shown that the treatment of V2O5 in low-temperature RF hydrogen plasma for 1-10 min leads to either hydration of vanadium pentoxide or its reduction (depending on the treatment conditions) to lower vanadium oxides. For some samples, which are subject to plasma treatment in the discharge active zone, a non-ordinary temperature dependence of resistance, with a maximum at T~100 K, is observed. For W-doped VO2 films, it is shown that substitution of V4+ with W6+ results in a decrease of the temperature of the metal-insulator transition. Also, it has been shown that the doping of initial films with ~3 at.% of W reduces the statistical scatter in the threshold parameters of the switching devices with S-shaped I-V characteristics on the basis of V2O5 gel films.

  18. Composite Cathode for High-Power Density Solid Oxide Fuel Cells

    SciTech Connect

    Ilwon Kim; Scott Barnett; Yi Jiang; Manoj Pillai; Nikkia McDonald; Dan Gostovic; Zhongryang Zhan; Jiang Liu

    2004-01-31

    Reduction of solid oxide fuel cell (SOFC) operating temperature will play a key role in reducing the stack cost by allowing the use of low-cost metallic interconnects and new approaches to sealing, while making applications such as transportation more feasible. Reported results for anode-supported SOFCs show that cathode polarization resistance is the primary barrier to achieving high power densities at operating temperatures of 700 C and lower. This project aims to identify and develop composite cathodes that could reduce SOFC operating temperatures below 700 C. This effort focuses on study and use of (La,Sr)(Co,Fe)O{sub 3} (LSCF) based composite cathodes, which have arguably the best potential to substantially improve on the currently-used, (La,Sr)MnO{sub 3}-Yttria-stabilized Zirconia. During this Phase I, it was successfully demonstrated that high performances can be achieved with LSCF/Gadolinium-Doped Ceria composite cathodes on Ni-based anode supported cells operating at 700 C or lower. We studied electrochemical reactions at LSCF/Yttria-stabilized Zirconia (YSZ) interfaces, and observed chemical reactions between LSCF and YSZ. By using ceria electrolytes or YSZ electrolytes with ceria diffusion barrier layers, the chemical reactions between LSCF and electrolytes were prevented under cathode firing conditions necessary for the optimal adhesion of the cathodes. The protection provided by ceria layer is expected to be adequate for stable long-term cathode performances, but more testing is needed to verify this. Using ceria-based barrier layers, high performance Ni-YSZ anode supported cells have been demonstrated with maximum power densities of 0.8W/cm2 at 700 C and 1.6W/cm{sup 2} at 800 C. Ni-SDC anode supported cells with SDC electrolytes yielded >1W/cm{sup 2} at 600 C. We speculate that the power output of Ni-YSZ anode supported cell at 700 C and lower, was limited by the quality of the Ceria and Ceria YSZ interface. Improvements in the low

  19. Auto-catalytic Ceria Nanoparticles Offer Neuroprotection to Adult Rat Spinal Cord Neurons

    PubMed Central

    Das, Mainak; Patil, Swanand; Bhargava, Neelima; Kang, Jung-Fong; Riedel, Lisa M.; Seal, Sudipta; Hickman, James J.

    2007-01-01

    This paper describes the evaluation of the auto-catalytic anti-oxidant behavior and biocompatibility of Cerium oxide nanoparticles for applications in spinal cord repair and other diseases of the CNS. The application of a single dose of nano-Ceria at a nano-molar concentration is biocompatible, regenerative and provides a significant neuroprotective effect on adult rat spinal cord neurons. Retention of neuronal function is demonstrated from electrophysiological recordings and the possibility of its application to prevent ischemic insult is suggested from an oxidative injury assay. A mechanism is proposed to explain the auto-catalytic properties of these nanoparticles. PMID:17222903

  20. Electrochemical oxidation of N-nitrosodimethylamine with boron-doped diamond film electrodes.

    PubMed

    Chaplin, Brian P; Schrader, Glenn; Farrell, James

    2009-11-01

    This research investigated NDMA oxidation by boron-doped diamond (BDD) film electrodes. Oxidation rates were measured as a function of electrode potential, current density, and temperature using rotating disk and flow-through reactors. Final NDMA reaction products were carbon dioxide, ammonium, and nitrate, with dimethylamine and methylamine as intermediate products. Reaction rates were first-order with respect to NDMA concentration and surface area normalized oxidation rates as high as 850 +/- 50 L/m(2)-hr were observed at a current density of 10 mA/cm(2). The flow-through reactor yielded mass transfer limited reaction rates that were first-order in NDMA concentration, with a half-life of 2.1 +/- 0.1 min. Experimental evidence indicates that NDMA oxidation proceeds via a direct electron transfer at potentials >1.8 V/SHE with a measured apparent activation energy of 3.1 +/- 0.5 kJ/mol at a potential of 2.5 V/SHE. Density functional theory calculations indicate that a direct two-electron transfer can produce a stable NDMA((+2)) species that is stabilized by forming an adduct with water. The transfer of two electrons from NDMA to the electrode allows an activation-less attack of hydroxyl radicals on the NDMA((+2)) water adduct. At higher overpotentials the oxidation of NDMA occurs by a combination of direct electron transfer and hydroxyl radicals produced via water electrolysis.