Surface coating of ceria nanostructures for high-temperature oxidation protection

NASA Astrophysics Data System (ADS)

Aadhavan, R.; Bhanuchandar, S.; Babu, K. Suresh

2018-04-01

Stainless steels are used in high-temperature structural applications but suffer from degradation at an elevated temperature of operation due to thermal stress which leads to spallation. Ceria coating over chromium containing alloys induces protective chromia layer formation at alloy/ceria interface thereby preventing oxidative degradation. In the present work, three metals of differing elemental composition, namely, AISI 304, AISI 410, and Inconel 600 were tested for high-temperature stability in the presence and absence of ceria coating. Nanoceria was used as the target to deposit the coating through electron beam physical vapor deposition method. After isothermal oxidation at 1243 K for 24 h, Ceria coated AISI 304 and Inconel 600 exhibited a reduced rate of oxidation by 4 and 1 orders, respectively, in comparison with the base alloy. The formation of spinel structure was found to be lowered in the presence of ceria due to the reduced migration of cations from the alloy.

Preparation and characterization of Pd doped ceria-ZnO nanocomposite catalyst for methyl tert-butyl ether (MTBE) photodegradation.

PubMed

Seddigi, Zaki S; Bumajdad, Ali; Ansari, Shahid P; Ahmed, Saleh A; Danish, Ekram Y; Yarkandi, Naeema H; Ahmed, Shakeel

2014-01-15

A series of binary oxide catalysts (ceria-ZnO) were prepared and doped with different amounts of palladium in the range of 0.5%-1.5%. The prepared catalysts were characterized by SEM, TEM, XRD and XPS, as well as by N2 sorptiometry study. The XPS results confirmed the structure of the Pd CeO2-x-ZnO. The photocatalytic activity of these catalysts was evaluated for degradation of MTBE in water. These photocatalyst efficiently degrade a 100ppm aqueous solution of MTBE upon UV irradiation for 5h in the presence of 100mg of each of these photocatalysts. The removal of 99.6% of the MTBE was achieved with the ceria-ZnO catalyst doped with 1% Pd. In addition to the Pd loading, the N2 sorptiometry study introduced other factors that might affect the catalytic efficiency is the catalyst average pore sizes. The photoreaction was determined to be a first order reaction. Copyright © 2013 Elsevier B.V. All rights reserved.

Lanthanide-Doped Ceria Nanoparticles as Backside Coaters to Improve Silicon Solar Cell Efficiency.

PubMed

Hajjiah, Ali; Samir, Effat; Shehata, Nader; Salah, Mohamed

2018-05-23

This paper introduces lanthanide-doped ceria nanoparticles as silicon solar cell back-side coaters, showing their influence on the solar cell efficiency. Ceria nanoparticles can be synthesized to have formed oxygen vacancies (O-vacancies), which are associated with converting cerium ions from the Ce 4+ state ions to the Ce 3+ ones. These O-vacancies follow the rule of improving silicon solar cell conductivity through a hopping mechanism. Besides, under near-ultra violet (near-UV) excitation, the reduced trivalent cerium Ce 3+ ions are directly responsible for down converting the un-absorbed UV wavelengths to a resultant green photo-luminescence emission at ~520 nm, which is absorbed through the silicon solar cell’s active layer. Adding lanthanide elements such as Neodymium “Nd” as ceria nanoparticle dopants helps in forming extra oxygen vacancies (O-vacancies), followed by an increase in the number of Ce 4+ to Ce 3+ ion reductions, thus enhancing the conductivity and photoluminescence down conversion mechanisms. After introducing lanthanide-doped ceria nanoparticles on a silicon solar cell surface, a promising enhancement in the behavior of the solar cell current-voltage curve is observed, and the efficiency is improved by about 25% of its initial value due to the mutual impact of improving both electric conductivity and optical conversions.

Sub-nanometer surface chemistry and orbital hybridization in lanthanum-doped ceria nano-catalysts revealed by 3D electron microscopy.

PubMed

Collins, Sean M; Fernandez-Garcia, Susana; Calvino, José J; Midgley, Paul A

2017-07-14

Surface chemical composition, electronic structure, and bonding characteristics determine catalytic activity but are not resolved for individual catalyst particles by conventional spectroscopy. In particular, the nano-scale three-dimensional distribution of aliovalent lanthanide dopants in ceria catalysts and their effect on the surface electronic structure remains unclear. Here, we reveal the surface segregation of dopant cations and oxygen vacancies and observe bonding changes in lanthanum-doped ceria catalyst particle aggregates with sub-nanometer precision using a new model-based spectroscopic tomography approach. These findings refine our understanding of the spatially varying electronic structure and bonding in ceria-based nanoparticle aggregates with aliovalent cation concentrations and identify new strategies for advancing high efficiency doped ceria nano-catalysts.

Converting ceria polyhedral nanoparticles into single-crystal nanospheres.

PubMed

Feng, Xiangdong; Sayle, Dean C; Wang, Zhong Lin; Paras, M Sharon; Santora, Brian; Sutorik, Anthony C; Sayle, Thi X T; Yang, Yi; Ding, Yong; Wang, Xudong; Her, Yie-Shein

2006-06-09

Ceria nanoparticles are one of the key abrasive materials for chemical-mechanical planarization of advanced integrated circuits. However, ceria nanoparticles synthesized by existing techniques are irregularly faceted, and they scratch the silicon wafers and increase defect concentrations. We developed an approach for large-scale synthesis of single-crystal ceria nanospheres that can reduce the polishing defects by 80% and increase the silica removal rate by 50%, facilitating precise and reliable mass-manufacturing of chips for nanoelectronics. We doped the ceria system with titanium, using flame temperatures that facilitate crystallization of the ceria yet retain the titania in a molten state. In conjunction with molecular dynamics simulation, we show that under these conditions, the inner ceria core evolves in a single-crystal spherical shape without faceting, because throughout the crystallization it is completely encapsulated by a molten 1- to 2-nanometer shell of titania that, in liquid state, minimizes the surface energy. The principle demonstrated here could be applied to other oxide systems.

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

Incorporating Rich Mesoporosity into a Ceria-Based Catalyst via Mechanochemistry

DOE PAGES

Zhan, Wangcheng; Yang, Shize; Zhang, Pengfei; ...

2017-08-15

Ceria-based materials possessing mesoporous structures afford higher activity than the corresponding bulk materials in CO oxidation and other catalytic applications, because of the wide pore channel and high surface area. The development of a direct, template-free, and scalable technology for directing porosity inside ceriabased materials is highly welcome. Here in this paper, a family of mesoporous transition-metaldoped ceria catalysts with specific surface areas up to 122 m 2 g -1 is constructed by mechanochemical grinding. No templates, additives, or solvents are needed in this process, while the mechanochemistry-mediated restructuring and the decomposing of the organic group led to plentiful mesopores.more » Interestingly, the copper species are evenly dispersed in the ceria matrix at the atomic scale, as observed in high resolution scanning transmission electron microscopy in high angle annular dark field. The copper-doped ceria materials show good activity in the CO oxidation.« less

Lattice thermal expansion and solubility limits of neodymium-doped ceria

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Jinhua, E-mail: jhzhang1212@126.com; State Key laboratory of Geological Process and Mineral Resources, China University of Geosciences, Wuhan 430074; Ke, Changming

2016-11-15

Nd{sub x}Ce{sub 1−x}O{sub 2−0.5x} (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 Nd{sup 3+}, and the heating temperature going up. The average thermal expansion coefficients of neodymium doped ceria with fluorite structure are highermore » than 13.5×10{sup −6} °C{sup −1} from room temperature to 1200 °C. - Graphical abstract: The crystal structure of Nd{sub x}Ce{sub 1−x}O{sub 2−0.5x} (x=0–1.0) 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.« less

The reduction and oxidation of ceria: A natural abundance triple oxygen isotope perspective

NASA Astrophysics Data System (ADS)

Hayles, Justin; Bao, Huiming

2015-06-01

Ceria (CeO2) is a heavily studied material in catalytic chemistry for use as an oxygen storage medium, oxygen partial pressure regulator, fuel additive, and for the production of syngas, among other applications. Ceria powders are readily reduced and lose structural oxygen when subjected to low pO2 and/or high temperature conditions. Such dis-stoichiometric ceria can then re-oxidize under higher pO2 and/or lower temperature by incorporating new oxygen into the previously formed oxygen site vacancies. Despite extensive studies on ceria, the mechanisms for oxygen adsorption-desorption, dissociation-association, and diffusion of oxygen species on ceria surface and within the crystal structure are not well known. We predict that a large kinetic oxygen isotope effect should accompany the release and incorporation of ceria oxygen. As the first attempt to determine the existence and the degree of the isotope effect, this study focuses on a set of simple room-temperature re-oxidation experiments that are also relevant to a laboratory procedure using ceria to measure the triple oxygen isotope composition of CO2. Triple-oxygen-isotope labeled ceria powders are heated at 700 °C and cooled under vacuum prior to exposure to air. By combining results from independent experimental sets with different initial oxygen isotope labels and using a combined mass-balance and triangulation approach, we have determined the isotope fractionation factors for both high temperature reduction in vacuum (⩽10-4 mbar) and room temperature re-oxidation in air. Results indicate that there is a 1.5‰ ± 0.8‰ increase in the δ18O value of ceria after being heated in vacuum at 700 °C for 1 h. When the vacuum is broken at room temperature, the previously heated ceria incorporates 3-19% of its final structural oxygen from air, with a δ18O value of 2.1-4.1+7.7 ‰ for the incorporated oxygen. The substantial incorporation of oxygen from air supports that oxygen mobility is high in vacancy

Simultaneous NOx and Particulate Matter Removal from Diesel Exhaust by Hierarchical Fe-Doped Ce–Zr Oxide

PubMed Central

2017-01-01

Particulate matter and NOx emissions from diesel exhaust remains one of the most pressing environmental problems. We explore the use of hierarchically ordered mixed Fe–Ce–Zr oxides for the simultaneous capture and oxidation of soot and reduction of NOx by ammonia in a single step. The optimized material can effectively trap the model soot particles in its open macroporous structure and oxidize the soot below 400 °C while completely removing NO in the 285–420 °C range. Surface characterization and DFT calculations emphasize the defective nature of Fe-doped ceria. The isolated Fe ions and associated oxygen vacancies catalyze facile NO reduction to N2. A mechanism for the reduction of NO with NH3 on Fe-doped ceria is proposed involving adsorbed O2. Such adsorbed O2 species will also contribute to the oxidation of soot. PMID:28603656

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

Characterization of ceria electrolyte in solid oxide fuel cell applications

NASA Astrophysics Data System (ADS)

Milliken, Christopher Edward

The goal of this research effort is to characterize cation doped cerium dioxide for use as an electrolyte material in solid oxide fuel cell applications. A variety of analytical techniques including thermogravimetric analysis, controlled atmosphere dilatometry, and AC/DC electronic measurements on single cells and stacks have been coupled with thermodynamic calculations to evaluate the suitability of several doping schemes. The results of this analysis indicate that doping CeOsb2 with 20% SmOsb{1.5} or codoping with 19% GdOsb{1.5} + 1% PrOsb{1.83} provides the best combination of stability and performance. Under dual atmosphere fuel cell conditions, these dopants do not provide sufficient stabilization energy to prevent the reduction of ceria. A significant oxygen leakage current can be expected, particularly near open circuit conditions. Incorporation of 10% SrO provides similar short-term advantages to the lanthanide doped system but this electrolyte material undergoes an irreversible degradation mechanism that results in cell failure within 1500 hours of test. Under fuel cell conditions, the maximum efficiency of such systems in stacks will be below 40% at 200 mW/cmsp2 when operated on humidified hydrogen fuels. This compares to an expected efficiency of 45-50% at a similar power density for nonmixed conducting electrolyte (e.g., YSZ).

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sanghavi, Rahul P.; Nandasiri, Manjula I.; Kuchibhatla, Satyanarayana V N T

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 generatedmore » 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« less

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

Structure, morphology and reducibility of ceria-doped zirconia

NASA Astrophysics Data System (ADS)

Aribi, Koubra; Soltani, Zohra; Ghelamallah, Madani; Granger, Pascal

2018-03-01

Zr1-xCexOx has been prepared by hydrolysis, in neutral medium, starting from rough ZrO2 and CeO2 materials as simple and cheaper synthesis method compared to sol-gel routes. The oxy-hydroxide precursors thus obtained were calcined under air at 450 °C, 900 °C and 1200 °C. The impact of those thermal treatments on the structure, texture and related redox properties has been investigated. Higher specific surface area than those observed on ceria were observed after calcination at low temperature, i.e., 450 °C. Above that temperature thermal sintering occurs having a detrimental effect on the specific surface area related to crystal growth more accentuated on CeO2. The formation of several Zrsbnd Ce mixed oxide phases formed by incorporation and substitution of Zr in the structure of ceria was characterized. A complete loss of specific surface area is noticeable after calcination at 1200 °C. XRD and SEM analysis revealed the formation of two mixed oxides structure, i.e. Ce2Zr2O7.04 and Ce2Zr2O7 corresponding to different redox behavior evidenced from H2-TPR experiments.

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

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

PubMed

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

2015-08-28

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.

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

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.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, Yuyuan; Wu, Zili; Wen, Jianguo

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 nanorodmore » 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.« less

A Novel Hybrid Axial-Radial Atmospheric Plasma Spraying Technique for the Fabrication of Solid Oxide Fuel Cell Anodes Containing Cu, Co, Ni, and Samaria-Doped Ceria

NASA Astrophysics Data System (ADS)

Cuglietta, Mark; Kuhn, Joel; Kesler, Olivera

2013-06-01

Composite coatings containing Cu, Co, Ni, and samaria-doped ceria (SDC) have been fabricated using a novel hybrid atmospheric plasma spraying technique, in which a multi-component aqueous suspension of CuO, Co3O4, and NiO was injected axially simultaneously with SDC injected radially in a dry powder form. Coatings were characterized for their microstructure, permeability, porosity, and composition over a range of plasma spray conditions. Deposition efficiency of the metal oxides and SDC was also estimated. Depending on the conditions, coatings displayed either layering or high levels of mixing between the SDC and metal phases. The deposition efficiencies of both feedstock types were strongly dependent on the nozzle diameter. Plasma-sprayed metal-supported solid oxide fuel cells utilizing anodes fabricated with this technique demonstrated power densities at 0.7 V as high as 366 and 113 mW/cm2 in humidified hydrogen and methane, respectively, at 800 °C.

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

NASA Astrophysics Data System (ADS)

Cuglietta, Mark; Kesler, Olivera

2012-06-01

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

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

PubMed

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

2012-06-01

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

Impact of structure and morphology of nanostructured ceria coating on AISI 304 oxidation kinetics

NASA Astrophysics Data System (ADS)

Aadhavan, R.; Suresh Babu, K.

2017-07-01

Nanostructured ceria-based coatings are shown to be protective against high-temperature oxidation of AISI 304 due to the dynamics of oxidation state and associated defects. However, the processing parameters of deposition have a strong influence in determining the structural and morphological aspects of ceria. The present work focuses on the effect of variation in substrate temperature (50-300 °C) and deposition rate (0.1-50 Å/s) of ceria in electron beam physical vapour evaporation method and correlates the changes in structure and morphology to high-temperature oxidation protection. Unlike deposition rate, substrate temperature exhibited a profound influence on crystallite size (7-18 nm) and oxygen vacancy concentration. Upon isothermal oxidation at 1243 K for 24 h, bare AISI 304 exhibited a linear mass gain with a rate constant of 3.0 ± 0.03 × 10-3 kg2 m-4 s-1 while ceria coating lowered the kinetics by 3-4 orders. Though the thickness of the coating was kept constant at 2 μm, higher deposition rate offered one order lower protection due to the porous nature of the coating. Variation in the substrate temperature modulated the porosity as well as oxygen vacancy concentration and displayed the best protection for coatings deposited at moderate substrate temperature. The present work demonstrates the significance of selecting appropriate processing parameters to obtain the required morphology for efficient high-temperature oxidation protection.

Methane oxidation on Pd–Ceria: A DFT study of the mechanism over PdxCe1-xO2, Pd, and PdO

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mayernick, Adam D.; Janik, Michael J.

2011-02-14

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 Pd xCe 1-xO 2(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 Pdmore » xCe 1-xO 2(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 Pd xCe 1-xO 2(1 1 1). The low barrier over the Pd xCe 1-xO 2(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.« less

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

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

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.

Sulfur poisoning of Ni/Gadolinium-doped ceria anodes: A long-term study outlining stable solid oxide fuel cell operation

NASA Astrophysics Data System (ADS)

Riegraf, Matthias; Zekri, Atef; Knipper, Martin; Costa, Rémi; Schiller, Günter; Friedrich, K. Andreas

2018-03-01

This work presents an analysis of the long-term behavior of nickel/gadolinium-doped ceria (CGO) anode-based solid oxide fuel cells (SOFC) under sulfur poisoning conditions. A parameter study of sulfur-induced irreversible long-term degradation of commercial, high-performance single cells was carried out at 900 °C for different H2/N2/H2S fuel gas atmospheres, current densities and Ni/CGO anodes. The poisoning periods of the cells varied from 200 to 1500 h. The possibility of stable long-term Ni/CGO anode operation under sulfur exposure is established and the critical operating regime is outlined. Depending on the operating conditions, two degradation phenomena can be observed. Small degradation of the ohmic resistance was witnessed for sulfur exposure times of approximately 1000 h. Moreover, degradation of the anode charge transfer resistance was observed to be triggered by the combination of a small anodic potential step and high sulfur coverage on Ni. The microstructural evolution of altered Ni/CGO anodes was examined post-mortem by means of SEM and FIB/SEM, and is correlated to the anode performance degradation under critical operating conditions, establishing Ni depletion, porosity increase and a tripe phase boundary density decrease in the anode functional layer. It is shown that short-term sulfur poisoning behavior can be used to assess long-term stability.

Nanoparticle Precipitation in Irradiated and Annealed Ceria Doped with Metals for Emulation of Spent Fuels

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jiang, Weilin; Conroy, Michele A.; Kruska, Karen

Epsilon alloy precipitates have been observed with varied compositions and sizes in spent nuclear fuels, such as UO2. Presence of the inclusions, along with other oxide precipitates, gas bubbles and irradiation-induced structural defects, can significantly degrade the physical properties of the fuel. To predict fuel performance, a fundamental study of the precipitation processes is needed. This study uses ceria (CeO2) as a surrogate for UO2. Polycrystalline CeO2 films doped with Mo, Ru, Rh, Pd and Re (surrogate for Tc) were grown at 823 K using pulsed laser deposition, irradiated at 673 K with He+ ions, and subsequently annealed at highermore » temperatures. A number of methods, including transmission electron microscopy and atom probe tomography, were applied to characterize the samples. The results indicate that there is a uniform distribution of the doped metals in the as-grown CeO2 film. Pd particles of ~3 nm in size appear near dislocation edges after He+ ion irradiation to ~13 dpa. Thermal annealing at 1073 K in air leads to formation of precipitates with Mo and Pd around grain boundaries. Further annealing at 1373 K produces 70 nm sized precipitates with small grains at cavities.« less

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

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

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

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. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

On direct internal methane steam reforming kinetics in operating solid oxide fuel cells with nickel-ceria anodes

NASA Astrophysics Data System (ADS)

Thallam Thattai, A.; van Biert, L.; Aravind, P. V.

2017-12-01

Major operating challenges remain to safely operate methane fuelled solid oxide fuel cells due to undesirable temperature gradients across the porous anode and carbon deposition. This article presents an experimental study on methane steam reforming (MSR) global kinetics for single operating SOFCs with Ni-GDC (gadolinium doped ceria) anodes for low steam to carbon (S/C) ratios and moderate current densities. The study points out the hitherto insufficient research on MSR global and intrinsic kinetics for operating SOFCs with complete Ni-ceria anodes. Further, it emphasizes the need to develop readily applicable global kinetic models as a subsequent step from previously reported state-of-art and complex intrinsic models. Two rate expressions of the Power law (PL) and Langmuir-Hinshelwood (LH) type have been compared and based on the analysis, limitations of using previously proposed rate expressions for Ni catalytic beds to study MSR kinetics for complete cermet anodes have been identified. Firstly, it has been shown that methane reforming on metallic (Ni) current collectors may not be always negligible, contrary to literature reports. Both PL and LH kinetic models predict significantly different local MSR reaction rate and species partial pressure distributions along the normalized reactor length, indicating a strong need for further experimental verifications.

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.

Sulfation of ceria-zirconia model automotive emissions control catalysts

NASA Astrophysics Data System (ADS)

Nelson, Alan Edwin

Cerium-zirconium mixed metal oxides are used in automotive emissions control catalysts to regulate the partial pressure of oxygen near the catalyst surface. The near surface oxygen partial pressure is regulated through transfer of atomic oxygen from the ceria-zirconia solid matrix to the platinum group metals to form metal oxides capable of oxidizing carbon monoxide and unburned hydrocarbons. Although the addition of zirconium in the cubic lattice of ceria increases the oxygen storage capacity and thermal stability of the ceria matrix, the cerium-zirconium oxide system remains particularly susceptible to deactivation from sulfur compounds. While the overall effect of sulfur on these systems is understood (partially irreversible deactivation), the fundamental and molecular interaction of sulfur with ceria-zirconia remains a challenging problem. Ceria-zirconia metal oxide solid solutions have been prepared through co-precipitation with nitrate precursors. The prepared powders were calcined and subsequently formed into planer wafers and characterized for chemical and physical attributes. The prepared samples were subsequently exposed to a sulfur dioxide based environment and characterized with spectroscopic techniques to characterize the extent of sulfation and the nature of surface sulfur species. The extent of sulfation of the model ceria-zirconia systems was characterized with Auger electron spectroscopy (AES) prior to and after treatment in a microreactor. Strong dependencies were observed between the atomic ratio of ceria to zirconia and the extent of sulfation. In addition, the partial pressure of sulfur dioxide during treatments also correlated to the extent of sulfation, while temperature only slightly effected the extent of sulfation. The AES data suggests the gas phase sulfur dioxide preferentially chemisorbs on surface ceria atoms and the extent of sulfation is heavily dependent on sulfur dioxide concentrations and only slightly dependent on catalyst

Effect of Dopants and Sintering Method on the Properties of Ceria-Based Electrolytes for IT-SOFCs Applications

NASA Astrophysics Data System (ADS)

Sharma, Payal; Sharma, Chetan; Singh, Kanchan L.; Singh, Anirudh P.

2018-05-01

Doped and co-doped ceria ceramics are used as electrolyte materials in solid oxide fuel cells. In this work, ceria-based oxides, Ce0.90Gd0.06Y0.02M0.02O2-δ (M = Ca, Fe, La, and Sr) were prepared by conventional as well as microwave processing from the precursors prepared by the mixed oxide method. The consolidated calcined powders in pellet form were sintered in microwave energy at 1400°C for 20 min and in an electric furnace of IR radiation at 1400°C for 6 h. The x-ray diffraction analysis confirmed that all the compositions were crystallized into a cubic fluorite structure. Surface morphology of the sintered products was studied using scanning electron microscopy and the microhardness was investigated using the Vickers hardness test. The comparative results analysis shows that the microwave-sintered samples have uniform grain growth, higher density and higher microhardness than the corresponding conventionally sintered products. The microwave-sintered sample of composition Ce0.90Gd0.06Y0.02Sr0.02O2-δ was found to have the highest microhardness among the four compositions due to its high density and smallest grain size.

Nickel Nanocatalyst Ex-Solution from Ceria-Nickel Oxide Solid Solution for Low Temperature CO Oxidation.

PubMed

Singhania, Amit; Gupta, Shipra Mital

2018-07-01

In this work, in situ growth of Ni nanocatalysts to attach onto the ceria (CeO2) surface through direct Ni ex-solution from the NiO-CeO2 solid solution in a reducing atmosphere at high temperatures with an aim to improve the catalytic activity, and stability for low temperature carbon monoxide (CO) oxidation reaction have been reported. The NiO-CeO2 solid solutions were prepared by solution combustion method, and the results of XRD and RAMAN showed that doping of Ni increases the oxygen vacancies due to charge compensation. Ni is clearly visible in XRD and TEM of Ni ex-solved sample (R-UCe5Ni10) after reduction of NiO-CeO2 (UCe5Ni10) sample by 5% H2/Ar reduction at 1000 °C. TEM analysis revealed a size of 9.2 nm of Ni nanoparticle that is ex-solved on the surface CeO2. This ex-solved sample showed very high catalytic activity (T50 ~ 110 °C), and stability (100 h) for CO oxidation reaction as compared to prepared solid solution samples. This is due to the highly active metallic nano-phase which is ex-solved on the surface of CeO2 and strongly adherent to the support. The apparent activation energy Ni ex-solved sample is found out to be 48.4 kJ mol-1. Thus, the above Ni ex-solved sample shows a practical applicability for the CO reaction.

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.

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

NASA Astrophysics Data System (ADS)

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

2009-08-01

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

Fabrication and electrochemical performance of nickel- and gadolinium-doped ceria-infiltrated La0·2Sr0·8TiO3 anodes for solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Lee, Min-Jin; Shin, Jae-Hwa; Ji, Mi-Jung; Hwang, Hae-Jin

2018-01-01

In this work, nickel and gadolinium-doped ceria (GDC)-infiltrated lanthanum strontium titanate (LST) anodes are fabricated, and their electrode performances under a hydrogen atmosphere is investigated in terms of the Ni:GDC ratios and cell operating temperature. The Ni/GDC-infiltrated LST anode exhibits excellent electrode performance in comparison with the Ni- or GDC-infiltrated anodes, which is attributed to the synergistic effect of an extended triple-phase boundary length by GDC and good catalytic activity for hydrogen oxidation because of the Ni particles. The polarization resistances (Rp) of Ni/GDC-infiltrated LST are 0.07, 0.08, and 0.12 Ω cm2 at 800, 750, and 700 °C, respectively, which are approximately three orders of magnitude lower than that of the LST anode (68.5 Ω cm2 at 700 °C). The effect of Ni and GDC on the electrochemical performance of LST was also investigated by using electrochemical impedance spectroscopy (EIS). The anode polarization resistance (Rp) is confirmed to be dependent on the content and dispersion state (microstructure) of the Ni and GDC nanoparticles.

Altering properties of cerium oxide thin films by Rh doping

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ševčíková, Klára, E-mail: klarak.sevcikova@seznam.cz; NIMS Beamline Station at SPring-8, National Institute for Materials Science, Sayo, Hyogo 679-5148; Nehasil, Václav, E-mail: nehasil@mbox.troja.mff.cuni.cz

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 diffractionmore » 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.« less

The Sulphur Poisoning Behaviour of Gadolinia Doped Ceria Model Systems in Reducing Atmospheres

PubMed Central

Gerstl, Matthias; Nenning, Andreas; Iskandar, Riza; Rojek-Wöckner, Veronika; Bram, Martin; Hutter, Herbert; Opitz, Alexander Karl

2016-01-01

An array of analytical methods including surface area determination by gas adsorption using the Brunauer, Emmett, Teller (BET) method, combustion analysis, XRD, ToF-SIMS, TEM and impedance spectroscopy has been used to investigate the interaction of gadolinia doped ceria (GDC) with hydrogen sulphide containing reducing atmospheres. It is shown that sulphur is incorporated into the GDC bulk and might lead to phase changes. Additionally, high concentrations of silicon are found on the surface of model composite microelectrodes. Based on these data, a model is proposed to explain the multi-facetted electrochemical degradation behaviour encountered during long term electrochemical measurements. While electrochemical bulk properties of GDC stay largely unaffected, the surface polarisation resistance is dramatically changed, due to silicon segregation and reaction with adsorbed sulphur. PMID:28773771

Ceria-based model catalysts: fundamental studies on the importance of the metal–ceria interface in CO oxidation, the water–gas shift, CO 2 hydrogenation, and methane and alcohol reforming

DOE PAGES

Rodriguez, José A.; Grinter, David C.; Liu, Zongyuan; ...

2017-02-17

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 CO 2, and the production of hydrogen through the water–gas shift reaction and the reforming of methane or alcohols. By using model catalysts it is been possible to examinemore » 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. Generally, 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.« less

Fuel cells with doped lanthanum gallate electrolyte

NASA Astrophysics Data System (ADS)

Feng, Man; Goodenough, John B.; Huang, Keqin; Milliken, Christopher

Single cells with doped lanthanum gallate electrolyte material were constructed and tested from 600 to 800°C. Both ceria and the electrolyte material were mixed with NiO powder respectively to form composite anodes. Doped lanthanum cobaltite was used exclusively as the cathode material. While high power density from the solid oxide fuel cells at 800°C was achieved. our results clearly indicate that anode overpotential is the dominant factor in the power loss of the cells. Better anode materials and anode processing methods need to be found to fully utilize the high ionic conductivity of the doped lanthanum galiate and achieve higher power density at 800°C from solid oxide fuel cells.

The role of CO 2 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

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

Preparation and properties of plate-like titanate (PLT)/calcia-doped ceria (CDC) composites by sol-gel coating method.

PubMed

Liu, Xiangwen; Liu, Jingxiao; Dong, Xiaoli; Yin, Shu; Sato, Tsugio

2009-08-01

In order to obtain UV-shielding materials with good comfort, higher safety and effective UV-shielding ability, lepidocrocite type plate-like titanate (K(0.8)Li(0.27)Ti(1.73)O(4), donated as: PLT)/calcia-doped ceria (donated as: CDC) composites were synthesized by a sol-gel method. After dissolving Ce(NO(3))(3).6H(2)O and Ca(NO(3))(2).4H(2)O into absolute ethanol at 40 degrees C, glacial acetic acid (HAc) and PLT particles dispersed into absolute ethanol were added. Then, the solution was heated at 60 degrees C to get gel-like substance. This gel was dried in a vacuum oven at 333 K for 5 h, and then, the product was collected and ground in an agate mortar followed by calcination at 1073 K for 2 h to form PLT/CDC composites. By optimization, 20 mass% of CDC was coated by one operation. PLT/CDC composites with higher CDC content were obtained by repeating the coating process. The morphology, catalytic activity for the oxidation of organic material, UV-shielding ability and dynamic friction coefficient of as-obtained PLT/CDC composites were characterized. As a result, broad-spectrum UV-shielding composite materials with good comfort and low oxidation catalytic activity were successfully synthesized.

A novel design of anode-supported solid oxide fuel cells with Y 2O 3-doped Bi 2O 3, LaGaO 3 and La-doped CeO 2 trilayer electrolyte

NASA Astrophysics Data System (ADS)

Guo, Weimin; Liu, Jiang

Anode-supported solid oxide fuel cells (SOFCs) with a trilayered yttria-doped bismuth oxide (YDB), strontium- and magnesium-doped lanthanum gallate (LSGM) and lanthanum-doped ceria (LDC) composite electrolyte film are developed. The cell with a YDB (18 μm)/LSGM (19 μm)/LDC (13 μm) composite electrolyte film (designated as cell-A) shows the open-circuit voltages (OCVs) slightly higher than that of a cell with an LSGM (31 μm)/LDC (17 μm) electrolyte film (designated as cell-B) in the operating temperature range of 500-700 °C. The cell-A using Ag-YDB composition as cathode exhibits lower polarization resistance and ohmic resistance than those of a cell-B at 700 °C. The results show that the introduction of YDB to an anode-supported SOFC with a LSGM/LDC composite electrolyte film can effectively block electronic transport through the cell and thus increased the OCVs, and can help the cell to achieve higher power output.

Mechanism analysis on finishing of reaction-sintered silicon carbide by combination of water vapor plasma oxidation and ceria slurry polishing

NASA Astrophysics Data System (ADS)

Shen, Xinmin; Tu, Qunzhang; Deng, Hui; Jiang, Guoliang; Yamamura, Kazuya

2015-05-01

Reaction-sintered silicon carbide (RS-SiC), which is considered as a promising mirror material for space telescope systems, requires a high surface property. An ultrasmooth surface with a Ra surface roughness of 0.480 nm was obtained after water vapor plasma oxidation for 90 min followed by ceria slurry polishing for 40 min. The oxidation process of RS-SiC by water vapor plasma was analyzed based on the Deal-Grove model, and the theoretical calculation results are consistent with the measured data obtained by scanning white light interferometer (SWLI), scanning electron microscopy/energy-dispersive x-ray, and atomic force microscope. The polishing process of oxidized RS-SiC by ceria slurry was investigated according to the Preston equation, which would theoretically forecast the evolutions of RS-SiC surfaces along with the increasing of polishing time, and it was experimentally verified by comparing the surface roughnesses obtained by SWLI and the surface morphologies obtained by SEM. The mechanism analysis on the finishing of RS-SiC would be effective for the optimization of water vapor plasma oxidation parameters and ceria slurry polishing parameters, which will promote the application of RS-SiC substrates by improving the surface property obtained by the oxidation-assisted polishing method.

Surface structure of coherently strained ceria ultrathin films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shi, Yezhou; Stone, Kevin H.; Guan, Zixuan

2016-11-14

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 CeO 2 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 andmore » 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 CeO 2 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. In conclusion, 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.« less

Ameliorative role of nano-ceria against amine coated Ag-NP induced toxicity in Labeo rohita

NASA Astrophysics Data System (ADS)

Khan, Muhammad Saleem; Qureshi, Naureen Aziz; Jabeen, Farhat

2018-03-01

Silver nanoparticles (Ag-NPs) and its byproducts can spread pollution in aquatic habitat. Liver and gills are key target for toxicity. Oxidative stress, tissue alterations, and hemotoxicity are assumed to be associated with Ag-NPs in target animals. Cerium oxide nanoparticles (nano-ceria) show antioxidant potential in scavenging the free radicals generated in Ag-NP-induced oxidative stress. We determined ameliorated role of nano-ceria against Ag-NP-induced toxicity in fresh water Labeo rohita (L. rohita). Four groups were used in study including control, nano-ceria, Ag-NPs, and Ag-NPs + nano-ceria. Ag-NPs (30 mg l-1) and nano-ceria (50 µg kg-1) were given through water and prepared feed, respectively. The samples were taken after 28 days. Results demonstrated that pre-treatment of nano-ceria recovered L. rohita from Ag-NP-induced toxicity and oxidative stress. Nano-ceria pre-treatment actively mimics the activity of GST, GSH, CAT, and SOD. Furthermore, Ag-NPs' treatment caused severe inflammation and necrosis in hepatic parenchyma which leaded to congestion of blood in hepatic tissues. Accumulation of a yellow pigment in hepatic tissue was also seen due to necrosis of affected cells. In nano-ceria pre-treatment, there was no congestion in hepatic tissue. Vacuolization of cells and necrosis in some area was recorded in nano-ceria pre-treated group, but the gill and hepatic tissue showed improvement against Ag-NP-induced damage. Nano-ceria pre-treatment also improved hematological parameters in Ag-NP-treated fish. This study concluded that Ag-NP-induced toxicity in treated fish and pre-treatment of nano-ceria show ameliorative role.

Ga and In modified ceria as supports for cobalt-catalyzed Fischer-Tropsch synthesis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gnanamani, Muthu Kumaran; Jacobs, Gary; Shafer, Wilson D.

Ga- and In-modified ceria (Ce 0.8Ga 0.2O 2, Ce 0.8In 0.2O 2) materials were used as supports for cobalt-catalyzed Fischer-Tropsch synthesis (FTS). The addition of Ga to ceria was found to improve CO conversion for cobalt-catalyzed FTS, while the addition of In tended to decrease it. A similar trend was observed with the Ag-promoted cobalt/ceria catalysts. Doping of ceria with Ga or In decreased methane and increased the selectivity to olefins and alcohols for Ag-promoted cobalt/ceria. The sum of the products of olefins and alcohols for various catalysts exhibited a decreasing trend as follows: Ag-Co/Ce-Ga > Ag-Co/Ce-In > Ag-Co/Ce. Resultsmore » of H 2-TPR-XANES showed that adding of Ga or In to ceria increases the fraction of Ce 3+ in the surface shell for both unpromoted and Ag-promoted catalysts in the range of temperature typical of catalyst activation. In conclusion, this partially reduced ceria plays an important role in controlling the product selectivity of cobalt-catalyzed FT synthesis.« less

Ga and In modified ceria as supports for cobalt-catalyzed Fischer-Tropsch synthesis

DOE PAGES

Gnanamani, Muthu Kumaran; Jacobs, Gary; Shafer, Wilson D.; ...

2017-08-24

Ga- and In-modified ceria (Ce 0.8Ga 0.2O 2, Ce 0.8In 0.2O 2) materials were used as supports for cobalt-catalyzed Fischer-Tropsch synthesis (FTS). The addition of Ga to ceria was found to improve CO conversion for cobalt-catalyzed FTS, while the addition of In tended to decrease it. A similar trend was observed with the Ag-promoted cobalt/ceria catalysts. Doping of ceria with Ga or In decreased methane and increased the selectivity to olefins and alcohols for Ag-promoted cobalt/ceria. The sum of the products of olefins and alcohols for various catalysts exhibited a decreasing trend as follows: Ag-Co/Ce-Ga > Ag-Co/Ce-In > Ag-Co/Ce. Resultsmore » of H 2-TPR-XANES showed that adding of Ga or In to ceria increases the fraction of Ce 3+ in the surface shell for both unpromoted and Ag-promoted catalysts in the range of temperature typical of catalyst activation. In conclusion, this partially reduced ceria plays an important role in controlling the product selectivity of cobalt-catalyzed FT synthesis.« less

Fe-doping effects on the structural, vibrational, magnetic, and electronic properties of ceria nanoparticles

NASA Astrophysics Data System (ADS)

Aragón, Fermin F. H.; Aquino, Juan C. R.; Ramos, Jesus E.; Coaquira, José A. H.; Gonzalez, Ismael; Macedo, Waldemar A. A.; da Silva, Sebastião W.; Morais, Paulo C.

2017-11-01

In this work, we report on a single-pot synthesis route based on a polymeric precursor method used for successfully producing undoped and iron-doped CeO2 nanoparticles with iron contents up to 10.0 mol. %. The formation of high-crystalline nanoparticles with a cubic fluorite structure is determined for all the studied samples. Meanwhile, the magnetic measurements of the undoped ceria nanoparticles revealed the occurrence of ferromagnetism of bound magnetic polarons of a fraction of Ce3+ at room temperature, and only a paramagnetic behavior of Fe3+ ions was determined for Fe-doped ceria nanoparticles. A monotonous reduction of the effective magnetic moment of the Fe3+ ions was determined. It suggests a change from a high-spin to low-spin state of Fe ions as the Fe content is increased. The 3+ valence state of the iron ions has been confirmed by the Fe K-edge X-ray absorption near-edge structure (XANES) and Mössbauer spectroscopy measurements. X-ray photoelectron spectroscopy data analysis evidenced a coexistence of Ce3+ and Ce4+ ions and a decreasing tendency of the relative fraction of Ce3+ ions in the surface region of the particles as the iron content is increased. Although the coexistence of Ce3+ and Ce4+ is confirmed by results obtained via Ce L3-edge XANES measurements, any clear dependence of the relative relation of Ce3+ ions on the iron content is determined, suggesting a homogeneous distribution of Ce3+ and Ce4+-ions in the whole volume of the particles. Ce L3-edge extended X-ray absorption fine structure revealed that the Ce-O bond distance shows a monotonous decrease as the Fe content is increased, which is in good agreement with the shrinking of the unit cell volume with the iron content determined from XRD data analysis, reinforcing the substitutional solution of Ce and Fe ions in the CeO2 matrix.

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. Copyright © 2010 Elsevier B.V. All rights reserved.

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.

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.

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

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

DOE PAGES

Madaan, Nitesh; Bao, Jie; Nandasiri, Manjula I.; ...

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.

Photoluminescent properties of spider silk coated with Eu-doped nanoceria

NASA Astrophysics Data System (ADS)

Dmitrović, Svetlana; Nikolić, Marko G.; Jelenković, Branislav; Prekajski, Marija; Rabasović, Mihailo; Zarubica, Aleksandra; Branković, Goran; Matović, Branko

2017-02-01

Spider dragline silk was coated with pure as well as Eu-doped ceria nanopowders at the room temperature. The treatment was done by immersion of the spider silk mesh into aqueous solutions of cerium nitrate (Ce(NO3)3) and ammonium hydroxide (NH4OH). Depending on the relationship between Ce3+ ion and ammonium hydroxide concentration, coated fibers exhibited a different thickness. Obtained materials were studied by means of FESEM. It was found that ceria nanoparticles of average size of 3 nm were coated along spider thread. X-ray diffraction (XRD) and selected-area electron diffraction (SAED) confirmed crystal nature of nanoparticle coating of spider silk. By using Williamson-Hall plots, crystallite size and strain were estimated. EDS measurement confirmed the presence of Eu in spider-Eu-doped ceria composite, and according to FTIR analysis, the interaction between CeO2 and spider silk was proposed. The morphology of obtained composite was observed by TEM. The photoluminescence emission spectra of spider silk coated with Eu-doped ceria were measured with two different excitations of 385 and 466 nm. The two-photon excited auto-fluorescence of spider silk coated with Eu-doped ceria was detected using a nonlinear laser scanning microscope. Obtained composite has a potential as a fluorescent labeling material in diverse applications.

Unique properties of ceria nanoparticles supported on metals: novel inverse ceria/copper catalysts for CO oxidation and the water-gas shift reaction.

PubMed

Senanayake, Sanjaya D; Stacchiola, Dario; Rodriguez, Jose A

2013-08-20

Oxides play a central role in important industrial processes, including applications such as the production of renewable energy, remediation of environmental pollutants, and the synthesis of fine chemicals. They were originally used as catalyst supports and were thought to be chemically inert, but now they are used to build catalysts tailored toward improved selectivity and activity in chemical reactions. Many studies have compared the morphological, electronic, and chemical properties of oxide materials with those of unoxidized metals. Researchers know much less about the properties of oxides at the nanoscale, which display distinct behavior from their bulk counterparts. More is known about metal nanoparticles. Inverse-model catalysts, composed of oxide nanoparticles supported on metal or oxide substrates instead of the reverse (oxides supporting metal nanoparticles), are excellent tools for systematically testing the properties of novel catalytic oxide materials. Inverse models are prepared in situ and can be studied with a variety of surface science tools (e.g. scanning tunneling microscopy, X-ray photoemission spectroscopy, ultraviolet photoemission spectroscopy, low-energy electron microscopy) and theoretical tools (e.g. density functional theory). Meanwhile, their catalytic activity can be tested simultaneously in a reactor. This approach makes it possible to identify specific functions or structures that affect catalyst performance or reaction selectivity. Insights gained from these tests help to tailor powder systems, with the primary objective of rational design (experimental and theoretical) of catalysts for specific chemical reactions. This Account describes the properties of inverse catalysts composed of CeOx nanoparticles supported on Cu(111) or CuOx/Cu(111) as determined through the methods described above. Ceria is an important material for redox chemistry because of its interchangeable oxidation states (Ce⁴⁺ and Ce³⁺). Cu(111), meanwhile, is

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

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

PubMed

Dong, Qiang; Yin, Shu; Guo, Chongshen; Sato, Tsugio

2012-10-01

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

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.

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.

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. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jones, John; Xiong, Haifeng; DelaRiva, Andrew

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 anchoringmore » the platinum. Performing synthesis at high temperatures ensures that only the most stable binding sites are occupied, yielding a sinter-resistant, atomically dispersed catalyst.« less

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 (CeO 2) and sodium-modified ceria (Ce-Na) were prepared through combustion synthesis. Palladium was deposited onto the supports (Pd/CeO 2 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/CeO 2. 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 supportmore » and independent of 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

XPS studies of Mg doped GDC (Ce0.8Gd0.2O2-δ) for IT-SOFC

NASA Astrophysics Data System (ADS)

Tyagi, Deepak; Rao, P. Koteswara; Wani, B. N.

2018-04-01

Fuel Cells have gained much attention as efficient and environment friendly device for both stationary as well as mobile applications. For intermediate temperature SOFC (IT-SOFC), ceria based electrolytes are the most promising one, due to their higher ionic conductivity at relatively lower temperatures. Gd doped ceria is reported to be having the highest ionic conductivity. In the present work, Mg is codoped along with Gd and the electronic structure of the constituents is studied by XPS. XPS confirm that the Cerium is present in +4 oxidation state only which indicates that electronic conduction can be completely avoided.

High performance novel gadolinium doped ceria/yttria stabilized zirconia/nickel layered and hybrid thin film anodes for application in solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Garcia-Garcia, F. J.; Beltrán, A. M.; Yubero, F.; González-Elipe, A. R.; Lambert, R. M.

2017-09-01

Magnetron sputtering under oblique angle deposition was used to produce Ni-containing ultra thin film anodes comprising alternating layers of gadolinium doped ceria (GDC) and yttria stabilized zirconia (YSZ) of either 200 nm or 1000 nm thickness. The evolution of film structure from initial deposition, through calcination and final reduction was examined by XRD, SEM, TEM and TOF-SIMS. After subsequent fuel cell usage, the porous columnar architecture of the two-component layered thin film anodes was maintained and their resistance to delamination from the underlying YSZ electrolyte was superior to that of corresponding single component Ni-YSZ and Ni-GDC thin films. Moreover, the fuel cell performance of the 200 nm layered anodes compared favorably with conventional commercially available thick anodes. The observed dependence of fuel cell performance on individual layer thicknesses prompted study of equivalent but more easily fabricated hybrid anodes consisting of simultaneously deposited Ni-GDC and Ni-YSZ, which procedure resulted in exceptionally intimate mixing and interaction of the components. The hybrids exhibited very unusual and favorable Isbnd V characteristics, along with exceptionally high power densities at high currents. Their discovery is the principal contribution of the present work.

Improvement of performance in low temperature solid oxide fuel cells operated on ethanol and air mixtures using Cu-ZnO-Al2O3 catalyst layer

NASA Astrophysics Data System (ADS)

Morales, M.; Espiell, F.; Segarra, M.

2015-10-01

Anode-supported single-chamber solid oxide fuel cells with and without Cu-ZnO-Al2O3 catalyst layers deposited on the anode support have been operated on ethanol and air mixtures. The cells consist of gadolinia-doped ceria electrolyte, Ni-doped ceria anode, and La0.6Sr0.4CoO3-δ-doped ceria cathode. Catalyst layers with different Cu-ZnO-Al2O3 ratios are deposited and sintered at several temperatures. Since the performance of single-chamber fuel cells strongly depends on catalytic properties of electrodes for partial oxidation of ethanol, the cells are electrochemically characterized as a function of the temperature, ethanol-air molar ratio and gas flow rate. In addition, catalytic activities of supported anode, catalytic layer-supported anode and cathode for partial oxidation of ethanol are analysed. Afterwards, the effect of composition and sintering temperature of catalyst layer on the cell performance are determined. The results indicate that the cell performance can be significantly enhanced using catalyst layers of 30:35:35 and 40:30:30 wt.% Cu-ZnO-Al2O3 sintered at 1100 °C, achieving power densities above 50 mW cm-2 under 0.45 ethanol-air ratio at temperatures as low as 450 °C. After testing for 15 h, all cells present a gradual loss of power density, without carbon deposition, which is mainly attributed to the partial re-oxidation of Ni at the anode.

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.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

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. In this paper, 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, wemore » 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. Finally, 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.« less

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

DOE PAGES

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

2016-12-05

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. In this paper, 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, wemore » 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. Finally, 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.« less

On the growth mechanisms of polar (100) surfaces of ceria on copper (100)

NASA Astrophysics Data System (ADS)

Hackl, Johanna; Duchoň, Tomáš; Gottlob, Daniel M.; Cramm, Stefan; Veltruská, Kateřina; Matolín, Vladimír; Nemšák, Slavomír; Schneider, Claus M.

2018-05-01

We present a study of temperature dependent growth of nano-sized ceria islands on a Cu (100) substrate. Low-energy electron microscopy, micro-electron diffraction, X-ray absorption spectroscopy, and photoemission electron microscopy are used to determine the morphology, shape, chemical state, and crystal structure of the grown islands. Utilizing real-time observation capabilities, we reveal a three-way interaction between the ceria, substrate, and local oxygen chemical potential. The interaction manifests in the reorientation of terrace boundaries on the Cu (100) substrate, characteristic of the transition between oxidized and metallic surface. The reorientation is initiated at nucleation sites of ceria islands, whose growth direction is influenced by the proximity of the terrace boundaries. The grown ceria islands were identified as fully stoichiometric CeO2 (100) surfaces with a (2 × 2) reconstruction.

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.

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.

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.

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

The Role of Dextran Coatings on the Cytotoxicity Properties of Ceria Nanoparticles Toward Bone Cancer Cells

NASA Astrophysics Data System (ADS)

Yazici, Hilal; Alpaslan, Ece; Webster, Thomas J.

2015-04-01

Cerium oxide nanoparticles have demonstrated great potential as antioxidant and radioprotective agents for nanomedicine applications especially for cancer therapy. The surface chemistry of nanoparticles is an important property that has a significant effect on their performance in biological applications including cancer diagnosis, cancer treatment, and bacterial infection. Recently, various nanosized cerium oxide particles with different types of polymer coatings have been developed to improve aqueous solubility and allow for surface functionalization for distinct applications. In this study, the role of ceria nanoparticles coated with dextran on the cytotoxicity properties of bone cancer cells was shown. Specifically, 0.1 M and 0.01 M dextran-coated, <5-nm ceria nanoparticles, were synthesized. The cytotoxicity of 0.1 M and 0.01 M dextran-coated ceria nanoparticles was evaluated against osteosarcoma cells. A change in cell viability was observed when treating osteosarcoma cells with 0.1 M dextran-coated ceria nanoparticles in the 250 -1000 μg/mL concentration range. In contrast, minimal toxicity to bone cancer cells was observed for the 0.01 M dextran coating after 3 days compared with the 0.1 M dextran coating. These results indicated that surface dextran functionalization had a positive impact on the cytotoxicity of cerium oxide nanoparticles against osteosarcoma cells.

Dynamic formation of single-atom catalytic active sites on ceria-supported gold nanoparticles

PubMed Central

Wang, Yang-Gang; Mei, Donghai; Glezakou, Vassiliki-Alexandra; Li, Jun; Rousseau, Roger

2015-01-01

Catalysis by gold supported on reducible oxides has been extensively studied, yet issues such as the nature of the catalytic site and the role of the reducible support remain fiercely debated topics. Here we present ab initio molecular dynamics simulations of an unprecedented dynamic single-atom catalytic mechanism for the oxidation of carbon monoxide by ceria-supported gold clusters. The reported dynamic single-atom catalytic mechanism results from the ability of the gold cation to strongly couple with the redox properties of the ceria in a synergistic manner, thereby lowering the energy of redox reactions. The gold cation can break away from the gold nanoparticle to catalyse carbon monoxide oxidation, adjacent to the metal/oxide interface and subsequently reintegrate back into the nanoparticle after the reaction is completed. Our study highlights the importance of the dynamic creation of active sites under reaction conditions and their essential role in catalysis. PMID:25735407

Conversion of Methane into Methanol and Ethanol over Nickel Oxide on Ceria-Zirconia Catalysts in a Single Reactor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Okolie, Chukwuemeka; Belhseine, Yasmeen F.; Lyu, Yimeng

Direct conversion of methane into alcohols is a promising technology for converting stranded methane reserves into liquids that can be transported in pipelines and upgraded to value-added chemicals. We demonstrate that a catalyst consisting of small nickel oxide clusters supported on ceria-zirconia (NiO/CZ) can selectively oxidize methane to methanol and ethanol in a single, steady-state process at 723 K using O2 as an abundantly available oxidant. The presence of steam is required to obtain alcohols rather than CO2 as the product of catalytic combustion. The unusual activity of this catalyst is attributed to the synergy between the small Lewis acidicmore » NiO clusters and the redox-active CZ support, which also stabilizes the small NiO clusters.« less

Direct ethanol solid oxide fuel cell operating in gradual internal reforming

NASA Astrophysics Data System (ADS)

Nobrega, S. D.; Galesco, M. V.; Girona, K.; de Florio, D. Z.; Steil, M. C.; Georges, S.; Fonseca, F. C.

2012-09-01

An electrolyte supported solid oxide fuel cell (SOFC) using standard electrodes, doped-lanthanum manganite cathode and Ni-cermet anode, was operated with direct (anhydrous) ethanol for more than 100 h, delivering essentially the same power output as running on hydrogen. A ceria-based layer provides the catalytic activity for the gradual internal reforming, which uses the steam formed by the electrochemical oxidation of hydrogen for the decomposition of ethanol. Such a concept opens up the way for multi-fuel SOFCs using standard components and a catalytic layer.

In Situ Spectroscopy and Mechanistic Insights into CO Oxidation on Transition-Metal-Substituted Ceria Nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Elias, Joseph S.; Stoerzinger, Kelsey A.; Hong, Wesley T.

Herein we investigate the reaction intermediates formed during CO oxidation on copper-substituted ceria nanoparticles (Cu0.1Ce0.9O2–x) by means of in situ spectroscopic techniques and identify an activity descriptor that rationalizes a trend with other metal substitutes (M0.1Ce0.9O2–x, M = Mn, Fe, Co, Ni). In situ X-ray absorption spectroscopy (XAS) performed under catalytic conditions demonstrates that O2– transfer occurs at dispersed copper centers, which are redox active during catalysis. In situ XAS reveals a dramatic reduction at the copper centers that is fully reversible under catalytic conditions, which rationalizes the high catalytic activity of Cu0.1Ce0.9O2–x. Ambient pressure X-ray photoelectron spectroscopy (AP-XPS) andmore » in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) show that CO can be oxidized to CO32– in the absence of O2. We find that CO32– desorbs as CO2 only under oxygen-rich conditions when the oxygen vacancy is filled by the dissociative adsorption of O2. These data, along with kinetic analyses, lend support to a mechanism in which the breaking of copper–oxygen bonds is rate-determining under oxygen-rich conditions, while refilling the resulting oxygen vacancy is rate-determining under oxygen-lean conditions. On the basis of these observations and density functional calculations, we introduce the computed oxygen vacancy formation energy (Evac) as an activity descriptor for substituted ceria materials and demonstrate that Evac successfully rationalizes the trend in the activities of M0.1Ce0.9O2–x catalysts that spans three orders of magnitude. The applicability of Evac as a useful design descriptor is demonstrated by the catalytic performance of the ternary oxide Cu0.1La0.1Ce0.8O2–x, which has an apparent activation energy rivaling those of state-of-the-art Au/TiO2 materials. Thus, we suggest that cost-effective catalysts for CO oxidation can be rationally designed by judicious choice of

Metal Doped Manganese Oxide Thin Films for Supercapacitor Application.

PubMed

Tung, Mai Thanh; Thuy, Hoang Thi Bich; Hang, Le Thi Thu

2015-09-01

Co and Fe doped manganese oxide thin films were prepared by anodic deposition at current density of 50 mA cm(-2) using the electrolyte containing manganese sulfate and either cobalt sulfate or ferrous sulfate. Surface morphology and crystal structure of oxides were studied by scanning electron microscope (SEM) and X-ray diffraction (XRD). Chemical composition of materials was analyzed by X-ray energy dispersive spectroscope (EDS), iodometric titration method and complexometric titration method, respectively. Supercapacitive behavior of Co and Fe doped manganese oxide films were characterized by cyclic voltammetry (CV) and impedance spectroscopy (EIS). The results show that the doped manganese oxides are composed of nano fiber-like structure with radius of 5-20 nm and remain amorphous structure after heat treatment at 100 degrees C for 2 hours. The average valence of manganese increases from +3.808 to +3.867 after doping Co and from +3.808 to +3.846 after doping Fe. The doped manganese oxide film electrodes exhibited preferably ideal pseudo-capacitive behavior. The specific capacitance value of deposited manganese oxide reaches a maximum of 175.3 F/g for doping Co and 244.6 F/g for doping Fe. The thin films retained about 84% of the initial capacity even after 500 cycles of charge-discharge test. Doping Co and Fe decreases diffusion and charge transfer resistance of the films. The electric double layer capacitance and capacitor response frequency are increased after doping.

Temperature Dependence Discontinuity in the Stability of Manganese doped Ceria Nanocrystals

DOE PAGES

Wu, Longjia; Dholabhai, Pratik; Uberuaga, Blas P.; ...

2017-01-05

CeO 2 has strong potential for chemical-looping water splitting. It has been shown that manganese doping decreases interface energies of CeO 2, allowing increased stability of high surface areas in this oxygen carrier oxide. The phenomenon is related to the segregation of Mn3+ at interfaces, which causes a measurable decrease in excess energy. Here in the present work, it is shown that, despite the stability of nanocrystals of manganese-doped CeO 2 with relation to undoped CeO 2, the effect is strongly dependent on the oxidation state of manganese, i.e., on the temperature. At temperatures below 800 °C, Mn is inmore » the 3+ valence state, and coarsening is hindered by the reduced interface energetics, showing smaller crystal sizes with increasing Mn content. At temperatures above 800 °C, Mn is reduced to its 2+ valence state, and coarsening is enhanced with increasing Mn content. Atomistic simulations show the segregation of Mn to grain boundaries is relatively insensitive to the charge state of the dopant. However, point defect modeling finds that the reduced state causes a decrease in cation vacancy concentration and an increase in cation interstitials, reducing drag forces for grain boundary mobility and increasing growth rates.« less

An open circuit voltage equation enabling separation of cathode and anode polarization resistances of ceria electrolyte based solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Zhang, Yanxiang; Chen, Yu; Yan, Mufu

2017-07-01

The open circuit voltage (OCV) of solid oxide fuel cells is generally overestimated by the Nernst equation and the Wagner equation, due to the polarization losses at electrodes. Considering both the electronic conduction of electrolyte and the electrode polarization losses, we express the OCV as an implicit function of the characteristic oxygen pressure of electrolyte (p* [atm], at which the electronic and ionic conductivities are the same), and the relative polarization resistance of electrodes (rc = Rc/Ri and ra = Ra/Ri, where Ri/c/a [Ωcm2] denotes the ionic resistance of electrolyte, and the polarization resistances of cathode and anode, respectively). This equation approaches to the Wagner equation when the electrodes are highly active (rc and ra → 0), and approaches to the Nernst equation when the electrolyte is a purely ionic conductor (p* → 0). For the fuel cells whose OCV is well below the prediction of the Wagner equation, for example with thin doped ceria electrolyte, it is demonstrated that the combination of OCV and impedance spectroscopy measurements allows the determination of p*, Rc and Ra. This equation can serve as a simple yet powerful tool to study the internal losses in the cell under open circuit condition.

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

DOE PAGES

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

2016-03-22

In this study, the growth of ceria nanoclusters on single-layer graphene on Ru(0001) has been examined, with a view towards fabricating a stable system for model catalysis studies. The surface morphology and cluster distribution as a function of oxide coverage and substrate temperature has been monitored by scanning tunneling microscopy (STM), whereas the chemical composition of the cluster deposits has been determined by Auger electron spectroscopy (AES). The ceria nanoparticles are of the CeO 2(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. Themore » 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.« less

Increased viability of fibroblasts when pretreated with ceria nanoparticles during serum deprivation.

PubMed

Genier, Francielli S; Bizanek, Maximilian; Webster, Thomas J; Roy, Amit K

2018-01-01

Conditions of cellular stress are often the cause of cell death or dysfunction. Sustained cell stress can lead to several health complications, such as extensive inflammatory responses, tumor growth, and necrosis. To prevent disease and protect human tissue during these conditions and to avoid medication side effects, nanomaterials with unique characteristics have been applied to biological systems. This paper introduces the pretreatment in human dermal fibroblasts with cerium oxide nanoparticles during nutritional stress. For this purpose, human dermal fibroblast cells received cell culture media with concentrations of 250 µg/mL and 500 µg/mL of nano-cerium oxide before being exposed to 24, 48, and 72 hours of serum starvation. Contrast images demonstrated higher cell confluence and cell integrity in cells pretreated with ceria nanoparticles compared to untreated cells. It was confirmed by MTS assay after 72 hours of serum starvation that higher cell viability was achieved with ceria nanoparticles. The results demonstrate the potential of cerium oxide nanoparticles as protective agents during cellular starvation.

Reduction in the Band Gap of Manganese-Doped Zinc Oxide: Role of the Oxidation State

NASA Astrophysics Data System (ADS)

Sharma, Sonia; Ramesh, Pranith; Swaminathan, P.

2015-12-01

Manganese-doped zinc oxide powders were synthesized by solid state reaction of the respective oxides. The high-temperature conditions were chosen such that multiple valence states of manganese were doped in the host zinc oxide lattice. Structural characterization was carried out to confirm the doping and to find the maximum amount of manganese that can be incorporated. Diffuse reflectance spectroscopy was used to measure the optical band gap of the doped sample and the lowering with respect to pure ZnO was attributed to the presence of higher oxidation states of manganese. The presence of these oxidation states was confirmed using x-ray photoelectron spectroscopy. The study shows that a solid state reaction is a viable route for synthesizing doped metal oxides with desired optical properties.

Effect of annealing on doping of graphene with molybdenum oxide

NASA Astrophysics Data System (ADS)

Ishikawa, Ryousuke; Watanabe, Sho; Nishida, Hiroki; Aoyama, Yuki; Oya, Tomoya; Nomoto, Takahiro; Tsuboi, Nozomu

2018-04-01

We investigated the effect of post-annealing on the doping of graphene with MoO3 in this study. The as-deposited molybdenum oxide thin film prepared using our method was not completely oxidized; in addition, it was in an amorphous state, due to which its doping effect was not significant. As the post-deposition annealing temperature was increased, the oxidation and crystallization of the molybdenum oxide progressed and the doping effect increased accordingly. After annealing at 350 °C, the holes were the most doped and the sheet resistance was the lowest. The doped graphene film obtained in this study shows higher doping effect and stability compared to other dopants.

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.

Hydrodeoxygenation of Guaiacol over Ceria-Zirconia Catalysts.

PubMed

Schimming, Sarah M; LaMont, Onaje D; König, Michael; Rogers, Allyson K; D'Amico, Andrew D; Yung, Matthew M; Sievers, Carsten

2015-06-22

The hydrodeoxygenation of guaiacol is investigated over bulk ceria and ceria-zirconia catalysts with different elemental compositions. The reactions are performed in a flow reactor at 1 atm and 275-400 °C. The primary products are phenol and catechol, whereas cresol and benzene are formed as secondary products. No products with hydrogenated rings are formed. The highest conversion of guaiacol is achieved over a catalyst containing 60 mol % CeO2 and 40 mol % ZrO2 . Pseudo-first-order activation energies of 97-114 kJ mol(-1) are observed over the mixed metal oxide catalysts. None of the catalysts show significant deactivation during 72 h on stream. The important physicochemical properties of the catalysts are characterized by X-ray diffraction (XRD), temperature-programmed reduction, titration of oxygen vacancies, and temperature-programmed desorption of ammonia. On the basis of these experimental results, the reasons for the observed reactivity trends are identified. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Giant onsite electronic entropy enhances the performance of ceria for water splitting.

PubMed

Naghavi, S Shahab; Emery, Antoine A; Hansen, Heine A; Zhou, Fei; Ozolins, Vidvuds; Wolverton, Chris

2017-08-18

Previous studies have shown that a large solid-state entropy of reduction increases the thermodynamic efficiency of metal oxides, such as ceria, for two-step thermochemical water splitting cycles. In this context, the configurational entropy arising from oxygen off-stoichiometry in the oxide, has been the focus of most previous work. Here we report a different source of entropy, the onsite electronic configurational entropy, arising from coupling between orbital and spin angular momenta in lanthanide f orbitals. We find that onsite electronic configurational entropy is sizable in all lanthanides, and reaches a maximum value of ≈4.7 k B per oxygen vacancy for Ce 4+ /Ce 3+ reduction. This unique and large positive entropy source in ceria explains its excellent performance for high-temperature catalytic redox reactions such as water splitting. Our calculations also show that terbium dioxide has a high electronic entropy and thus could also be a potential candidate for solar thermochemical reactions.Solid-state entropy of reduction increases the thermodynamic efficiency of ceria for two-step thermochemical water splitting. Here, the authors report a large and different source of entropy, the onsite electronic configurational entropy arising from coupling between orbital and spin angular momenta in f orbitals.

[Preparation and photocatalytic activity of boron doped CeO2/TiO2 mixed oxides].

PubMed

Tang, Xin-hu; Wei, Chao-hai; Liang, Jie-rong; Wang, Bo-guang

2006-07-01

Boron doped CeO2/TiO2 mixed oxides photocatalysts were prepared by adding boric acid and cerous nitrate during the hydrolyzation of titanium trichloride and tetrabutyl titanate. XRD, UV-Vis DRS and XPS techniques were used to characterize the crystalline structure, light absorbing ability and the chemical state of Boron element in the photocatalyst sample. The photocatalytic activities were evaluated by monitoring the degradation of acid red B under UV irradiation. These results indicate that the wavelengths at adsorbing edge are affected by the content of cerous nitrate and the maximum absorption wavelength is about 481 nm when the mole ratio of Ce/Ti is 1.0. For higher dosage of Cerium, the absorbance edge shifts to blue slightly. The prepared photocatalyst is composed of anatase TiO2 and cubic CeO2 when calcined at 500 degrees C. An increase in the calcination temperature transforms the crystalline structure of the titanium oxides from anatase to rutile, and has no obvious influence on crystalline structure of CeO2 but crystallites growth up. The absorbance edge decreases drastically with the increase of calcination temperature. With a view to the stability of photocatalyst and utilization of sun energy, 500 degrees C of calcination temperature is recommended. The XP spectrum for B1s exhibits that only a few boron ions dope into titania and ceria matrix, others exist in B2O3. The photocatalytic activity increases with increase of cerous nitrate dosage, and decreases drastically due to higher dosage (the mol ratio of Ce/Ti > 0.5). After 10 min UV irradiation, 96% of acid red B is degraded completely over photocatalyst under optimum reaction condition.

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.

Selection Rule of Preferred Doping Site for n-Type Oxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, C.; Li, J.; Li, S. S.

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 bemore » used.« less

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 CO 2 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 CO 2 , we incorporated samarium-stabilized ceria (SDC) into a SrCo 0.85 Ta 0.15 O 3-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% CO 2 , 21% O 2 , and 69% N 2 . We observed that the CO 2 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 CO 2 adsorption and reactivity of the SDC protective layer, which are demonstrated through thermogravimetric analysis, energy-dispersive spectroscopy, and electrical conductivity study.

Conversion of Methane to Methanol and Ethanol over Nickel Oxide on Ceria-Zirconia Catalysts in a Single Reactor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Okolie, Chukwuemeka; Belhseine, Yasmeen F.; Lyu, Yimeng

Here, the conversion of methane into alcohols under moderate reaction conditions is a promising technology for converting stranded methane reserves into liquids that can be transported in pipelines and upgraded to value-added chemicals. We demonstrate that a catalyst consisting of small nickel oxide clusters supported on ceria-zirconia (NiO/CZ) can convert methane to methanol and ethanol in a single, steady-state process at 723 K using O 2 as an abundantly available oxidant. The presence of steam is required to obtain alcohols rather than CO 2 as the product of catalytic combustion. The unusual activity of this catalyst is attributed to themore » synergy between the small Lewis acidic NiO clusters and the redox-active CZ support, which also stabilizes the small NiO clusters.« less

Conversion of Methane to Methanol and Ethanol over Nickel Oxide on Ceria-Zirconia Catalysts in a Single Reactor

DOE PAGES

Okolie, Chukwuemeka; Belhseine, Yasmeen F.; Lyu, Yimeng; ...

2017-08-08

Here, the conversion of methane into alcohols under moderate reaction conditions is a promising technology for converting stranded methane reserves into liquids that can be transported in pipelines and upgraded to value-added chemicals. We demonstrate that a catalyst consisting of small nickel oxide clusters supported on ceria-zirconia (NiO/CZ) can convert methane to methanol and ethanol in a single, steady-state process at 723 K using O 2 as an abundantly available oxidant. The presence of steam is required to obtain alcohols rather than CO 2 as the product of catalytic combustion. The unusual activity of this catalyst is attributed to themore » synergy between the small Lewis acidic NiO clusters and the redox-active CZ support, which also stabilizes the small NiO clusters.« less

Synthesis and characterization of mesoporous ceria/alumina nanocomposite materials via mixing of the corresponding ceria and alumina gel precursors.

PubMed

Khalil, Kamal M S

2007-03-01

Mesoporous ceria/alumina, CeO(2)/Al(2)O(3), composites containing 10, 20 and 30% (w/w) ceria were prepared by a novel gel mixing method. In the method, ceria gel (formed via hydrolysis of ammonium cerium(IV) nitrate by aqueous ammonium carbonate solution) and alumina gel (formed via controlled hydrolysis of aluminum tri-isopropoxide) were mixed together. The mixed gel was subjected to subsequent drying and calcination for 3 h at 400, 600, 800 and 1000 degrees C. The uncalcined (dried at 110 degrees C) and the calcined composites were investigated by different techniques including TGA, DSC, FTIR, XRD, SEM and nitrogen adsorption/desorption isotherms. Results indicated that composites calcined for 3 h at 800 degrees C mainly kept amorphous alumina structure and gamma-alumina formed only upon calcinations at 1000 degrees C. On the other hand, CeO(2) was found to crystallize in the common ceria, cerinite, phase and it kept this structure over the entire calcination range (400-1000 degrees C). Therefore, high surface areas, stable surface textures, and non-aggregated nano-sized ceria dispersions were obtained. A systematic texture change based on ceria ratio was observed, however in all cases mesoporous composite materials exposing thermally stable texture and structure were obtained. The presented method produces composite ceria/alumina materials that suit different applications in the field of catalysis and membranes technology, and throw some light on physicochemical factors that determine textural morphology and thermal stability of such important composite.

Composite ceria-coated aerogels and methods of making the same

DOEpatents

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

2013-05-07

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

Anisotropic chemical strain in cubic ceria due to oxygen-vacancy-induced elastic dipoles.

PubMed

Das, Tridip; Nicholas, Jason D; Sheldon, Brian W; Qi, Yue

2018-06-06

Accurate characterization of chemical strain is required to study a broad range of chemical-mechanical coupling phenomena. One of the most studied mechano-chemically active oxides, nonstoichiometric ceria (CeO2-δ), has only been described by a scalar chemical strain assuming isotropic deformation. However, combined density functional theory (DFT) calculations and elastic dipole tensor theory reveal that both the short-range bond distortions surrounding an oxygen-vacancy and the long-range chemical strain are anisotropic in cubic CeO2-δ. The origin of this anisotropy is the charge disproportionation between the four cerium atoms around each oxygen-vacancy (two become Ce3+ and two become Ce4+) when a neutral oxygen-vacancy is formed. Around the oxygen-vacancy, six of the Ce3+-O bonds elongate, one of the Ce3+-O bond shorten, and all seven of the Ce4+-O bonds shorten. Further, the average and maximum chemical strain values obtained through tensor analysis successfully bound the various experimental data. Lastly, the anisotropic, oxygen-vacancy-elastic-dipole induced chemical strain is polarizable, which provides a physical model for the giant electrostriction recently discovered in doped and non-doped CeO2-δ. Together, this work highlights the need to consider anisotropic tensors when calculating the chemical strain induced by dilute point defects in all materials, regardless of their symmetry.

Near-Road Modeling and Measurement of Particles Generated by Nanoparticle Diesel Fuel Additive Use

EPA Science Inventory

Cerium oxide (ceria) nanoparticles (n-Ce) are used as a fuel-borne catalyst in diesel engines to reduce particulate emissions, yet the environmental and human health impacts of the ceria-doped diesel exhaust aerosols are not well understood. To bridge the gap between emission mea...

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

PubMed

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

2015-04-04

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

Giant onsite electronic entropy enhances the performance of ceria for water splitting

DOE PAGES

Naghavi, S. Shahab; Emery, Antoine A.; Hansen, Heine A.; ...

2017-08-18

Previous studies have shown that a large solid-state entropy of reduction increases the thermodynamic efficiency of metal oxides, such as ceria, for two-step thermochemical water splitting cycles. In this context, the configurational entropy arising from oxygen off-stoichiometry in the oxide, has been the focus of most previous work. Here we report a different source of entropy, the onsite electronic configurational entropy, arising from coupling between orbital and spin angular momenta in lanthanide f orbitals. We find that onsite electronic configurational entropy is sizable in all lanthanides, and reaches a maximum value of ≈4.7 k B per oxygen vacancy for Cemore » 4+/Ce 3+ reduction. This unique and large positive entropy source in ceria explains its excellent performance for high-temperature catalytic redox reactions such as water splitting. Our calculations also show that terbium dioxide has a high electronic entropy and thus could also be a potential candidate for solar thermochemical reactions.« less

Water-gas-shift over metal-free nanocrystalline ceria: An experimental and theoretical study

DOE PAGES

Guild, Curtis J.; Vovchok, Dimitriy; Kriz, David A.; ...

2017-01-23

A tandem experimental and theoretical investigation of a mesoporous ceria catalyst reveals the properties of the metal oxide are conducive for activity typically ascribed to metals, suggesting reduced Ce 3+ and oxygen vacancies are responsible for the inherent bi-functionality of CO oxidation and dissociation of water required for facilitating the production of H 2. The degree of reduction of the ceria, specifically the (1 0 0) face, is found to significantly influence the binding of reagents, suggesting reduced surfaces harbor the necessary reactive sites. The metal-free catalysis of the reaction is significant for catalyst design considerations, and the suite ofmore » in situ analyses provides a comprehensive study of the dynamic nature of the high surface area catalyst system. Finally, this study postulates feasible improvements in catalytic activity may redirect the purpose of the water-gas shift reaction from CO purification to primary hydrogen production.« less

Water-gas-shift over metal-free nanocrystalline ceria: An experimental and theoretical study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guild, Curtis J.; Vovchok, Dimitriy; Kriz, David A.

A tandem experimental and theoretical investigation of a mesoporous ceria catalyst reveals the properties of the metal oxide are conducive for activity typically ascribed to metals, suggesting reduced Ce 3+ and oxygen vacancies are responsible for the inherent bi-functionality of CO oxidation and dissociation of water required for facilitating the production of H 2. The degree of reduction of the ceria, specifically the (1 0 0) face, is found to significantly influence the binding of reagents, suggesting reduced surfaces harbor the necessary reactive sites. The metal-free catalysis of the reaction is significant for catalyst design considerations, and the suite ofmore » in situ analyses provides a comprehensive study of the dynamic nature of the high surface area catalyst system. Finally, this study postulates feasible improvements in catalytic activity may redirect the purpose of the water-gas shift reaction from CO purification to primary hydrogen production.« less

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.

High performance electrodes for reduced temperature solid oxide fuel cells with doped lanthanum gallate electrolyte. I. Ni-SDC cermet anode

NASA Astrophysics Data System (ADS)

Ohara, S.; Maric, R.; Zhang, X.; Mukai, K.; Fukui, T.; Yoshida, H.; Inagaki, T.; Miura, K.

A Ni-samaria-doped ceria (SDC) cermet was selected as the anode material for reduced temperature (800°C) solid oxide fuel cells. The NiO-SDC composite powder, synthesized by spray pyrolysis, was employed as the starting anode powder in this study. The influence of Ni content in Ni-SDC cermets on the electrode performance was investigated in order to create the most suitable microstructures. It was found that anodic polarization was strongly influenced by the Ni content in Ni-SDC cermets. The best results were obtained for anode cermets with Ni content of around 50 vol.%; anodic polarization was about 30 mV at a current density of 300 mA/cm 2. This high performance seems to be attributable to the microstructure, in which Ni grains form a skeleton with well-connected SDC grains finely distributed over the Ni grains surfaces; such microstructure was also conducive to high stability of the anode.

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.

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.

Synthesis of nanocrystalline Ni/Ce-YSZ powder via a polymerization route

NASA Astrophysics Data System (ADS)

Abolghasemi, Z.; Tamizifar, M.; Arzani, K.; Nemati, A.; Khanfekr, A.; Bolandi, M.

2013-08-01

Pechini process was used for preparation of three kinds of nanocrystalline powders of yttria-stabilized zirconia (YSZ): doped with 1.5 mol% nickel oxide, doped with 15 mol% ceria, and doped with 1.5 mol% nickel oxide plus 15 mol% ceria. Zirconium chloride, yttrium nitrate, cerium nitrate, nickel nitrate, citric acid and ethylene glycol were polymerized at 80 °C to produce a gel. XRD, SEM and TEM analyses were used to investigate the crystalline phases and microstructures of obtained compounds. The results of XRD revealed the formation of nanocrystalline powder at 900 °C. Morphology of the powder calcined at 900 °C, examined with a scanning electron microscope, showed that the presence of nickel and cerium inhibited the grain growth in the system. The average crystallite size of the material doped with nickel oxide (9.33 nm) was bigger than the one doped with cerium oxide (9.29 nm), while the YSZ doping with the two oxides simultaneously promoted the grain growth with crystallite size of 11.37 nm. Yttria-stabilized zirconia powder with a mean crystallite size of 9.997 nm was prepared successfully by this method.

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.

Gadolinium doped ceria interlayers for Solid Oxide Fuel Cells cathodes: Enhanced reactivity with sintering aids (Li, Cu, Zn), and improved densification by infiltration

NASA Astrophysics Data System (ADS)

Nicollet, Clement; Waxin, Jenny; Dupeyron, Thomas; Flura, Aurélien; Heintz, Jean-Marc; Ouweltjes, Jan Pieter; Piccardo, Paolo; Rougier, Aline; Grenier, Jean-Claude; Bassat, Jean-Marc

2017-12-01

This paper reports the study of the densification of 20% Gd doped ceria (Ce0.8Gd0.2O1.9 (GDC)) interlayers in SOFC cathodes through two different routes: the well-known addition of sintering elements, and an innovative densification process by infiltration. First, Li, Cu, and Zn nitrates were added to GDC powders. The effect of these additives on the densification was studied by dilatometry on pellets, and show a large decrease of the sintering temperature from 1330 °C (pure GDC), down to 1080 °C, 950 °C, and 930 °C for Zn, Cu, and Li addition, respectively. However, this promising result does not apply to screen-printed layers, which are more porous than pellets and in which the shrinkage is constrained by the substrate. The second approach consists in preparing a pre-sintered GDC layer, which is subsequently infiltrated with Ce and Gd nitrates and sintered at 1250 °C to increase its density. Such an approach results in highly dense GDC interlayers. Using La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) as electrode, the influence of the interlayers on the cathode performance was studied. The addition of sintering aids dramatically increases the cell resistances, most likely because the additives increase the reactivity between GDC and either Yttria Stabilized Zirconia (YSZ) or LSCF, thus losing the expected benefit related to the decrease of sintering temperatures. The interlayers prepared by infiltration do not induce additional resistances in the cell, which results in power densities of single cells 40-50% higher than those of cells prepared with commercial GDC interlayers, making this approach a valuable alternative to sintering aids.

Copper Doping of Zinc Oxide by Nuclear Transmutation

DTIC Science & Technology

2014-03-27

Copper Doping of Zinc Oxide by Nuclear Transmutation THESIS Matthew C. Recker, Captain, USAF AFIT-ENP-14-M-30 DEPARTMENT OF THE AIR FORCE AIR...NUCLEAR TRANSMUTATION THESIS Presented to the Faculty Department of Engineering Physics Graduate School of Engineering and Management Air Force...COPPER DOPING OF ZINC OXIDE BY NUCLEAR TRANSMUTATION Matthew C. Recker, BS Captain, USAF Approved: //signed// 27 February 2014 John W. McClory, PhD

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.

Deactivation of Ceria Supported Palladium through C–C Scission during Transfer Hydrogenation of Phenol with Alcohols

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nelson, Nicholas C.; Manzano, J. Sebastián; Slowing, Igor I.

The stability of palladium supported on ceria (Pd/CeO 2) 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.

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/CeO 2) 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.

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

Portable Oxygen Generation for Medical Applications.

DTIC Science & Technology

1997-07-01

stabilized zirconia; these include scandia- stabilized zirconia, lanthanum gallate , ceria, and bismuth oxide. Scandia-stabilized zirconia [1] exhibits...uncertainty of using doped ceria is its high thermal expansion coefficient (ceria -13-14 ppm/°C, YSZ -10.5 ppm/°C). Lanthanum gallate (LaGa03) [2-4...the conductivity of lanthanum gallate approximately 2-3 times that of YSZ in the 600- 1000°C temperature range. The enhanced conductivity in lanthanum

Zr-doped ceria additives for enhanced PEM fuel cell durability and radical scavenger stability

DOE PAGES

Baker, Andrew M.; Williams, Stefan Thurston DuBard; Mukundan, Rangachary; ...

2017-06-06

Doped ceria compounds demonstrate excellent radical scavenging abilities and are promising additives to improve the chemical durability of polymer electrolyte membrane (PEM) fuel cells. Here in this paper, Ce 0.85Zr 0.15O 2 (CZO) nanoparticles were incorporated into the cathode catalyst layers (CLs) of PEM fuel cells (based on Nafion XL membranes containing 6.0 μg cm -2 ion-exchanged Ce) at loadings of 10 and 55 μg cm -2. When compared to a CZO-free baseline, CZO-containing membrane electrode assemblies (MEAs) demonstrated extended lifetimes during PEM chemical stability accelerated stress tests (ASTs), exhibiting reduced electrochemical gas crossover, open circuit voltage decay, and fluoridemore » emission rates. The MEA with high CZO loading (55 μg cm -2) demonstrated performance losses, which are attributed to Ce poisoning of the PEM and CL ionomer regions, which is supported by X-ray fluorescence (XRF) analysis. In the MEA with the low CZO loading (10 μg cm -2), both the beginning of life (BOL) performance and the performance after 500 hours of ASTs were nearly identical to the BOL performance of the CZO-free baseline MEA. XRF analysis of the MEA with low CZO loading reveals that the BOL PEM Ce concentrations are preserved after 1408 hours of ASTs and that Ce contents in the cathode CL are not significant enough to reduce performance. Therefore, employing a highly effective radical scavenger such as CZO, at a loading of 10 μg cm -2 in the cathode CL, dramatically mitigates degradation effects, which improves MEA chemical durability and minimizes performance losses.« less

Zr-doped ceria additives for enhanced PEM fuel cell durability and radical scavenger stability

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baker, Andrew M.; Williams, Stefan Thurston DuBard; Mukundan, Rangachary

Doped ceria compounds demonstrate excellent radical scavenging abilities and are promising additives to improve the chemical durability of polymer electrolyte membrane (PEM) fuel cells. Here in this paper, Ce 0.85Zr 0.15O 2 (CZO) nanoparticles were incorporated into the cathode catalyst layers (CLs) of PEM fuel cells (based on Nafion XL membranes containing 6.0 μg cm -2 ion-exchanged Ce) at loadings of 10 and 55 μg cm -2. When compared to a CZO-free baseline, CZO-containing membrane electrode assemblies (MEAs) demonstrated extended lifetimes during PEM chemical stability accelerated stress tests (ASTs), exhibiting reduced electrochemical gas crossover, open circuit voltage decay, and fluoridemore » emission rates. The MEA with high CZO loading (55 μg cm -2) demonstrated performance losses, which are attributed to Ce poisoning of the PEM and CL ionomer regions, which is supported by X-ray fluorescence (XRF) analysis. In the MEA with the low CZO loading (10 μg cm -2), both the beginning of life (BOL) performance and the performance after 500 hours of ASTs were nearly identical to the BOL performance of the CZO-free baseline MEA. XRF analysis of the MEA with low CZO loading reveals that the BOL PEM Ce concentrations are preserved after 1408 hours of ASTs and that Ce contents in the cathode CL are not significant enough to reduce performance. Therefore, employing a highly effective radical scavenger such as CZO, at a loading of 10 μg cm -2 in the cathode CL, dramatically mitigates degradation effects, which improves MEA chemical durability and minimizes performance losses.« less

Probing and tuning the size, morphology, chemistry and structure of nanoscale cerium oxide

NASA Astrophysics Data System (ADS)

Kuchibhatla, Satyanarayana Vnt

Cerium oxide (ceria)-based materials in the nanoscale regime are of significant fundamental and technological interest. Nanoceria in pure and doped forms has current and potential use in solid oxide fuel cells, catalysis, UV-screening, chemical mechanical planarization, oxygen sensors, and bio-medical applications. The characteristic feature of Ce to switch between the +3 and +4 oxidation states renders oxygen buffering capability to ceria. The ease of this transformation was expected to be enhanced in the nanoceria. In most the practical scenarios, it is necessary to have a stable suspension of ceria nanoparticles (CNPs) over longer periods of time. However, the existing literature is confined to short term studies pertaining to synthesis and property evaluation. Having understood the need for a comprehensive understanding of the CNP suspensions, this dissertation is primarily aimed at understanding the behavior of CNPs in various chemical and physical environments. We have synthesized CNPs in the absence of any surfactants at room temperature and studied the aging characteristics. After gaining some understanding about the behavior of this functional oxide, the synthesis environment and aging temperature were varied, and their affects were carefully analyzed using various materials analysis techniques such as high resolution transmission electron microscopy (HRTEM), UV-Visible spectroscopy (UV-Vis), and X-ray photoelectron spectroscopy (XPS). When the CNPs were aged at room temperature in as-synthesized condition, they were observed to spontaneously assemble and evolve as fractal superoctahedral structures. The reasons for this unique polycrystalline morphology were attributed to the symmetry driven assembly of the individual truncated octahedral and octahedral seed of the ceria. HRTEM and Fast Fourier Transform (FFT) analyses were used to explain the agglomeration behavior and evolution of the octahedral morphology. Some of the observations were supported by

Effect of solvents on optical band gap of silicon-doped graphene oxide

NASA Astrophysics Data System (ADS)

Tul Ain, Qura; Al-Modlej, Abeer; Alshammari, Abeer; Naeem Anjum, Muhammad

2018-03-01

The objective of this study was to determine the influence on the optical band gap when the same amount of silicon-doped graphene oxide was dissolved in three different solvents namely, distilled water, benzene, and dichloroethane. Ultraviolet-visible spectroscopy was used to analyse the optical properties of the solutions. Among all these solutions distilled water containing silicon-doped graphene oxide has the smallest optical band gap of 2.9 eV and is considered a semiconductor. Other solutions are not considered as semiconductors as they have optical band gaps greater than 4 eV. It was observed that there is an increase in the value of optical band gap of distilled water, benzene, and dichloroethane solutions indicating a rise in the insulating behaviour. In this experiment, graphene oxide was synthesised from graphite powder by modified Hummer’s method and was then doped with silicon. Synthesis and doping of graphene oxide were confirmed by various characterization techniques. Fourier transmission infrared spectroscopy was used for identification of surface functional groups. X-ray diffraction was carried out to confirm the formation of crystalline graphene oxide and silicon doped graphene oxide. In x-ray diffraction pattern, shifting of intensity peak from a 2θ value of 26.5° to 10° confirmed the synthesis of graphene oxide and various intensity peaks at different values of 2θ confirmed doping of graphene oxide with silicon. Scanning electron microscopy images indicated that graphene oxide sheets were decorated with spherical silicon nanoparticles. Energy dispersive x-ray spectroscopy showed that silicon doped graphene oxide powder contained 63.36% carbon, 34.05% oxygen, and 2.6% silicon.

The surface chemistry of cerium oxide

DOE PAGES

Mullins, David R.

2015-01-29

Our review covers the structure of, and chemical reactions on, well-defined cerium oxide surfaces. Ceria, or mixed oxides containing ceria, are critical components in automotive three-way catalysts due to their well-known oxygen storage capacity. Ceria is also emerging as an important material in a number of other catalytic processes, particularly those involving organic oxygenates and the water–gas shift reaction. Ceria's acid–base properties, and thus its catalytic behavior, are closely related to its surface structure where different oxygen anion and cerium cation environments are present on the low-index structural faces. The actual structure of these various faces has been the focusmore » of a number of theoretical and experimental investigations. Ceria is also easily reducible from CeO 2 to CeO 2-X. The presence of oxygen vacancies on the surface often dramatically alters the adsorption and subsequent reactions of various adsorbates, either on a clean surface or on metal particles supported on the surface. We conducted surface science studies on the surfaces of thin-films rather than on the surfaces of bulk single crystal oxides. The growth, characterization and properties of these thin-films are also examined.« less

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

NASA Astrophysics Data System (ADS)

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

2010-07-01

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

Long-Term Stability of Oxide Nanowire Sensors via Heavily Doped Oxide Contact.

PubMed

Zeng, Hao; Takahashi, Tsunaki; Kanai, Masaki; Zhang, Guozhu; He, Yong; Nagashima, Kazuki; Yanagida, Takeshi

2017-12-22

Long-term stability of a chemical sensor is an essential quality for long-term collection of data related to exhaled breath, environmental air, and other sources in the Internet of things (IoT) era. Although an oxide nanowire sensor has shown great potential as a chemical sensor, the long-term stability of sensitivity has not been realized yet due to electrical degradation under harsh sensing conditions. Here, we report a rational concept to accomplish long-term electrical stability of metal oxide nanowire sensors via introduction of a heavily doped metal oxide contact layer. Antimony-doped SnO 2 (ATO) contacts on SnO 2 nanowires show much more stable and lower electrical contact resistance than conventional Ti contacts for high temperature (200 °C) conditions, which are required to operate chemical sensors. The stable and low contact resistance of ATO was confirmed for at least 1960 h under 200 °C in open air. This heavily doped oxide contact enables us to realize the long-term stability of SnO 2 nanowire sensors while maintaining the sensitivity for both NO 2 gas and light (photo) detections. The applicability of our method is confirmed for sensors on a flexible polyethylene naphthalate (PEN) substrate. Since the proposed fundamental concept can be applied to various oxide nanostructures, it will give a foundation for designing long-term stable oxide nanomaterial-based IoT sensors.

Morphological Control of Metal Oxide-Doped Zinc Oxide and Application to Cosmetics

NASA Astrophysics Data System (ADS)

Goto, Takehiro; Yin, Shu; Sato, Tsugio; Tanaka, Takumi

2012-06-01

Zinc oxide shows excellent transparency and ultraviolet radiation shielding ability, and is used for various cosmetics.1-3 However, it possesses high catalytic activity and lower dispersibility. Therefore, spherical particles of zinc oxide have been synthesized by soft solution reaction using zinc nitrate, ethylene glycol, sodium hydroxide and triethanolamine as starting materials. After dissolving these compounds in water, the solution was heated at 90°C for 1 h to form almost mono-dispersed spherical zinc oxide particles. The particle size changed depending on zinc ion concentration, ethylene glycol concentration and so on. Furthermore, with doping some metal ions, the phtocatalytic activity could be decreased. The obtained monodispersed metal ion-doped spherical zinc oxides showed excellent UV shielding ability and low photocatalytic activity. Therefore, they are expected to be used as cosmetics ingredients.

Gas-generated thermal oxidation of a coordination cluster for an anion-doped mesoporous metal oxide.

PubMed

Hirai, Kenji; Isobe, Shigehito; Sada, Kazuki

2015-12-18

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.

Dehydrogenation of methanol to formaldehyde catalyzed by pristine and defective ceria surfaces.

PubMed

Beste, Ariana; Overbury, Steven H

2016-04-21

We have explored the dehydrogenation of methoxy on pristine and defective (111), (100), and (110) ceria surfaces with density functional methods. Methanol conversion is used as a probe reaction to understand structure sensitivity of the oxide catalysis. Differences in reaction selectivity have been observed experimentally as a function of crystallographically exposed faces and degree of reduction. We find that the barrier for carbon-hydrogen cleavage in methoxy is similar for the pristine and defective (111), (100), and (110) surfaces. However, there are large differences in the stability of the surface intermediates on the different surfaces. The variations in experimentally observed product selectivities are a consequence of the interplay between barrier controlled bond cleavage and desorption processes. Subtle differences in activation energies for carbon-hydrogen cleavage on the different crystallographic faces of ceria could not be correlated with structural or electronic descriptors.

Thermodynamic stability of perovskite and lanthanum nickelate-type cathode materials for solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Cetin, Deniz

The need for cleaner and more efficient alternative energy sources is becoming urgent as concerns mount about climate change wrought by greenhouse gas emissions. Solid oxide fuel cells (SOFCs) are one of the most efficient options if the goal is to reduce emissions while still operating on fossil energy resources. One of the foremost problems in SOFCs that causes efficiency loss is the polarization resistance associated with the oxygen reduction reaction(ORR) at the cathodes. Hence, improving the cathode design will greatly enhance the overall performance of SOFCs. Lanthanum nickelate, La2NiO4+delta (LNO), is a mixed ionic and electronic conductor that has competitive surface oxygen exchange and transport properties and excellent electrical conductivity compared to perovskite-type oxides. This makes it an excellent candidate for solid oxide fuel cell (SOFC) applications. It has been previously shown that composites of LNO with Sm0.2Ce0.8O2-delta (SDC20) as cathode materials lead to higher performance than standalone LNO. However, in contact with lanthanide-doped ceria, LNO decomposes resulting in free NiO and ceria with higher lanthanide dopant concentration. In this study, the aforementioned instability of LNO has been addressed by compositional tailoring of LNO: lanthanide doped ceria (LnxCe 1-xO2,LnDC)composite. By increasing the lanthanide dopant concentration in the ceria phase close to its solubility limit, the LNO phase has been stabilized in the LNO:LnDC composites. Electrical conductivity of the composites as a function of LNO volume fraction and temperature has been measured, and analyzed using a resistive network model which allows the identification of a percolation threshold for the LNO phase. The thermomechanical compatibility of these composites has been investigated with SOFC systems through measurement of the coefficients of thermal expansion. LNO:LDC40 composites containing LNO lower than 50 vol%and higher than 40 vol% were identified as being

Enhancement of Catalytic Activity of Reduced Graphene Oxide Via Transition Metal Doping Strategy

NASA Astrophysics Data System (ADS)

Lee, Hangil; Hong, Jung A.

2017-06-01

To compare the catalytic oxidation activities of reduced graphene oxide (rGO) and rGO samples doped with five different transition metals (TM-rGO), we determine their effects on the oxidation of L-cysteine (Cys) in aqueous solution by performing electrochemistry (EC) measurements and on the photocatalytic oxidation of Cys by using high-resolution photoemission spectroscopy (HRPES) under UV illumination. Our results show that Cr-, Fe-, and Co-doped rGO with 3+ charge states (stable oxide forms: Cr3+, Fe3+, and Co3+) exhibit enhanced catalytic activities that are due to the charge states of the doped metal ions as we compare them with Cr-, Fe-, and Co-doped rGO with 2+ charge states.

Spray deposited gallium doped tin oxide thinfilm for acetone sensor application

NASA Astrophysics Data System (ADS)

Preethi, M. S.; Bharath, S. P.; Bangera, Kasturi V.

2018-04-01

Undoped and gallium doped (1 at.%, 2 at.% and 3 at.%) tin oxide thin films were prepared using spray pyrolysis technique by optimising the deposition conditions such as precursor concentration, substrate temperature and spraying rate. X-ray diffraction analysis revealed formation of tetragonally structured polycrystalline films. The SEM micrographs of Ga doped films showed microstructures. The electrical resistivity of the doped films was found to be more than that of the undoped films. The Ga-doped tin oxide thin films were characterised for gas sensors. 1 at.% Ga doped thin films were found to be better acetone gas sensor, showed 68% sensitivity at 350°C temperature.

Fast MAS 1H NMR Study of Water Adsorption and Dissociation on the (100) Surface of Ceria Nanocubes: A Fully Hydroxylated, Hydrophobic Ceria Surface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gill, Lance; Beste, Ariana; Chen, Banghao

1H nuclear magnetic resonance (NMR) spectroscopy was used to study hydroxylic surface species on ceria nanocubes, a crystalline, high-surface-area CeO 2 that presents mostly (100) facets. Water adsorption and desorption experiments in combination with fast magic angle spinning (MAS, 20–40 kHz) 1H NMR provide high-resolution 1H spectra that allow the observation of ten resonance bands (water or hydroxyl) on or under the (100) surface. Assignments were made using a combination of adsorption and temperature-programmed desorption, quantitative spin counting, deuterium exchange, spin–lattice (T 1) and spin–spin (T 2) relaxation, and DFT calculations. In air, the (100) surface exists as a fullymore » hydroxylated surface. Water adsorption and dissociation on dry ceria surfaces occur first at oxygen vacancies, but Ce 3+ centers are not required since water dissociation is barrier-less on the fully oxidized surface. Surface $-$OH functionality occurs in two resolved bands representing isolated $-$OH (1 ppm) and hydrogen-bonded $-$OH (9 ppm), the latter being dominant. Deuterium exchange of surface hydroxyls with D 2O does not occur under mild or forcing conditions. Despite large differences in the T 1 of surface hydroxyls and physisorbed water, surface hydroxyl T 1 values are independent of the presence or absence of physisorbed water, demonstrating that the protons within these two functional group pools are not in intimate contact. These observations show that, once hydroxylated, the surface $-$OH functionality preferentially forms hydrogen bonds with surface lattice oxygen, i.e., the hydroxylated (100) surface of ceria is hydrophobic. Near this surface it is energetically more favorable for physisorbed water to hydrogen bond to itself rather than to the surface. DFT calculations support this notion. Impurity Na + remaining in incompletely washed ceria nanocubes increases the surface hydrophilicity. In conclusion, sharp, low-field resonances observed in spectra

Fast MAS 1H NMR Study of Water Adsorption and Dissociation on the (100) Surface of Ceria Nanocubes: A Fully Hydroxylated, Hydrophobic Ceria Surface

DOE PAGES

Gill, Lance; Beste, Ariana; Chen, Banghao; ...

2017-03-22

1H nuclear magnetic resonance (NMR) spectroscopy was used to study hydroxylic surface species on ceria nanocubes, a crystalline, high-surface-area CeO 2 that presents mostly (100) facets. Water adsorption and desorption experiments in combination with fast magic angle spinning (MAS, 20–40 kHz) 1H NMR provide high-resolution 1H spectra that allow the observation of ten resonance bands (water or hydroxyl) on or under the (100) surface. Assignments were made using a combination of adsorption and temperature-programmed desorption, quantitative spin counting, deuterium exchange, spin–lattice (T 1) and spin–spin (T 2) relaxation, and DFT calculations. In air, the (100) surface exists as a fullymore » hydroxylated surface. Water adsorption and dissociation on dry ceria surfaces occur first at oxygen vacancies, but Ce 3+ centers are not required since water dissociation is barrier-less on the fully oxidized surface. Surface $-$OH functionality occurs in two resolved bands representing isolated $-$OH (1 ppm) and hydrogen-bonded $-$OH (9 ppm), the latter being dominant. Deuterium exchange of surface hydroxyls with D 2O does not occur under mild or forcing conditions. Despite large differences in the T 1 of surface hydroxyls and physisorbed water, surface hydroxyl T 1 values are independent of the presence or absence of physisorbed water, demonstrating that the protons within these two functional group pools are not in intimate contact. These observations show that, once hydroxylated, the surface $-$OH functionality preferentially forms hydrogen bonds with surface lattice oxygen, i.e., the hydroxylated (100) surface of ceria is hydrophobic. Near this surface it is energetically more favorable for physisorbed water to hydrogen bond to itself rather than to the surface. DFT calculations support this notion. Impurity Na + remaining in incompletely washed ceria nanocubes increases the surface hydrophilicity. In conclusion, sharp, low-field resonances observed in spectra

Enhance the pyroelectricity of polyvinylidene fluoride by graphene-oxide doping.

PubMed

Hu, Yuh-Chung; Hsu, Wei-Li; Wang, Yi-Ta; Ho, Cheng-Tao; Chang, Pei-Zen

2014-04-16

The high quality properties and benefits of graphene-oxide have generated an active area of research where many investigations have shown potential applications in various technological fields. This paper proposes a methodology for enhancing the pyro-electricity of PVDF by graphene-oxide doping. The PVDF film with graphene-oxide is prepared by the sol-gel method. Firstly, PVDF and graphene-oxide powders are dispersed into dimethylformamide as solvent to form a sol solution. Secondly, the sol solution is deposited on a flexible ITO/PET substrate by spin-coating. Thirdly, the particles in the sol solution are polymerized through baking off the solvent to produce a gel in a state of a continuous network of PVDF and graphene-oxide. The final annealing process pyrolyzes the gel and form a β-phase PVDF film with graphene-oxide doping. A complete study on the process of the graphene oxide doping of PVDF is accomplished. Some key points about the process are addressed based on experiments. The solutions to some key issues are found in this work, such as the porosity of film, the annealing temperature limitation by the use of flexible PET substrate, and the concentrations of PVDF and graphene-oxide.

Dehydrogenation of methanol to formaldehyde catalyzed by pristine and defective ceria surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Beste, Ariana; Overbury, Steven H.

We have explored the dehydrogenation of methoxy on pristine and defective (111), (100), and (110) ceria surfaces with density functional methods. Methanol conversion is used as a probe reaction to understand structure sensitivity of the oxide catalysis. Differences in reaction selectivity have been observed experimentally as a function of crystallographically exposed faces and degree of reduction. We find that the barrier for carbon-hydrogen cleavage in methoxy is similar for the pristine and defective (111), (100), and (110) surfaces. However, there are large differences in the stability of the surface intermediates on the different surfaces. The variations in experimentally observed productmore » selectivities are a consequence of the interplay between barrier controlled bond cleavage and desorption processes. Ultimately, subtle differences in activation energies for carbon-hydrogen cleavage on the different crystallographic faces of ceria could not be correlated with structural or electronic descriptors.« less

Dehydrogenation of methanol to formaldehyde catalyzed by pristine and defective ceria surfaces

DOE PAGES

Beste, Ariana; Overbury, Steven H.

2016-03-09

We have explored the dehydrogenation of methoxy on pristine and defective (111), (100), and (110) ceria surfaces with density functional methods. Methanol conversion is used as a probe reaction to understand structure sensitivity of the oxide catalysis. Differences in reaction selectivity have been observed experimentally as a function of crystallographically exposed faces and degree of reduction. We find that the barrier for carbon-hydrogen cleavage in methoxy is similar for the pristine and defective (111), (100), and (110) surfaces. However, there are large differences in the stability of the surface intermediates on the different surfaces. The variations in experimentally observed productmore » selectivities are a consequence of the interplay between barrier controlled bond cleavage and desorption processes. Ultimately, subtle differences in activation energies for carbon-hydrogen cleavage on the different crystallographic faces of ceria could not be correlated with structural or electronic descriptors.« less

Ceria based inverse opals for thermochemical fuel production: Quantification and prediction of high temperature behavior

NASA Astrophysics Data System (ADS)

Casillas, Danielle Courtney

Solar energy has the potential to supply more than enough energy to meet humanity's energy demands. Here, a method for thermochemical solar energy storage through fuel production is presented. A porous non-stoichiometric oxide, ceria, undergoes partial thermal reduction and oxidation with concentrated solar energy as a heat source, and water as an oxidant. The resulting yields for hydrogen fuel and oxygen are produced in two discrete steps, while the starting material maintains its original phase. Ordered porosity has been shown superior to random porosity for thermochemical fuel production applications, but stability limits for these structures are currently undefined. Ceria-based inverse opals are currently being investigated to assess the architectural influence on thermochemical hydrogen production. Low tortuosity and continuous interconnected pore network allow for facile gas transport and improved reaction kinetics. Ceria-based ordered materials have recently been shown to increase maximum hydrogen production over non-ordered porous ceria. Thermal stability of ordered porosity was quantified using quantitative image analysis. Fourier analysis was applied to SEM images of the material. The algorithm results in an order parameter gamma that describes the degree of long range order maintained by these structures, where gamma>4 signifies ordered porosity. According to this metric, a minimum zirconium content of 20 atomic percent (at%) is necessary for these architectures to survive aggressive annealing up to 1000°C. Zirconium substituted ceria (ZSC) with Zr loadings in excess of 20at% developed undesired tetragonal phases. Through gamma, we were able to find a balance between the benefit of zirconium additions on structural stability and its negative impact on phase. This work demonstrates the stability of seemingly delicate architectures, and the operational limit for ceria based inverse opals to be 1000°C for 1microm pore size. Inverse opals having sub

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tripathi, Madhvendra Nath, E-mail: ommadhav27@gmail.com

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 ofmore » 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.« less

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

NASA Astrophysics Data System (ADS)

Tripathi, Madhvendra Nath

2015-06-01

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 (In32-xSnxO48+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.

Catalytic properties of new anode materials for solid oxide fuel cells operated under methane at intermediary temperature

NASA Astrophysics Data System (ADS)

Sauvet, A.-L.; Fouletier, J.

The recent trend in solid oxide fuel cell concerns the use of natural gas as fuel. Steam reforming of methane is a well-established process for producing hydrogen directly at the anode side. In order to develop new anode materials, the catalytic activities of several oxides for the steam reforming of methane were characterized by gas chromatography. We studied the catalytic activity as a function of steam/carbon ratios r. The methane and the steam content were varied between 5 and 30% and between 1.5 and 3.5%, respectively, corresponding to r-values between 0.07 and 0.7. Catalyst (ruthenium and vanadium)-doped lanthanum chromites substituted with strontium, gadolinium-doped ceria (Ce 0.9Gd 0.1O 2) referred as to CeGdO 2, praseodymium oxide, molybdenum oxide and copper oxide were tested. The working temperature was fixed at 850°C, except for 5% ruthenium-doped La 1- xSr xCrO 3 where the temperature was varied between 700 and 850°C. Two types of behavior were observed as a function of the activity of the catalyst. The higher steam reforming efficiency was observed with 5% of ruthenium above 750°C.

Oxidation Induced Doping of Nanoparticles Revealed by in Situ X-ray Absorption Studies.

PubMed

Kwon, Soon Gu; Chattopadhyay, Soma; Koo, Bonil; Dos Santos Claro, Paula Cecilia; Shibata, Tomohiro; Requejo, Félix G; Giovanetti, Lisandro J; Liu, Yuzi; Johnson, Christopher; Prakapenka, Vitali; Lee, Byeongdu; Shevchenko, Elena V

2016-06-08

Doping is a well-known approach to modulate the electronic and optical properties of nanoparticles (NPs). However, doping at nanoscale is still very challenging, and the reasons for that are not well understood. We studied the formation and doping process of iron and iron oxide NPs in real time by in situ synchrotron X-ray absorption spectroscopy. Our study revealed that the mass flow of the iron triggered by oxidation is responsible for the internalization of the dopant (molybdenum) adsorbed at the surface of the host iron NPs. The oxidation induced doping allows controlling the doping levels by varying the amount of dopant precursor. Our in situ studies also revealed that the dopant precursor substantially changes the reaction kinetics of formation of iron and iron oxide NPs. Thus, in the presence of dopant precursor we observed significantly faster decomposition rate of iron precursors and substantially higher stability of iron NPs against oxidation. The same doping mechanism and higher stability of host metal NPs against oxidation was observed for cobalt-based systems. Since the internalization of the adsorbed dopant at the surface of the host NPs is driven by the mass transport of the host, this mechanism can be potentially applied to introduce dopants into different oxidized forms of metal and metal alloy NPs providing the extra degree of compositional control in material design.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bi, Kedong, E-mail: lishi@mail.utexas.edu, E-mail: kedongbi@seu.edu.cn; Department of Mechanical Engineering, University of Texas at Austin, Austin, Texas 78712; Weathers, Annie

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, themore » 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.« less

Reduced-graphene-oxide supported tantalum-based electrocatalysts: Controlled nitrogen doping and oxygen reduction reaction

NASA Astrophysics Data System (ADS)

Yang, Xiaoyun; Mo, Qijie; Guo, Yulin; Chen, Nana; Gao, Qingsheng

2018-03-01

Controlled N-doping is feasible to engineer the surface stoichiometry and the electronic configuration of metal-oxide electrocatalysts toward efficient oxygen reduction reactions (ORR). Taking reduced graphene oxide supported tantalum-oxides (TaOx/RGO) for example, this work illustrated the controlled N-doping in both metal-oxides and carbon supports, and the contribution to the improved ORR activity. The active N-doped TaOx/RGO electrocatalysts were fabricated via SiO2-assisted pyrolysis, in which the amount and kind of N-doping were tailored toward efficient electrocatalysis. The optimal nanocomposites showed a quite positive half-wave potential (0.80 V vs. RHE), the excellent long-term stability, and the outstanding tolerance to methanol crossing. The improvement in ORR was reasonably attributed to the synergy between N-doped TaOx and N-doped RGO. Elucidating the importance of controlled N-doping for electrocatalysis, this work will open up new opportunities to explore noble-metal-free materials for renewable energy applications.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kumar, Amit; Kumari, Monika; Kumar, Mintu

2016-05-06

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 CeO{sub 2} was increased. Synthesized nanoparticle were characterized by the XRDmore » and UV absorption techniques.« less

Ceria-thoria pellet manufacturing in preparation for plutonia-thoria LWR fuel production

NASA Astrophysics Data System (ADS)

Drera, Saleem S.; Björk, Klara Insulander; Sobieska, Matylda

2016-10-01

Thorium dioxide (thoria) has potential to assist in niche roles as fuel for light water reactors (LWRs). One such application for thoria is its use as the fertile component to burn plutonium in a mixed oxide fuel (MOX). Thor Energy and an international consortium are currently irradiating plutonia-thoria (Th-MOX) fuel in an effort to produce data for its licensing basis. During fuel-manufacturing research and development (R&D), surrogate materials were utilized to highlight procedures and build experience. Cerium dioxide (ceria) provides a good surrogate platform to replicate the chemical nature of plutonium dioxide. The project's fuel manufacturing R&D focused on powder metallurgical techniques to ensure manufacturability with the current commercial MOX fuel production infrastructure. The following paper highlights basics of the ceria-thoria fuel production including powder milling, pellet pressing and pellet sintering. Green pellets and sintered pellets were manufactured with average densities of 67.0% and 95.5% that of theoretical density respectively.

Performance of colloidal silica and ceria based slurries on CMP of Si-face 6H-SiC substrates

NASA Astrophysics Data System (ADS)

Chen, Guomei; Ni, Zifeng; Xu, Laijun; Li, Qingzhong; Zhao, Yongwu

2015-12-01

Colloidal silica and ceria based slurries, both using KMnO4 as an oxidizer, for chemical mechanical polishing (CMP) of Si-face (0 0 0 1) 6H-SiC substrate, were investigated to obtain higher material removal rate (MRR) and ultra-smooth surface. The results indicate that there was a significant difference in the CMP performance of 6H-SiC between silica and ceria based slurries. For the ceria based slurries, a higher MRR was obtained, especially in strong acid KMnO4 environment, and the maximum MRR (1089 nm/h) and a smoother surface with an average roughness Ra of 0.11 nm was achieved using slurries containing 2 wt% colloidal ceria, 0.05 M KMnO4 at pH 2. In contrast, due to the attraction between negative charged silica particles and positive charged SiC surface below pH 5, the maximum MRR of silica based slurry was only 185 nm/h with surface roughness Ra of 0.254 nm using slurries containing 6 wt% colloidal silica, 0.05 M KMnO4 at pH 6. The polishing mechanism was discussed based on the zeta potential measurements of the abrasives and the X-ray photoelectron spectroscopy (XPS) analysis of the polished SiC surfaces.

Surface characterization of acidic ceria-zirconia prepared by direct sulfation

NASA Astrophysics Data System (ADS)

Azambre, B.; Zenboury, L.; Weber, J. V.; Burg, P.

2010-05-01

Acidic ceria-zirconia (SCZ) solid acid catalysts with a nominal surface density of ca 2 SO 42-/nm 2 were prepared by a simple route consisting in soaking high specific surface area Ce xZr 1- xO 2 (with x = 0.21 and 0.69) mixed oxides solutions in 0.5 M sulphuric acid. Characterizations by TPD-MS, TP-DRIFTS and FT-Raman revealed that most of surface structures generated by sulfation are stable at least up to 700 °C under inert atmosphere and consist mainly as isolated sulfates located on defects or crystal planes and to a lesser extent as polysulfates. Investigations by pyridine adsorption/desorption have stated that: SCZ possess both strong Brønsted (B) and Lewis (L) acid sites, some of them being presumably superacidic; the B/L site ratio was found to be more dependent on the temperature and hydration degree than on the composition of the ceria-zirconia. By contrast, the reactivity of the parent Ce xZr 1- xO 2 materials towards pyridine is mostly driven by redox properties resulting in the formation of Py-oxide with the participation of Lewis acid sites of moderate strength ( cus Ce x+ and Zr x+ cations). Basicity studies by CO 2 adsorption/desorption reveal that SCZ surfaces are solely acidic whereas the number and strength of Lewis basic sites increases with the Ce content for the parent Ce xZr 1- xO 2 materials.

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.

[Lead adsorption and arsenite oxidation by cobalt doped birnessite].

PubMed

Yin, Hui; Feng, Xiong-Han; Qiu, Guo-Hong; Tan, Wen-Feng; Liu, Fan

2011-07-01

In order to study the effects of transition metal ions on the physic-chemical properties of manganese dioxides as environmental friendly materials, three-dimensional nano-microsphere cobalt-doped birnessite was synthesized by reduction of potassium permanganate by mixtures of concentrated hydrochloride and cobalt (II) chloride. Powder X-ray diffraction, chemical analysis, N2 physical adsorption, field emission scanning electron microscopy (FE-SEM) and X-ray photoelectron spectra (XPS) were used to characterize the crystal structure, chemical composition and micro-morphologies of products. In the range of molar ratios from 0.05 to 0.20, birnessite was fabricated exclusively. It was observed that cobalt incorporated into the layers of birnessite and had little effect on the crystal structure and micromorpholgy, but crystallinity decreased after cobalt doping. Both chemical analysis and XPS results showed that manganese average oxidation state decreased after cobalt doping, and the percentage of Mn3+ increased. Co(III) OOH existed mainly in the structure. With the increase of cobalt, hydroxide oxygen percentage in molar increased from 12.79% for undoped birnessite to 13.05%, 17.69% and 17.79% for doped samples respectively. Adsorption capacity for lead and oxidation of arsenite of birnessite were enhanced by cobalt doping. The maximum capacity of Pb2+ adsorption increased in the order HB (2 538 mmol/kg) < CoB5 (2798 mmol/kg) < CoB10 (2932 mmol/kg) < CoB20 (3 146 mmol/kg). Oxidation percentage of arsenite in simulated waste water by undoped birnessite was 76.5%, those of doped ones increased by 2.0%, 12.8% and 18.9% respectively. Partial of Co3+ substitution for Mn4+ results in the increase of negative charge of the layer and the content of hydroxyl group, which could account for the improved adsorption capacity of Pb2+. After substitution of manganese by cobalt, oxidation capacity of arsenite by birnessite increases likely due to the higher standard redox potential of

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.

Two-stage epitaxial growth of vertically-aligned SnO 2 nano-rods on(001) ceria

DOE PAGES

Solovyov, Vyacheslav F.; Wu, Li-jun; Rupich, Martin W.; ...

2014-09-20

Growth of high-aspect ratio oriented tin oxide, SnO 2, nano-rods is complicated by a limited choice of matching substrates. We show that a (001) cerium oxide, CeO 2, surface uniquely enables epitaxial growth of tin-oxide nano-rods via a two-stage process. First, (100) oriented nano-wires coat the ceria surface by lateral growth, forming a uniaxially-textured SnO 2 deposit. Second, vertical SnO 2nano-rods nucleate on the deposit by homoepitaxy. We demonstrate growth of vertically oriented 1-2 μm long nano-rods with an average diameter of ≈20 nm.

Preparation of Carbon-Platinum-Ceria and Carbon-Platinum-Cerium catalysts and its application in Polymer Electrolyte Fuel Cell: Hydrogen, Methanol, and Ethanol

NASA Astrophysics Data System (ADS)

Guzman Blas, Rolando Pedro

This thesis is focused on fuel cells using hydrogen, methanol and ethanol as fuel. Also, in the method of preparation of catalytic material for the anode: Supercritical Fluid Deposition (SFD) and impregnation method using ethylenediaminetetraacetic acid (EDTA) as a chelating agent. The first part of the thesis describes the general knowledge about Hydrogen Polymer Exchange Membrane Fuel Cell (HPEMFC),Direct Methanol Fuel Cell (DMFC) and Direct Ethanol Fuel Cell (DEFC), as well as the properties of Cerium and CeO2 (Ceria). The second part of the thesis describes the preparation of catalytic material by Supercritical Fluid Deposition (SFD). SFD was utilized to deposit Pt and ceria simultaneously onto gas diffusion layers. The Pt-ceria catalyst deposited by SFD exhibited higher methanol oxidation activity compared to the platinum catalyst alone. The linear sweep traces of the cathode made for the methanol cross over study indicate that Pt-Ceria/C as the anode catalyst, due to its better activity for methanol, improves the fuel utilization, minimizing the methanol permeation from anode to cathode compartment. The third and fourth parts of the thesis describe the preparation of material catalytic material Carbon-Platinum-Cerium by a simple and cheap impregnation method using EDTA as a chelating agent to form a complex with cerium (III). This preparation method allows the mass production of the material catalysts without additional significant cost. Fuel cell polarization and power curves experiments showed that the Carbon-Platinum-Cerium anode materials exhibited better catalytic activity than the only Vulcan-Pt catalysts for DMFC, DEFC and HPEMFC. In the case of Vulcan-20%Pt-5%w Cerium, this material exhibits better catalytic activity than the Vulcan-20%Pt in DMFC. In the case of Vulcan-40% Pt-doped Cerium, this material exhibits better catalytic activity than the Vulcan-40% Pt in DMFC, DEFC and HPEMFC. Finally, I propose a theory that explains the reason why the

Quantitative depth profiling of Ce(3+) in Pt/CeO2 by in situ high-energy XPS in a hydrogen atmosphere.

PubMed

Kato, Shunsuke; Ammann, Markus; Huthwelker, Thomas; Paun, Cristina; Lampimäki, Markus; Lee, Ming-Tao; Rothensteiner, Matthäus; van Bokhoven, Jeroen A

2015-02-21

The redox property of ceria is a key factor in the catalytic activity of ceria-based catalysts. The oxidation state of well-defined ceria nanocubes in gas environments was analysed in situ by a novel combination of near-ambient pressure X-ray Photoelectron Spectroscopy (XPS) and high-energy XPS at a synchrotron X-ray source. In situ high-energy XPS is a promising new tool to determine the electronic structure of matter under defined conditions. The aim was to quantitatively determine the degree of cerium reduction in a nano-structured ceria-supported platinum catalyst as a function of the gas environment. To obtain a non-destructive depth profile at near-ambient pressure, in situ high-energy XPS analysis was performed by varying the kinetic energy of photoelectrons from 1 to 5 keV, and, thus, the probing depth. In ceria nanocubes doped with platinum, oxygen vacancies formed only in the uppermost layers of ceria in an atmosphere of 1 mbar hydrogen and 403 K. For pristine ceria nanocubes, no change in the cerium oxidation state in various hydrogen or oxygen atmospheres was observed as a function of probing depth. In the absence of platinum, hydrogen does not dissociate and, thus, does not lead to reduction of ceria.

Electrical Transport Ability of Nanostructured Potassium-Doped Titanium Oxide Film

NASA Astrophysics Data System (ADS)

Lee, So-Yoon; Matsuno, Ryosuke; Ishihara, Kazuhiko; Takai, Madoka

2011-02-01

Potassium-doped nanostructured titanium oxide films were fabricated using a wet corrosion process with various KOH solutions. The doped condition of potassium in TiO2 was confirmed by Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). Nanotubular were synthesized at a dopant concentration of <0.27% when the dopant concentration increased to >0.27%, these structures disappeared. To investigate the electrical properties of K-doped TiO2, pseudo metal-oxide-semiconductor field-effect transistor (MOSFET) samples were fabricated. The samples exhibited a distinct electrical behavior and p-type characteristics. The electrical behavior was governed by the volume of the dopant when the dopant concentration was <0.10% and the volume of the TiO2 phase when the dopant concentration was >0.18%.

Splitting CO2 with a ceria‐based redox cycle in a solar‐driven thermogravimetric analyzer

PubMed Central

Takacs, M.; Ackermann, S.; Bonk, A.; Neises‐von Puttkamer, M.; Haueter, Ph.; Scheffe, J. R.; Vogt, U. F.

2016-01-01

Thermochemical splitting of CO2 via a ceria‐based redox cycle was performed in a solar‐driven thermogravimetric analyzer. Overall reaction rates, including heat and mass transport, were determined under concentrated irradiation mimicking realistic operation of solar reactors. Reticulated porous ceramic (RPC) structures and fibers made of undoped and Zr4+‐doped CeO2, were endothermally reduced under radiative fluxes of 1280 suns in the temperature range 1200–1950 K and subsequently re‐oxidized with CO2 at 950–1400 K. Rapid and uniform heating was observed for 8 ppi ceria RPC with mm‐sized porosity due to its low optical thickness and volumetric radiative absorption, while ceria fibers with μm‐sized porosity performed poorly due to its opacity to incident irradiation. The 10 ppi RPC exhibited higher fuel yield because of its higher sample density. Zr4+‐doped ceria showed increasing reduction extents with dopant concentration but decreasing specific CO yield due to unfavorable oxidation thermodynamics and slower kinetics. © 2016 American Institute of Chemical Engineers AIChE J, 63: 1263–1271, 2017 PMID:28405030

Nitrogen-doped graphene: effect of graphite oxide precursors and nitrogen content on the electrochemical sensing properties.

PubMed

Megawati, Monica; Chua, Chun Kiang; Sofer, Zdenek; Klímová, Kateřina; Pumera, Martin

2017-06-21

Graphene, produced via chemical methods, has been widely applied for electrochemical sensing due to its structural and electrochemical properties as well as its ease of production in large quantity. While nitrogen-doped graphenes are widely studied materials, the literature showing an effect of graphene oxide preparation methods on nitrogen quantity and chemical states as well as on defects and, in turn, on electrochemical sensing is non-existent. In this study, the properties of nitrogen-doped graphene materials, prepared via hydrothermal synthesis using graphite oxide produced by various classical methods using permanganate or chlorate oxidants Staudenmaier, Hummers, Hofmann and Brodie oxidation methods, were studied; the resulting nitrogen-doped graphene oxides were labeled as ST-GO, HU-GO, HO-GO and BR-GO, respectively. The electrochemical oxidation of biomolecules, such as ascorbic acid, uric acid, dopamine, nicotinamide adenine nucleotide and DNA free bases, was carried out using cyclic voltammetry and differential pulse voltammetry techniques. The nitrogen content in doped graphene oxides increased in the order ST-GO < BR-GO < HO-GO < HU-GO. In the same way, the pyridinic form of nitrogen increased and the electrocatalytic effect of N-doped graphene followed this trend, as shown in the cyclic voltammograms. This is a very important finding that provides insight into the electrocatalytic effect of N-doped graphene. The nitrogen-doped graphene materials exhibited improved sensitivity over bare glassy carbon for ascorbic acid, uric acid and dopamine detection. These studies will enhance our understanding of the effects of graphite oxide precursors on the electrochemical sensing properties of nitrogen-doped graphene materials.

Surface engineering on CeO2 nanorods by chemical redox etching and their enhanced catalytic activity for CO oxidation

NASA Astrophysics Data System (ADS)

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

2015-07-01

Controllable surface properties of nanocerias are desired for various catalytic processes. There is a lack of efficient approaches to adjust the surface properties of ceria to date. Herein, a redox chemical etching method was developed to controllably engineer the surface properties of ceria nanorods. Ascorbic acid and hydrogen peroxide were used to perform the redox chemical etching process, resulting in a rough surface and/or pores on the surface of ceria nanorods. Increasing the etching cycles induced a steady increase of the specific surface area, oxygen vacancies and surface Ce3+ fractions. As a result, the etched nanorods delivered enhanced catalytic activity for CO oxidation, compared to the non-etched ceria nanorods. Our method provides a novel and facile approach to continuously adjust the surface properties of ceria for practical applications.Controllable surface properties of nanocerias are desired for various catalytic processes. There is a lack of efficient approaches to adjust the surface properties of ceria to date. Herein, a redox chemical etching method was developed to controllably engineer the surface properties of ceria nanorods. Ascorbic acid and hydrogen peroxide were used to perform the redox chemical etching process, resulting in a rough surface and/or pores on the surface of ceria nanorods. Increasing the etching cycles induced a steady increase of the specific surface area, oxygen vacancies and surface Ce3+ fractions. As a result, the etched nanorods delivered enhanced catalytic activity for CO oxidation, compared to the non-etched ceria nanorods. Our method provides a novel and facile approach to continuously adjust the surface properties of ceria for practical applications. Electronic supplementary information (ESI) available: Diameter distributions of as-prepared and etched samples, optical images, specific catalytic data of CO oxidation and comparison of CO oxidation. See DOI: 10.1039/c5nr01846c

Transparent conducting oxides: A δ-doped superlattice approach

PubMed Central

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

2014-01-01

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. PMID:25109668

Structural, optical and electrochemical properties of F-doped vanadium oxide transparent semiconducting thin films

NASA Astrophysics Data System (ADS)

Mousavi, M.; Khorrami, Gh. H.; Kompany, A.; Yazdi, Sh. Tabatabai

2017-12-01

In this study, F-doped vanadium oxide thin films with doping levels up to 60 at % were prepared by spray pyrolysis method on glass substrates. To measure the electrochemical properties, some films were deposited on fluorine-tin oxide coated glass substrates. The effect of F-doping on the structural, electrical, optical and electrochemical properties of vanadium oxide samples was investigated. The X-ray diffractographs analysis has shown that all the samples grow in tetragonal β-V2O5 phase structure with the preferred orientation of [200]. The intensity of (200) peak belonging to β-V2O5 phase was strongest in the undoped vanadium oxide film. The scanning electron microscopy images show that the samples have nanorod- and nanobelt-shaped structure. The size of the nanobelts in the F-doped vanadium oxide films is smaller than that in the pure sample and the width of the nanobelts increases from 30 to 70 nm with F concentration. With increasing F-doping level from 10 to 60 at %, the resistivity, the transparency and the optical band gap decrease from 111 to 20 Ω cm, 70 to 50% and 2.4 to 2.36 eV, respectively. The cyclic voltammogram (CV) results show that the undoped sample has the most extensive CV and by increasing F-doping level from 20 to 60 at %, the area of the CV is expanded. The anodic and cathodic peaks in F-doped samples are stronger.

Two-stage epitaxial growth of vertically-aligned SnO2 nano-rods on (001) ceria

DOE Office of Scientific and Technical Information (OSTI.GOV)

Solovyov, VF; Wu, LJ; Rupich, MW

2014-12-15

Growth of high-aspect ratio oriented tin oxide, SnO2, nano-rods is complicated by a limited choice of matching substrates. We show that a (001) cerium oxide, CeO2, surface uniquely enables epitaxial growth of tin-oxide nano-rods via a two-stage process. First, (100) oriented nano-wires coat the ceria surface by lateral growth, forming a uniaxially-textured SnO2 deposit. Second, vertical SnO2 nano-rods nucleate on the deposit by homoepitaxy. We demonstrate growth of vertically oriented 1-2 mu m long nano-rods with an average diameter of approximate to 20 nm. 2014 Elsevier B.V. All rights reserved.

Improved Thermal Stability of Lithium-Rich Layered Oxide by Fluorine Doping.

PubMed

Kapylou, Andrei; Song, Jay Hyok; Missiul, Aleksandr; Ham, Dong Jin; Kim, Dong Han; Moon, San; Park, Jin Hwan

2018-01-05

The thermal stability of lithium-rich layered oxide with the composition Li(Li 1/6 Ni 1/6 Co 1/6 Mn 1/2 )O 2-x F x (x=0.00 and 0.05) is evaluated for use as a cathode material in lithium-ion batteries. Thermogravimetric analysis, evolved gas analysis, and differential scanning calorimetry show that, upon fluorine doping, degradation of the lithium-rich layered oxides commences at higher temperatures and the exothermic reaction is suppressed. Hot box tests also reveal that the prismatic cell with the fluorine-doped powder does not explode, whereas that with the undoped one explodes at about 135 °C with a sudden temperature increase. XRD analysis indicates that fluorine doping imparts the lithium-rich layered oxide with better thermal stability by mitigating oxygen release at elevated temperatures that cause an exothermic reaction with the electrolyte. The origin of the reduced oxygen release from the fluorinated lithium-rich layered oxide is also discussed. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrocatalytic N-Doped Graphitic Nanofiber - Metal/Metal Oxide Nanoparticle Composites.

PubMed

Tang, Hongjie; Chen, Wei; Wang, Jiangyan; Dugger, Thomas; Cruz, Luz; Kisailus, David

2018-03-01

Carbon-based nanocomposites have shown promising results in replacing commercial Pt/C as high-performance, low cost, nonprecious metal-based oxygen reduction reaction (ORR) catalysts. Developing unique nanostructures of active components (e.g., metal oxides) and carbon materials is essential for their application in next generation electrode materials for fuel cells and metal-air batteries. Herein, a general approach for the production of 1D porous nitrogen-doped graphitic carbon fibers embedded with active ORR components, (M/MO x , i.e., metal or metal oxide nanoparticles) using a facile two-step electrospinning and annealing process is reported. Metal nanoparticles/nanoclusters nucleate within the polymer nanofibers and subsequently catalyze graphitization of the surrounding polymer matrix and following oxidation, create an interconnected graphite-metal oxide framework with large pore channels, considerable active sites, and high specific surface area. The metal/metal oxide@N-doped graphitic carbon fibers, especially Co 3 O 4 , exhibit comparable ORR catalytic activity but superior stability and methanol tolerance versus Pt in alkaline solutions, which can be ascribed to the synergistic chemical coupling effects between Co 3 O 4 and robust 1D porous structures composed of interconnected N-doped graphitic nanocarbon rings. This finding provides a novel insight into the design of functional electrocatalysts using electrospun carbon nanomaterials for their application in energy storage and conversion fields. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Space charge induced surface stresses: implications in ceria and other ionic solids.

PubMed

Sheldon, Brian W; Shenoy, Vivek B

2011-05-27

Volume changes associated with point defects in space charge layers can produce strains that substantially alter thermodynamic equilibrium near surfaces in ionic solids. For example, near-surface compressive stresses exceeding -10 GPa are predicted for ceria. The magnitude of this effect is consistent with anomalous lattice parameter increases that occur in ceria nanoparticles. These stresses should significantly alter defect concentrations and key transport properties in a wide range of materials (e.g., ceria electrolytes in fuel cells). © 2011 American Physical Society

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.

Cobalt doped CuMnOx catalysts for the preferential oxidation of carbon monoxide

NASA Astrophysics Data System (ADS)

Dey, Subhashish; Dhal, Ganesh Chandra; Mohan, Devendra; Prasad, Ram; Gupta, Rajeev Nayan

2018-05-01

Carbon monoxide (CO) is a poisonous gas, recognized as a silent killer for the 21st century. It is produced from the partial oxidation of carbon containing compounds. The catalytic oxidation of CO receives a huge attention due to its applications in different fields. In the present work, hopcalite (CuMnOx) catalysts were synthesized using a co-precipitation method for CO oxidation purposes. Also, it was doped with the cobalt by varying concentration from 1 to 5wt%. It was observed that the addition of cobalt into the CuMnOx catalyst (by the deposition-precipitation method) improved the catalytic performance for the low-temperature CO oxidation. CuMnOx catalyst doped with 3wt% of cobalt exhibited most active performance and showed the highest activity than other cobalt concentrations. Different analytical tools (i.e. XRD, FTIR, BET, XPS and SEM-EDX) were used to characterize the as-synthesized catalysts. It was expected that the introduction of cobalt will introduce new active sites into the CuMnOx catalyst that are associated with the cobalt nano-particles. The order of calcination strategies based on the activity for cobalt doped CuMnOx catalysts was observed as: Reactive calcinations (RC) > flowing air > stagnant air. Therefore, RC (4.5% CO in air) route can be recommended for the synthesis of highly active catalysts. The catalytic activity of doped CuMnOx catalysts toward CO oxidation shows a correlation among average oxidation number of Mn and the position and the nature of the doped cobalt cation.

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.

Continuous Precipitation of Ceria Nanoparticles from a Continuous Flow Micromixer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tseng, Chih Heng; Paul, Brian; Chang, Chih-hung

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.

Anchoring ceria nanoparticles on graphene oxide and their radical scavenge properties under gamma irradiation environment.

PubMed

Xia, Wei; Zhao, Jun; Wang, Tao; Song, Li; Gong, Hao; Guo, Hu; Gao, Bing; Fan, Xiaoli; He, Jianping

2017-06-28

Polymer networks such as those of epoxy resin, as common protection materials, possess radiolytic oxidation degradation effects under gamma irradiation environment, which have a great accelerating effect on the ageing rate and severely limit their potential applications for metal protection in the nuclear industry. To overcome this, we report a simple scheme of anchoring crystalline ceria nanoparticles onto graphene sheets (CG) and incorporate it into the epoxy resin, followed by thermal polymerization to obtain CeO 2 /graphene-epoxy nanocomposite coating (CGNS). We had proven that graphene might act as "interwalls" in the epoxy matrix, which will result in space location-obstruct effect as well as absorb the radicals induced by γ-ray irradiation. Moreover, owing to the interconversion of cerium ions between their +3 and +4 states coupled with the formation of oxygen vacancy defects, electron spin resonance (ESR) detection shows that CeO 2 /graphene (CG) could act as a preferable radical scavenger and achieve better performance in trapping radicals than single graphene based composite. Electrochemical data strongly demonstrate that CeO 2 /graphene is capable of maintaining the anti-corrosion properties under gamma irradiation environment. Therefore, the designed hybrid CeO 2 /graphene-epoxy composite can be considered as potential candidates for protective coatings in nuclear industry.

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.

Adsorption and desorption characteristics of arsenic onto ceria nanoparticles

PubMed Central

2012-01-01

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

Synthesis, characterization and photocatalytic activity of porous manganese oxide doped titania for toluene decomposition.

PubMed

Jothiramalingam, R; Wang, M K

2007-08-17

The present study describes the photocatalytic degradation of toluene in gas phase on different porous manganese oxide doped titanium dioxide. As synthesized birnessite and cryptomelane type porous manganese oxide were doped with titania and tested for photocatalytic decomposition of toluene in gas phase. The effects of the inlet concentration of toluene, flow rate (retention time) were examined and the relative humidity was maintained constantly. Thermal and textural characterization of manganese oxide doped titania materials were characterized by X-ray diffraction (XRD), thermogravemetry (TG), BET and TEM-EDAX studies. The aim of the present study is to synthesize the porous manganese oxide doped titania and to study its photocatalytic activity for toluene degradation in gas phase. Cryptomelane doped titania catalyst prepared in water medium [K-OMS-2 (W)] is shown the good toluene degradation with lower catalysts loading compared to commercial bulk titania in annular type photo reactor. The higher photocatalytic activity due to various factors such as catalyst preparation method, experimental conditions, catalyst loading, surface area, etc. In the present study manganese oxide OMS doped titania materials prepared by both aqueous and non-aqueous medium, aqueous medium prepared catalyst shows the good efficiency due to the presence of OH bonded groups on the surface of catalyst. The linear forms of different kinetic equations were applied to the adsorption data and their goodness of fit was evaluated based on the R2 and standard error. The goodness to the linear fit was observed for Elovich model with high R2 (>or=0.9477) value.

Electrochemical investigation of mixed metal oxide nanocomposite electrode for low temperature solid oxide fuel cell

NASA Astrophysics Data System (ADS)

Abbas, Ghazanfar; Raza, Rizwan; Ashfaq Ahmad, M.; Ajmal Khan, M.; Jafar Hussain, M.; Ahmad, Mukhtar; Aziz, Hammad; Ahmad, Imran; Batool, Rida; Altaf, Faizah; Zhu, Bin

2017-10-01

Zinc-based nanostructured nickel (Ni) free metal oxide electrode material Zn0.60/Cu0.20Mn0.20 oxide (CMZO) was synthesized by solid state reaction and investigated for low temperature solid oxide fuel cell (LTSOFC) applications. The crystal structure and surface morphology of the synthesized electrode material were examined by XRD and SEM techniques respectively. The particle size of ZnO phase estimated by Scherer’s equation was 31.50 nm. The maximum electrical conductivity was found to be 12.567 S/cm and 5.846 S/cm in hydrogen and air atmosphere, respectively at 600∘C. The activation energy of the CMZO material was also calculated from the DC conductivity data using Arrhenius plots and it was found to be 0.060 and 0.075 eV in hydrogen and air atmosphere, respectively. The CMZO electrode-based fuel cell was tested using carbonated samarium doped ceria composite (NSDC) electrolyte. The three layers 13 mm in diameter and 1 mm thickness of the symmetric fuel cell were fabricated by dry pressing. The maximum power density of 728.86 mW/cm2 was measured at 550∘C.

High catalytic activity of Au/CeOx/TiO2(110) controlled by the nature of the mixed-metal oxide at the nanometer level.

PubMed

Park, Joon B; Graciani, Jesus; Evans, Jaime; Stacchiola, Dario; Ma, Shuguo; Liu, Ping; Nambu, Akira; Sanz, Javier Fernández; Hrbek, Jan; Rodriguez, José A

2009-03-31

Mixed-metal oxides play a very important role in many areas of chemistry, physics, materials science, and geochemistry. Recently, there has been a strong interest in understanding phenomena associated with the deposition of oxide nanoparticles on the surface of a second (host) oxide. Here, scanning tunneling microscopy, photoemission, and density-functional calculations are used to study the behavior of ceria nanoparticles deposited on a TiO(2)(110) surface. The titania substrate imposes nontypical coordination modes on the ceria nanoparticles. In the CeO(x)/TiO(2)(110) systems, the Ce cations adopt an structural geometry and an oxidation state (+3) that are quite different from those seen in bulk ceria or for ceria nanoparticles deposited on metal substrates. The increase in the stability of the Ce(3+) oxidation state leads to an enhancement in the chemical and catalytic activity of the ceria nanoparticles. The codeposition of ceria and gold nanoparticles on a TiO(2)(110) substrate generates catalysts with an extremely high activity for the production of hydrogen through the water-gas shift reaction (H(2)O + CO --> H(2) + CO(2)) or for the oxidation of carbon monoxide (2CO + O(2) --> 2CO(2)). The enhanced stability of the Ce(3+) state is an example of structural promotion in catalysis described here on the atomic level. The exploration of mixed-metal oxides at the nanometer level may open avenues for optimizing catalysts through stabilization of unconventional surface structures with special chemical activity.

Humidity sensing properties of Al-doped zinc oxide coating films

NASA Astrophysics Data System (ADS)

Saidi, S. A.; Mamat, M. H.; Ismail, A. S.; Malek, M. F.; Yusoff, M. M.; Sin, N. D. Md.; Zoolfakar, A. S.; Khusaimi, Z.; Rusop, M.

2018-05-01

Humidity sensor was fabricated using Al-doped zinc oxide (ZnO) coating films through spin-coating at room temperature. The sensing mechanism was discussed based on their nanostructures, such as surface area and porous nanostructures. Surface area and water adsorption are an important component in the low humidity, while at high humidity, porous nanostructures and capillary condensation become important. The results showed that the sensitivity of the Al-doped ZnO coating improved compared to that of the Al-doped ZnO nanorod arrays, with values of 7.38 at 40% to 90%RH (Relative humidity). All these results indicated that Al-doped ZnO coating had high potential for humidity-sensor applications.

Supercapacitors based on nitrogen-doped reduced graphene oxide and borocarbonitrides

NASA Astrophysics Data System (ADS)

Gopalakrishnan, K.; Moses, Kota; Govindaraj, A.; Rao, C. N. R.

2013-12-01

Nitrogen-doped reduced graphene oxide (RGO) samples with different nitrogen content, prepared by two different methods, as well as nitrogen-doped few-layer graphene have been investigated as supercapacitor electrodes. Two electrode measurements have been carried out both in aqueous (6M KOH) and in ionic liquid media. Nitrogen-doped reduced graphene oxides exhibit satisfactory specific capacitance, the values reaching 126F/g at a scan rate of 10mV/s in aqueous medium. Besides providing supercapacitor characteristics, the study has shown the nitrogen content and surface area to be important factors. High surface-area borocarbonitrides, BxCyNz, prepared by the urea route appear to be excellent supercapacitor electrode materials. Thus, BC4.5N exhibits a specific capacitance of 169F/g at a scan rate of 10mV/s in aqueous medium. In an ionic liquid medium, nitrogen-doped RGO and BC4.5N exhibit specific capacitance values of 258F/g and 240F/g at a scan rate of 5mV/s. The ionic liquid enables a larger operating voltage range of 0.0-2.5V compared to 0.0-1V in aqueous medium.

Spectroscopic studies on samarium oxide (Sm2O3) doped tungsten tellurite glasses

NASA Astrophysics Data System (ADS)

Shekhawat, M. S.; Basha, S. K. Shahenoor; Rao, M. C.

2018-05-01

Samarium oxide (Sm2O3) doped tungsten tellurite glasses have been prepared by conventional rapid melt quenching method. The optical absorption spectrum of Samarium oxide doped tellurite glasses showed an absorption peak at 301 nm. FT-Raman studies suggested that Sm2O3 could modify the properties of glass and CIE chromaticity coordinates were calculated for the generation of white light from the luminescence spectra.

Nitrogen-doped partially reduced graphene oxide rewritable nonvolatile memory.

PubMed

Seo, Sohyeon; Yoon, Yeoheung; Lee, Junghyun; Park, Younghun; Lee, Hyoyoung

2013-04-23

As memory materials, two-dimensional (2D) carbon materials such as graphene oxide (GO)-based materials have attracted attention due to a variety of advantageous attributes, including their solution-processability and their potential for highly scalable device fabrication for transistor-based memory and cross-bar memory arrays. In spite of this, the use of GO-based materials has been limited, primarily due to uncontrollable oxygen functional groups. To induce the stable memory effect by ionic charges of a negatively charged carboxylic acid group of partially reduced graphene oxide (PrGO), a positively charged pyridinium N that served as a counterion to the negatively charged carboxylic acid was carefully introduced on the PrGO framework. Partially reduced N-doped graphene oxide (PrGODMF) in dimethylformamide (DMF) behaved as a semiconducting nonvolatile memory material. Its optical energy band gap was 1.7-2.1 eV and contained a sp2 C═C framework with 45-50% oxygen-functionalized carbon density and 3% doped nitrogen atoms. In particular, rewritable nonvolatile memory characteristics were dependent on the proportion of pyridinum N, and as the proportion of pyridinium N atom decreased, the PrGODMF film lost memory behavior. Polarization of charged PrGODMF containing pyridinium N and carboxylic acid under an electric field produced N-doped PrGODMF memory effects that followed voltage-driven rewrite-read-erase-read processes.

Phosphate modified ceria as a Brønsted acidic/redox multifunctional catalyst

DOE PAGES

Nelson, Nicholas C.; Wang, Zhuoran; Naik, Pranjali; ...

2017-01-06

Deposition of trimethylphosphate onto ceria followed by thermal treatment resulted in the formation of surface phosphates with retention of the ceria fluorite structure. The structural and chemical properties of the phosphate-functionalized ceria were studied using 31P solid-state NMR, XPS, zeta titration, ammonia thermal desorption, pyridine adsorption, and model reactions. The introduction of phosphates generated Brønsted acid sites and decreased the number of Lewis acid sites on the surface. The relative amount of Lewis and Brønsted acids can be controlled by the amount of trimethylphosphate used in the synthesis. Upon deposition of Pd, the multifunctional material showed enhanced activity for themore » hydrogenolysis of eugenol and guaiacol compared to Pd on the unmodified ceria support. As a result, this was attributed to the cooperativity between the Lewis acid sites, which activate the substrate for dearomatization, and the redox/Brønsted acid properties, which catalyze hydrogenolysis.« less

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.

Structural study of VO {sub x} doped aluminium fluoride and aluminium oxide catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Scheurell, Kerstin; Scholz, Gudrun; Kemnitz, Erhard

The structural properties of vanadium doped aluminium oxyfluorides and aluminium oxides, prepared by a modified sol-gel synthesis route, were thoroughly investigated. The influence of the preparation technique and the calcination temperature on the coordination of vanadium, aluminium and fluorine was analysed by different spectroscopic methods such as Raman, MAS NMR and ESR spectroscopy. In all samples calcined at low temperatures (350 deg. C), vanadium coexists in two oxidation states V{sup IV} and V{sup V}, with V{sup IV} as dominating species in the vanadium doped aluminium oxyfluorides. In the fluoride containing solids aluminium as well as vanadium are coordinated by fluorinemore » and oxygen. Thermal annealing of 800 deg. C leads to an extensive reorganisation of the original matrices and to the oxidation of V{sup IV} to V{sup V} in both systems. - Graphical abstract: Structure model for VO {sub x} doped aluminium oxide.« less

Ceria-containing uncoated and coated hydroxyapatite-based galantamine nanocomposites for formidable treatment of Alzheimer's disease in ovariectomized albino-rat model.

PubMed

Wahba, Sanaa M R; Darwish, Atef S; Kamal, Sara M

2016-08-01

This paper upraises delivery and therapeutic actions of galantamine drug (GAL) against Alzheimer's disease (AD) in rat brain through attaching GAL to ceria-containing hydroxyapatite (GAL@Ce-HAp) as well ceria-containing carboxymethyl chitosan-coated hydroxyapatite (GAL@Ce-HAp/CMC) nanocomposites. Physicochemical features of such nanocomposites were analyzed by XRD, FT-IR, Raman spectroscopy, UV-vis spectrophotometer, N2-BET, DLS, zeta-potential measurements, SEM, and HR-TEM. Limited interactions were observed in GAL@Ce-HAp with prevailed existence of dispersed negatively charged rod-like particles conjugated with ceria nanodots. On contrary, GAL@Ce-HAp/CMC was well-structured developing aggregates of uncharged tetragonal-shaped particles laden with accession of ceria quantum dots. Such nanocomposites were i.p. injected into ovariectomized AD albino-rats at galantamine dose of 2.5mg/kg/day for one month, then brain tissues were collected for biochemical and histological tests. GAL@Ce-HAp adopted as a promising candidate for AD curativeness, whereas oxidative stress markers were successfully upregulated, degenerated neurons in hippocampal and cerebral tissues were wholly recovered and Aβ-plaques were vanished. Also, optimizable in-vitro release for GAL and nanoceria were displayed from GAL@Ce-HAp, while delayed in-vitro release for those species were developed from GAL@Ce-HAp/CMC. This proof of concept work allow futuristic omnipotency of rod-like hydroxyapatite particles for selective delivery of GAL and nanoceria to AD affected brain areas. Copyright © 2016 Elsevier B.V. All rights reserved.

Partial Oxidation of Hydrocarbons in a Segmented Bed Using Oxide-based Catalysts and Oxygen-conducting Supports

NASA Astrophysics Data System (ADS)

Smith, Mark W.

Two objectives for the catalytic reforming of hydrocarbons to produce synthesis gas are investigated herein: (1) the effect of oxygen-conducting supports with partially substituted mixed-metal oxide catalysts, and (2) a segmented bed approach using different catalyst configurations. Excess carbon deposition was the primary cause of catalyst deactivation, and was the focus of the experiments for both objectives. The formation and characterization of deposited carbon was examined after reaction for one of the selected catalysts to determine the quantity and location of the carbon on the catalyst surface leading to deactivation. A nickel-substituted barium hexaaluminate (BNHA), with the formula BaAl 11.6Ni0.4O18.8, and a Rh-substituted lanthanum zirconate pyrochlore (LCZR) with the formula La1.89Ca0.11 Zr1.89Rh0.11, were combined with two different doped ceria supports. These supports were gadolinium-doped ceria (GDC) and zirconium-doped ceria (ZDC). The active catalyst phases were combined with the supports in different ratios using different synthesis techniques. The catalysts were characterized using several different techniques and were tested under partial oxidation (POX) of n-tetradecane (TD), a diesel fuel surrogate. It was found that the presence of GDC and ZDC reduced the formation of carbon for both catalysts; the optimal ratio of catalyst to support was different for the hexaaluminate and the pyrochlore; a loading of 20 wt% of the pyrochlore with ZDC produced the most stable performance in the presence of common fuel contaminants (>50 h); and, the incipient wetness impregnation synthesis method of applying the active catalyst to the support produced more stable product yields than the catalyst prepared by a solid-state mixing technique. Different hexaaluminate and pyrochlore catalysts were used in different configurations in a segmented bed approach. The first strategy was to promote the indirect reforming mechanism by placing a combustion catalyst in the

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.

Metal oxide nanorod arrays on monolithic substrates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gao, Pu-Xian; Guo, Yanbing; Ren, Zheng

A metal oxide nanorod array structure according to embodiments disclosed herein includes a monolithic substrate having a surface and multiple channels, an interface layer bonded to the surface of the substrate, and a metal oxide nanorod array coupled to the substrate surface via the interface layer. The metal oxide can include ceria, zinc oxide, tin oxide, alumina, zirconia, cobalt oxide, and gallium oxide. The substrate can include a glass substrate, a plastic substrate, a silicon substrate, a ceramic monolith, and a stainless steel monolith. The ceramic can include cordierite, alumina, tin oxide, and titania. The nanorod array structure can includemore » a perovskite shell, such as a lanthanum-based transition metal oxide, or a metal oxide shell, such as ceria, zinc oxide, tin oxide, alumina, zirconia, cobalt oxide, and gallium oxide, or a coating of metal particles, such as platinum, gold, palladium, rhodium, and ruthenium, over each metal oxide nanorod. Structures can be bonded to the surface of a substrate and resist erosion if exposed to high velocity flow rates.« less

Sonochemically synthesized iron-doped zinc oxide nanoparticles: Influence of precursor composition on characteristics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Roy, Anirban; Maitra, Saikat; Ghosh, Sobhan

Highlights: • Sonochemical synthesis of iron-doped zinc oxide nanoparticles. • Green synthesis without alkali at room temperature. • Characterization by UV–vis spectroscopy, FESEM, XRD and EDX. • Influence of precursor composition on characteristics. • Composition and characteristics are correlated. - Abstract: Iron-doped zinc oxide nanoparticles have been synthesized sonochemically from aqueous acetyl acetonate precursors of different proportions. Synthesized nanoparticles were characterized with UV–vis spectroscopy, X-ray diffraction and microscopy. Influences of precursor mixture on the characteristics have been examined and modeled. Linear correlations have been proposed between dopant dosing, extent of doping and band gap energy. Experimental data corroborated with themore » proposed models.« less

The impact of thermal treatment conditions on the formation of crystalline structure of Ce-Zr-oxide composite obtained by a modified sol-gel technique

NASA Astrophysics Data System (ADS)

Trusova, E. A.; Khrushcheva, A. A.; Shvorneva, L. I.

2012-02-01

We present the results of the modified sol-gel synthesis of ultrafine ceria-doped zirconia powder for medical ceramics (implants) and catalytic purposes (environmental catalysis and petrochemistry). Special attention has been paid to study the influence of thermal treatment on crystallite size and crystal lattice parameters of zirconia doped by ceria. Zirconyl chloride and cerium nitrate were used as metal sources, and tetraethylammonium hydroxide (TEAH) was used as a sol stabilizer at molar ratio TEAH/Σ (Ce + Zr) equal to 0.5. It was proved that zirconium and cerium practically completely were included in the obtained solid solutions, since their phase compositions fully correspond to initial quantities of cerium and zirconium in reaction mixture. It was shown that average crystallite size of the obtained powders did not exceed 75Å, and the powders were resistant to thermal treatment. It was established that stabilization of the crystal lattice of ZrO2 occurs through formation of a cubic ceria sublattice.

Tunable infrared absorption and visible transparency of colloidal aluminum-doped zinc oxide nanocrystals.

PubMed

Buonsanti, Raffaella; Llordes, Anna; Aloni, Shaul; Helms, Brett A; Milliron, Delia J

2011-11-09

Plasmonic nanocrystals have been attracting a lot of attention both for fundamental studies and different applications, from sensing to imaging and optoelectronic devices. Transparent conductive oxides represent an interesting class of plasmonic materials in addition to metals and vacancy-doped semiconductor quantum dots. Herein, we report a rational synthetic strategy of high-quality colloidal aluminum-doped zinc oxide nanocrystals. The presence of substitutional aluminum in the zinc oxide lattice accompanied by the generation of free electrons is proved for the first time by tunable surface plasmon absorption in the infrared region both in solution and in thin films.

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

Alkaline earth metal doped tin oxide as a novel oxygen storage material

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dong, Qiang, E-mail: dong@tagen.tohoku.ac.jp; Yin, Shu; Yoshida, Mizuki

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 tinmore » 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.« less

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.

Effects of donor doping and acceptor doping on rutile TiO2 particles for photocatalytic O2 evolution by water oxidation

NASA Astrophysics Data System (ADS)

Amano, Fumiaki; Tosaki, Ryosuke; Sato, Kyosuke; Higuchi, Yamato

2018-02-01

Crystalline defects of photocatalyst particles may be considered to be the recombination center of photoexcited electrons and holes. In this study, we investigated the photocatalytic activity of cation-doped rutile TiO2 photocatalysts for O2 evolution from an aqueous silver nitrate solution under ultraviolet light irradiation. The photocatalytic activity of rutile TiO2 was enhanced by donor doping of Ta5+ and Nb5+ with a valence higher than that of Ti4+, regardless of increased density of electrons and Ti3+ species (an electron trapped in Ti4+ sites). Conversely, acceptor doping of lower valence cations such as In3+ and Ga3+ decreased photocatalytic activity for O2 evolution by water oxidation. The doping of equal valence cations such as Sn4+ and Ge4+ hardly changed the activity of non-doped TiO2. This study demonstrates that Ti3+ species, which is a crystalline defect, enhanced the photocatalytic activity of semiconductor oxides, for example rutile TiO2 with large crystalline size.

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.

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.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nasir, M. F., E-mail: babaibaik2002@yahoo.com; Zainol, M. N., E-mail: nizarzainol@yahoo.com; Hannas, M., E-mail: mhannas@gmail.com

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 thinmore » 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 × 10{sup 3} Ωcm{sup −1}. The absorption coefficient spectrum obtained shows all films exhibit very low absorption in the visible (400-800 nm) and near infrared (NIR) (>800 nm) range but exhibit high absorption in the UV range.« less

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.

Exploring routes to tailor the physical and chemical properties of oxides via doping: an STM study

NASA Astrophysics Data System (ADS)

Nilius, Niklas

2015-08-01

Doping opens fascinating possibilities for tailoring the electronic, optical, magnetic, and chemical properties of oxides. The dopants perturb the intrinsic behavior of the material by generating charge centers for electron transfer into adsorbates, by inducing new energy levels for electronic and optical excitations, and by altering the surface morphology and hence the adsorption and reactivity pattern. Despite a vivid scientific interest, knowledge on doped oxides is limited when compared to semiconductors, which reflects the higher complexity and the insulating nature of many oxides. In fact, atomic-scale studies, aiming at a mechanistic understanding of dopant-related processes, are still scarce. In this article, we review our scanning tunneling microscopy (STM) experiments on thin, crystalline oxide films with a defined doping level. We demonstrate how the impurities alter the surface morphology and produce cationic/anionic vacancies in order to keep the system charge neutral. We discuss how individual dopants can be visualized in the lattice, even if they reside in subsurface layers. By means of STM-conductance and x-ray photoelectron spectroscopy, we determine the electronic impact of dopants, including the energies of their eigen states and local band-bending effects in the host oxide. Electronic transitions between dopant-induced gap states give rise to new optical modes, as detected with STM luminescence spectroscopy. From a chemical perspective, dopants are introduced to improve the redox potential of oxide materials. Electron transfer from Mo-donors, for example, alters the growth behavior of gold and activates O2 molecules on a wide-gap CaO surface. Such results demonstrate the enormous potential of doped oxides in heterogeneous catalysis. Our experiments address the issue of doping from a fundamental viewpoint, posing questions on the lattice position, charge state, and electron-transfer potential of the impurity ions. Whether doped oxides are

Atomic layer deposition of ultrathin blocking layer for low-temperature solid oxide fuel cell on nanoporous substrate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yu, Wonjong; Cho, Gu Young; Noh, Seungtak

2015-01-15

An ultrathin yttria-stabilized zirconia (YSZ) blocking layer deposited by atomic layer deposition (ALD) was utilized for improving the performance and reliability of low-temperature solid oxide fuel cells (SOFCs) supported by an anodic aluminum oxide substrate. Physical vapor-deposited YSZ and gadolinia-doped ceria (GDC) electrolyte layers were deposited by a sputtering method. The ultrathin ALD YSZ blocking layer was inserted between the YSZ and GDC sputtered layers. To investigate the effects of an inserted ultrathin ALD blocking layer, SOFCs with and without an ultrathin ALD blocking layer were electrochemically characterized. The open circuit voltage (1.14 V) of the ALD blocking-layered SOFC was visiblymore » higher than that (1.05 V) of the other cell. Furthermore, the ALD blocking layer augmented the power density and improved the reproducibility.« less

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%.

Surface oxidation and thermoelectric properties of indium-doped tin telluride nanowires.

PubMed

Li, Zhen; Xu, Enzhi; Losovyj, Yaroslav; Li, Nan; Chen, Aiping; Swartzentruber, Brian; Sinitsyn, Nikolai; Yoo, Jinkyoung; Jia, Quanxi; Zhang, Shixiong

2017-09-14

The recent discovery of excellent thermoelectric properties and topological surface states in SnTe-based compounds has attracted extensive attention in various research areas. Indium doped SnTe is of particular interest because, depending on the doping level, it can either generate resonant states in the bulk valence band leading to enhanced thermoelectric properties, or induce superconductivity that coexists with topological states. Here we report on the vapor deposition of In-doped SnTe nanowires and the study of their surface oxidation and thermoelectric properties. The nanowire growth is assisted by Au catalysts, and their morphologies vary as a function of substrate position and temperature. Transmission electron microscopy characterization reveals the formation of an amorphous surface in single crystalline nanowires. X-ray photoelectron spectroscopy studies suggest that the nanowire surface is composed of In 2 O 3 , SnO 2 , Te and TeO 2 which can be readily removed by argon ion sputtering. Exposure of the cleaned nanowires to atmosphere leads to rapid oxidation of the surface within only one minute. Characterization of electrical conductivity σ, thermopower S, and thermal conductivity κ was performed on the same In-doped nanowire which shows suppressed σ and κ but enhanced S yielding an improved thermoelectric figure of merit ZT compared to the undoped SnTe.

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.

Production and characterization of europium doped sol-gel yttrium oxide

NASA Astrophysics Data System (ADS)

Krebs, J. K.; Hobson, Christopher; Silversmith, Ann

2004-03-01

Sol-gel produced materials have recently gained attention for their use in producing nanoscale dielectric materials for confinement studies. Lanthanide impurities in the dielectric enable experimenters to optically probe the structure and dynamic properties of the nanoparticle hosts. We report on an alkoxide sol-gel production method used to produce trivalent europium doped yttrium oxide. Our process follows the standard hydrolysis of an alkoxide precursor with water containing the lanthanide ions. The sol is then aged and calcined at 800 ^oC to produce the powder samples. X-ray diffraction confirms the structure of the powder is that of Y_2O_3. The emission and excitation of the europium impurities is consistent with that of europium doped single crystal yttrium oxide, where it is known that the europium ions substitute for yttrium in the lattice. We therefore conclude that the sol-gel process enables the incorporation of europium ions into the yttrium oxide structure at temperatures far below the melting temperature. The results of preliminary dynamics measurements will also be discussed.

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.

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.

Bipolar doping and band-gap anomalies in delafossite transparent conductive oxides.

PubMed

Nie, Xiliang; Wei, Su-Huai; Zhang, S B

2002-02-11

Doping wide-gap materials p type is highly desirable but often difficult. This makes the recent discovery of p-type delafossite oxides, CuM(III)O2, very attractive. The CuM(III)O2 also show unique and unexplained physical properties: Increasing band gap from M(III) = Al,Ga, to In, not seen in conventional semiconductors. The largest gap CuInO2 can be mysteriously doped both n and p type but not the smaller gaps CuAlO2 and CuGaO2. Here, we show that both properties are results of a large disparity between the fundamental gap and the apparent optical gap, a finding that could lead to a breakthrough in the study of bipolarly dopable wide-gap semiconductor oxides.

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

NASA Astrophysics Data System (ADS)

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

2015-08-01

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 Gd3+. 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.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

Zinc oxide doped graphene oxide films for gas sensing applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chetna,, E-mail: chetna2288@gmail.com; Kumar, Shani; Chaudhary, S.

Graphene Oxide (GO) is analogous to graphene, but presence of many functional groups makes its physical and chemical properties essentially different from those of graphene. GO is found to be a promising material for low cost fabrication of highly versatile and environment friendly gas sensors. Selectivity, reversibility and sensitivity of GO based gas sensor have been improved by hybridization with Zinc Oxide nanoparticles. The device is fabricated by spin coating of deionized water dispersed GO flakes (synthesized using traditional hummer’s method) doped with Zinc Oxide on standard glass substrate. Since GO is an insulator and functional groups on GO nanosheetsmore » play vital role in adsorbing gas molecules, it is being used as an adsorber. Additionally, on being exposed to certain gases the electric and optical characteristics of GO material exhibit an alteration in behavior. For the conductivity, we use Zinc Oxide, as it displays a high sensitivity towards conduction. The effects of the compositions, structural defects and morphologies of graphene based sensing layers and the configurations of sensing devices on the performances of gas sensors were investigated by Raman Spectroscopy, X-ray diffraction(XRD) and Keithley Sourcemeter.« less

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Curran, Christopher D.; Lu, Li; Jia, Yue

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 singlemore » 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.« less

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.

Promoting mechanism of N-doped single-walled carbon nanotubes for O2 dissociation and SO2 oxidation

NASA Astrophysics Data System (ADS)

Chen, Yanqiu; Yin, Shi; Chen, Yang; Cen, Wanglai; Li, Jianjun; Yin, Huaqiang

2018-03-01

Although heteroatom doping in carbon based catalysts have recently received intensive attentions, the role of the intrinsically porous structure of practical carbon materials and their potential synergy with doping atoms are still unclear. To investigate the complex effects, a range of N-doped single-walled carbon nanotubes (SWCNTs) were used to investigate their potential use for O2 dissociation and the subsequent SO2 oxidation using density functional theory. It is found that graphite N doping can synergize with the outer surface of SWCNTs to facilitate the dissociation of O2. The barrier for the dissociation on dual graphite N-doped SWCNT-(8, 8) is as low as 0.3 eV, and the subsequent SO2 oxidation is thermodynamically favorable and kinetically feasible. These results spotlight on developing promising carboncatalyst via utilization of porous gemometry and heteroatom-doping of carbon materials simultaneously.

Influence of xc functional on thermal-elastic properties of Ceria: A DFT-based Debye-Grüneisen model approach

NASA Astrophysics Data System (ADS)

Lee, Ji-Hwan; Tak, Youngjoo; Lee, Taehun; Soon, Aloysius

Ceria (CeO2-x) is widely studied as a choice electrolyte material for intermediate-temperature (~ 800 K) solid oxide fuel cells. At this temperature, maintaining its chemical stability and thermal-mechanical integrity of this oxide are of utmost importance. To understand their thermal-elastic properties, we firstly test the influence of various approximations to the density-functional theory (DFT) xc functionals on specific thermal-elastic properties of both CeO2 and Ce2O3. Namely, we consider the local-density approximation (LDA), the generalized gradient approximation (GGA-PBE) with and without additional Hubbard U as applied to the 4 f electron of Ce, as well as the recently popularized hybrid functional due to Heyd-Scuseria-Ernzehof (HSE06). Next, we then couple this to a volume-dependent Debye-Grüneisen model to determine the thermodynamic quantities of ceria at arbitrary temperatures. We find an explicit description of the strong correlation (e.g. via the DFT + U and hybrid functional approach) is necessary to have a good agreement with experimental values, in contrast to the mean-field treatment in standard xc approximations (such as LDA or GGA-PBE). We acknowledge support from Samsung Research Funding Center of Samsung Electronics (SRFC-MA1501-03).

Effect of Zinc Oxide Doping on Electroluminescence and Electrical Behavior of Metalloporphyrins-Doped Samarium Complex

NASA Astrophysics Data System (ADS)

Janghouri, Mohammad; Amini, Mostafa M.

2018-02-01

Samarium complex [(Sm(III)] as a new host material was used for preparation of red organic light-emitting diodes (OLEDs). Devices with configurations of indium-doped tin oxide (ITO)/poly(3,4-ethylenedioxythiophene):(poly(styrenesulfonate) (PEDOT:PSS (50 nm)/polyvinyl carbazole (PVK):[zinc oxide (ZnO)] (50 nm)/[(Sm(III)]:[zinc(II) 2,3-tetrakis(dihydroxyphenyl)-porphyrin and Pt(II) 2,3-dimethoxyporphyrin] (60 nm)/2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) (15 nm)/Al (150 nm) have been fabricated and investigated. An electroplex occurring at the (PVK/Sm: Pt(II) 2,3-dimethoxyporphyrin) interface has been suggested when ZnO nanoparticles were doped in PVK. OLED studies have revealed that the photophysical characteristics and electrical behavior of devices with ZnO nanoparticles are much better than those of devices with pure PVK. The efficiency of devices based on [(Sm(III)] was superior than that of known aluminum tris(8-hydroxyquinoline) (Alq3) and also our earlier reports on red OLEDs under the same conditions.

A method to explore the quantitative interactions between metal and ceria for M/CeO2 catalysts

NASA Astrophysics Data System (ADS)

Zhu, Kong-Jie; Liu, Jie; Yang, Yan-Ju; Xu, Yu-Xing; Teng, Bo-Tao; Wen, Xiao-Dong; Fan, Maohong

2018-03-01

To explore the quantitative relationship of metal interaction with ceria plays a key role in the theoretical design of M/CeO2 catalysts, especially for the new hot topic of atomically dispersed catalysts. A method to quantitatively explore the interactions between metal and ceria is proposed in the present work on the basis of the qualitative analysis of the effects of different factors on metal adsorption at different ceria surfaces by using Ag/CeO2 as a case. Two parameters are firstly presented, Ep which converts the total adsorption energy into the interaction energy per Agsbnd O bond, and θdiff which measures the deviation of Agsbnd Osbnd Ce bond angle from the angle of the sp3 orbital hybridization of O atom. Using the two parameters, the quantitative relationship of the interaction energy between Ag and ceria is established. There is a linear correlation between Ep and dAgsbndO with θdiff. The higher θdiff, the weaker Ep, and the longer Agsbnd O bond. This method is also suitable for other metals (Cu, Ni, Pd, and Rh, etc.) on ceria. It is the first time to establish the quantitative relationship for the interaction between metal and ceria, and sheds light into the theoretical design of M/CeO2 catalysts.

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).

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

EPA Science Inventory

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

Influence of low concentration V and Co oxide doping on the dissolution behaviors of simplified nuclear waste glasses

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lu, Xiaonan; Neeway, James J.; Ryan, Joseph V.

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 tomore » 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.« less

Zirconium doped nano-dispersed oxides of Fe, Al and Zn for destruction of warfare agents

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stengl, Vaclav, E-mail: stengl@uach.cz; Houskova, Vendula; Bakardjieva, Snejana

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 resultingmore » 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.« less

Metal Composition and Polyethylenimine Doping Capacity Effects on Semiconducting Metal Oxide-Polymer Blend Charge Transport.

PubMed

Huang, Wei; Guo, Peijun; Zeng, Li; Li, Ran; Wang, Binghao; Wang, Gang; Zhang, Xinan; Chang, Robert P H; Yu, Junsheng; Bedzyk, Michael J; Marks, Tobin J; Facchetti, Antonio

2018-04-25

Charge transport and film microstructure evolution are investigated in a series of polyethylenimine (PEI)-doped (0.0-6.0 wt%) amorphous metal oxide (MO) semiconductor thin film blends. Here, PEI doping generality is broadened from binary In 2 O 3 to ternary (e.g., In+Zn in IZO, In+Ga in IGO) and quaternary (e.g., In+Zn+Ga in IGZO) systems, demonstrating the universality of this approach for polymer electron doping of MO matrices. Systematic comparison of the effects of various metal ions on the electronic transport and film microstructure of these blends are investigated by combined thin-film transistor (TFT) response, AFM, XPS, XRD, X-ray reflectivity, and cross-sectional TEM. Morphological analysis reveals that layered MO film microstructures predominate in PEI-In 2 O 3 , but become less distinct in IGO and are not detectable in IZO and IGZO. TFT charge transport measurements indicate a general coincidence of a peak in carrier mobility (μ peak ) and overall TFT performance at optimal PEI doping concentrations. Optimal PEI loadings that yield μ peak values depend not only on the MO elemental composition but also, equally important, on the metal atomic ratios. By investigating the relationship between the MO energy levels and PEI doping by UPS, it is concluded that the efficiency of PEI electron-donation is highly dependent on the metal oxide matrix work function in cases where film morphology is optimal, as in the IGO compositions. The results of this investigation demonstrate the broad generality and efficacy of PEI electron doping applied to electronically functional metal oxide systems and that the resulting film microstructure, morphology, and energy level modifications are all vital to understanding charge transport in these amorphous oxide blends.

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 MoO 3 , WO 3 , CrO 3 , and V 2 O 5 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.

Li-doped MgO as catalysts for oxidative coupling of methane: A positron annihilation study

NASA Astrophysics Data System (ADS)

Dai, G. H.; Yan, Q. J.; Wang, Y.; Liu, Q. S.

1991-08-01

Magnesium oxides intentionally doped with lithium (with a maximum Li content of 40 tool%) for use as catalysts for oxidative coupling of methane were characterized by means of positron annihilation. The positron lifetime spectra, which could be reasonably well interpreted within the framework of the well-known trapping model, depend on the amount of Li doping of the MgO suggesting that positrons are trapped at dispersed small Li 2CO 3 precipitates. Very similar dependencies on lithium doping of the C 2 selectivity and the positron trapping rate ϰ imply an intimate relationship between the concentration of [Li] 0-centers (also referred to as [Li +O -] centers) and the selective activity of Li/MgO during catalytic reactions.

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.

Stabilizing Nanocrystalline Oxide Nanofibers at Elevated Temperatures by Coating Nanoscale Surface Amorphous Films.

PubMed

Yao, Lei; Pan, Wei; Luo, Jian; Zhao, Xiaohui; Cheng, Jing; Nishijima, Hiroki

2018-01-10

Nanocrystalline materials often exhibit extraordinary mechanical and physical properties but their applications at elevated temperatures are impaired by the rapid grain growth. Moreover, the grain growth in nanocrystalline oxide nanofibers at high temperatures can occur at hundreds of degrees lower than that would occur in corresponding bulk nanocrystalline materials, which would eventually break the fibers. Herein, by characterizing a model system of scandia-stabilized zirconia using hot-stage in situ scanning transmission electron microscopy, we discover that the enhanced grain growth in nanofibers is initiated at the surface. Subsequently, we demonstrate that coating the fibers with nanometer-thick amorphous alumina layer can enhance their temperature stability by nearly 400 °C via suppressing the surface-initiated grain growth. Such a strategy can be effectively applied to other oxide nanofibers, such as samarium-doped ceria, yttrium-stabilized zirconia, and lanthanum molybdate. The nanocoatings also increase the flexibility of the oxide nanofibers and stabilize the high-temperature phases that have 10 times higher ionic conductivity. This study provides new insights into the surface-initiated grain growth in nanocrystalline oxide nanofibers and develops a facile yet innovative strategy to improve the high-temperature stability of nanofibers for a broad range of applications.

First principles study of vibrational dynamics of ceria-titania hybrid clusters

NASA Astrophysics Data System (ADS)

Majid, Abdul; Bibi, Maryam

2017-04-01

Density functional theory based calculations were performed to study vibrational properties of ceria, titania, and ceria-titania hybrid clusters. The findings revealed the dominance of vibrations related to oxygen when compared to those of metallic atoms in the clusters. In case of hybrid cluster, the softening of normal modes related to exterior oxygen atoms in ceria and softening/hardening of high/low frequency modes related to titania dimmers are observed. The results calculated for monomers conform to symmetry predictions according to which three IR and three Raman active modes were detected for TiO2, whereas two IR active and one Raman active modes were observed for CeO2. The comparative analysis indicates that the hybrid cluster CeTiO4 contains simultaneous vibrational fingerprints of the component dimmers. The symmetry, nature of vibrations, IR and Raman activity, intensities, and atomic involvement in different modes of the clusters are described in detail. The study points to engineering of CeTiO4 to tailor its properties for technological visible region applications in photocatalytic and electrochemical devices.

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. Copyright © 2015 Elsevier Inc. All rights reserved.

Fabrication of low-temperature solid oxide fuel cells with a nanothin protective layer by atomic layer deposition

PubMed Central

2013-01-01

Anode aluminum oxide-supported thin-film fuel cells having a sub-500-nm-thick bilayered electrolyte comprising a gadolinium-doped ceria (GDC) layer and an yttria-stabilized zirconia (YSZ) layer were fabricated and electrochemically characterized in order to investigate the effect of the YSZ protective layer. The highly dense and thin YSZ layer acted as a blockage against electron and oxygen permeation between the anode and GDC electrolyte. Dense GDC and YSZ thin films were fabricated using radio frequency sputtering and atomic layer deposition techniques, respectively. The resulting bilayered thin-film fuel cell generated a significantly higher open circuit voltage of approximately 1.07 V compared with a thin-film fuel cell with a single-layered GDC electrolyte (approximately 0.3 V). PMID:23342963

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

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

Formation of hydroxyl radicals and kinetic study of 2-chlorophenol photocatalytic oxidation using C-doped TiO2, N-doped TiO2, and C,N Co-doped TiO2 under visible light.

PubMed

Ananpattarachai, Jirapat; Seraphin, Supapan; Kajitvichyanukul, Puangrat

2016-02-01

This work reports on synthesis, characterization, adsorption ability, formation rate of hydroxyl radicals (OH(•)), photocatalytic oxidation kinetics, and mineralization ability of C-doped titanium dioxide (TiO2), N-doped TiO2, and C,N co-doped TiO2 prepared by the sol-gel method. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and UV-visible spectroscopy were used to analyze the titania. The rate of formation of OH(•) for each type of titania was determined, and the OH-index was calculated. The kinetics of as-synthesized TiO2 catalysts in photocatalytic oxidation of 2-chlorophenol (2-CP) under visible light irradiation were evaluated. Results revealed that nitrogen was incorporated into the lattice of titania with the structure of O-Ti-N linkages in N-doped TiO2 and C,N co-doped TiO2. Carbon was joined to the Ti-O-C bond in the C-doped TiO2 and C,N co-doped TiO2. The 2-CP adsorption ability of C,N co-doped TiO2 and C-doped TiO2 originated from a layer composed of a complex carbonaceous mixture at the surface of TiO2. C,N co-doped TiO2 had highest formation rate of OH(•) and photocatalytic activity due to a synergistic effect of carbon and nitrogen co-doping. The order of photocatalytic activity per unit surface area was the same as that of the formation rate of OH(•) unit surface area in the following order: C,N co-doped TiO2 > C-doped TiO2 > N-doped TiO2 > undoped TiO2.

Effect of nitrogen doping on structural, morphological, optical and electrical properties of radio frequency magnetron sputtered zinc oxide thin films

NASA Astrophysics Data System (ADS)

Perumal, R.; Hassan, Z.

2016-06-01

Zinc oxide receives remarkable attention due to its several attractive physical properties. Zinc oxide thin films doped with nitrogen were grown by employing RF magnetron sputtering method at room temperature. Doping was accomplished in gaseous medium by mixing high purity nitrogen gas along with argon sputtering gas. Structural studies confirmed the high crystalline nature with c-axis oriented growth of the nitrogen doped zinc oxide thin films. The tensile strain was developed due to the incorporation of the nitrogen into the ZnO crystal lattice. Surface roughness of the grown films was found to be decreased with increasing doping level was identified through atomic force microscope analysis. The presenting phonon modes of each film were confirmed through FTIR spectral analysis. The increasing doping level leads towards red-shifting of the cut-off wavelength due to decrement of the band gap was identified through UV-vis spectroscopy. All the doped films exhibited p-type conductivity was ascertained using Hall measurements and the obtained results were presented.

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.

Doped δ-bismuth oxides to investigate oxygen ion transport as a metric for condensed phase thermite ignition.

PubMed

Wang, Xizheng; Zhou, Wenbo; DeLisio, Jeffery B; Egan, Garth C; Zachariah, Michael R

2017-05-24

Nanothermites offer high energy density and high burn rates, but are mechanistically only now being understood. One question of interest is how initiation occurs and how the ignition temperature is related to microscopic controlling parameters. In this study, we explored the potential role of oxygen ion transport in Bi 2 O 3 as a controlling mechanism for condensed phase ignition reaction. Seven different doped δ-Bi 2 O 3 were synthesized by aerosol spray pyrolysis. The ignition temperatures of Al/doped Bi 2 O 3 , C/doped Bi 2 O 3 and Ta/doped Bi 2 O 3 were measured by temperature-jump/time-of-flight mass spectrometer coupled with a high-speed camera respectively. These results were then correlated to the corresponding oxygen ion conductivity (directly proportional to ion diffusivity) for these doped Bi 2 O 3 measured by impedance spectroscopy. We find that ignition of thermite with doped Bi 2 O 3 as oxidizer occurs at a critical oxygen ion conductivity (∼0.06 S cm -1 ) of doped Bi 2 O 3 in the condensed-phase so long as the aluminum is in a molten state. These results suggest that oxygen ion transport limits the condensed state Bi 2 O 3 oxidized thermite ignition. We also find that the larger oxygen vacancy concentration and the smaller metal-oxide bond energy in doped Bi 2 O 3 , the lower the ignition temperature. The latter suggests that we can consider the possibility of manipulating microscopic properties within a crystal, to tune the resultant energetic properties.

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

Alteration of hepatic structure and oxidative stress induced by intravenous nanoceria

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tseng, Michael T., E-mail: mttsen01@louisville.edu; Lu, Xiaoqin, E-mail: x0lu0003@louisville.edu; Duan, Xiaoxian, E-mail: x0duan02@louisville.edu

2012-04-15

Beyond the traditional use of ceria as an abrasive, the scope of nanoceria applications now extends into fuel cell manufacturing, diesel fuel additives, and for therapeutic intervention as a putative antioxidant. However, the biological effects of nanoceria exposure have yet to be fully defined, which gave us the impetus to examine its systemic biodistribution and biological responses. An extensively characterized nanoceria (5 nm) dispersion was vascularly infused into rats, which were terminated 1 h, 20 h or 30 days later. Light and electron microscopic tissue characterization was conducted and hepatic oxidative stress parameters determined. We observed acute ceria nanoparticle sequestrationmore » by Kupffer cells with subsequent bioretention in parenchymal cells as well. The internalized ceria nanoparticles appeared as spherical agglomerates of varying dimension without specific organelle penetration. In hepatocytes, the agglomerated nanoceria frequently localized to the plasma membrane facing bile canaliculi. Hepatic stellate cells also sequestered nanoceria. Within the sinusoids, sustained nanoceria bioretention was associated with granuloma formations comprised of Kupffer cells and intermingling CD3{sup +} T cells. A statistically significant elevation of serum aspartate aminotransferase (AST) level was seen at 1 and 20 h, but subsided by 30 days after ceria administration. Further, elevated apoptosis was observed on day 30. These findings, together with increased hepatic protein carbonyl levels on day 30, indicate ceria-induced hepatic injury and oxidative stress, respectively. Such observations suggest a single vascular infusion of nanoceria can lead to persistent hepatic retention of particles with possible implications for occupational and therapeutic exposures. -- Highlights: ► Time course study on nanoceria induced hepatic alterations in rats. ► Serum AST elevation indicated acute hepatotoxicity. ► Ceria is retained for up to 30 days in Kupffer

Graphene oxide vs. reduced graphene oxide as saturable absorbers for Er-doped passively mode-locked fiber laser.

PubMed

Sobon, Grzegorz; Sotor, Jaroslaw; Jagiello, Joanna; Kozinski, Rafal; Zdrojek, Mariusz; Holdynski, Marcin; Paletko, Piotr; Boguslawski, Jakub; Lipinska, Ludwika; Abramski, Krzysztof M

2012-08-13

In this work we demonstrate comprehensive studies on graphene oxide (GO) and reduced graphene oxide (rGO) based saturable absorbers (SA) for mode-locking of Er-doped fiber lasers. The paper describes the fabrication process of both saturable absorbers and detailed comparison of their parameters. Our results show, that there is no significant difference in the laser performance between the investigated SA. Both provided stable, mode-locked operation with sub-400 fs soliton pulses and more than 9 nm optical bandwidth at 1560 nm center wavelength. It has been shown that GO might be successfully used as an efficient SA without the need of its reduction to rGO. Taking into account simpler manufacturing technology and the possibility of mass production, GO seems to be a good candidate as a cost-effective material for saturable absorbers for Er-doped fiber lasers.

Temperature dependent selective detection of hydrogen and acetone using Pd doped WO3/reduced graphene oxide nanocomposite

NASA Astrophysics Data System (ADS)

Kaur, Jasmeet; Anand, Kanica; Kohli, Nipin; Kaur, Amanpreet; Singh, Ravi Chand

2018-06-01

Reduced graphene oxide (RGO) and Pd doped WO3 nanocomposites were fabricated by employing electrostatic interactions between poly (diallyldimethylammonium chloride) (PDDA) modified Pd doped WO3 nanostructures and graphite oxide (GO) and studied for their gas sensing application. XRD, Raman, FTIR, FESEM-EDX, TEM, TGA, XPS and Photoluminescence techniques were used for characterization of as-synthesized samples. Gas sensing studies revealed that the sensor with optimized doping of 1.5 mol% Pd and 1 wt% GO shows temperature dependent selectivity towards hydrogen and acetone. The role of WO3, Pd and RGO has been discussed in detail for enhanced sensing performance.

Rational design of mixed ionic and electronic conducting perovskite oxides for solid oxide fuel cell anode materials: A case study for doped SrTiO3

DOE Office of Scientific and Technical Information (OSTI.GOV)

Suthirakun, Suwit; Xiao, Guoliang; Ammal, Salai Cheettu

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-more » 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.« less

SolarSyngas: Results from a virtual institute developing materials and key components for solar thermochemical fuel production

NASA Astrophysics Data System (ADS)

Roeb, Martin; Steinfeld, Aldo; Borchardt, Günter; Feldmann, Claus; Schmücker, Martin; Sattler, Christian; Pitz-Paal, Robert

2016-05-01

The Helmholtz Virtual Institute (VI) SolarSynGas brings together expertise from solar energy research and materials science to develop metal oxide based redox materials and to integrate them in a suitable way into related process technologies for two-step thermochemical production of hydrogen and carbon monoxide from water and CO2. One of the foci of experimental investigation was exploring the impact of doping on the feasibility of ceria-based materials - mainly by Zr-doping. The results indicate that a certain Zr-content enhances the reducibility and therefore the splitting performance. Increasing the Zr-content to x = 0.15 improved the specific CO2-splitting performance by 50% compared to pure ceria. This finding agrees with theoretical studies attributing the improvements to lattice modification caused by the introduction of Zr4+. Thermogravimetric relaxation experiments and equilibrium oxygen isotope exchange experiments with subsequent depth profiling analysis were carried out on ceria. As a result the reduction reaction of even dense samples of pure ceria with a grain size of about 20 µm is surface reaction controlled. The structure of the derived expression for the apparent activation energy suggests that the chemical surface exchange coefficient should show only a very weak dependence on temperature for ceria doped with lower valence cations. A solar receiver reactor exhibiting a foam-type reticulated porous ceramics made of ceria was tested. It could be shown that applying dual-scale porosity to those foams with mm-size pores for effective radiative heat transfer during reduction and μm-size pores within its struts for enhanced kinetics during oxidation allows enhancing the performance of the reactor significantly. Also a particle process concept applying solid-solid heat recovery from redox particles in a high temperature solar thermochemical process was analysed that uses ceramic spheres as solid heat transfer medium. This concept can be implemented

Effective Heat and Mass Transport Properties of Anisotropic Porous Ceria for Solar Thermochemical Fuel Generation

PubMed Central

Haussener, Sophia; Steinfeld, Aldo

2012-01-01

High-resolution X-ray computed tomography is employed to obtain the exact 3D geometrical configuration of porous anisotropic ceria applied in solar-driven thermochemical cycles for splitting H2O and CO2. The tomography data are, in turn, used in direct pore-level numerical simulations for determining the morphological and effective heat/mass transport properties of porous ceria, namely: porosity, specific surface area, pore size distribution, extinction coefficient, thermal conductivity, convective heat transfer coefficient, permeability, Dupuit-Forchheimer coefficient, and tortuosity and residence time distributions. Tailored foam designs for enhanced transport properties are examined by means of adjusting morphologies of artificial ceria samples composed of bimodal distributed overlapping transparent spheres in an opaque medium. PMID:28817039

Electrical properties of aluminum-doped zinc oxide (AZO) nanoparticles synthesized by chemical vapor synthesis.

PubMed

Hartner, Sonja; Ali, Moazzam; Schulz, Christof; Winterer, Markus; Wiggers, Hartmut

2009-11-04

Aluminum-doped zinc oxide nanoparticles have been prepared by chemical vapor synthesis, which facilitates the incorporation of a higher percentage of dopant atoms, far above the thermodynamic solubility limit of aluminum. The electrical properties of aluminum-doped and undoped zinc oxide nanoparticles were investigated by impedance spectroscopy. The impedance is measured under hydrogen and synthetic air between 323 and 673 K. The measurements under hydrogen as well as under synthetic air show transport properties depending on temperature and doping level. Under hydrogen atmosphere, a decreasing conductivity with increasing dopant content is observed, which can be explained by enhanced scattering processes due to an increasing disorder in the nanocrystalline material. The temperature coefficient for the doped samples switches from positive temperature coefficient behavior to negative temperature coefficient behavior with increasing dopant concentration. In the presence of synthetic air, the conductivity firstly increases with increasing dopant content by six orders of magnitude. The origin of the increasing conductivity is the generation of free charge carriers upon dopant incorporation. It reaches its maximum at a concentration of 7.7% of aluminum, and drops for higher doping levels. In all cases, the conductivity under hydrogen is higher than under synthetic air and can be changed reversibly by changing the atmosphere.

Doping profile measurements in silicon using terahertz time domain spectroscopy (THz-TDS) via electrochemical anodic oxidation

NASA Astrophysics Data System (ADS)

Tulsyan, Gaurav

Doping profiles are engineered to manipulate device properties and to determine electrical performances of microelectronic devices frequently. To support engineering studies afterward, essential information is usually required from physically characterized doping profiles. Secondary Ion Mass Spectrometry (SIMS), Spreading Resistance Profiling (SRP) and Electrochemical Capacitance Voltage (ECV) profiling are standard techniques for now to map profile. SIMS yields a chemical doping profile via ion sputtering process and owns a better resolution, whereas ECV and SRP produce an electrical doping profile detecting free carriers in microelectronic devices. The major difference between electrical and chemical doping profiles is at heavily doped regions greater than 1020 atoms/cm3. At the profile region over the solubility limit, inactive dopants induce a flat plateau and detected by electrical measurements only. Destructive techniques are usually designed as stand-alone systems to study impurities. For an in-situ process control purpose, non-contact methods, such as ellipsometry and non-contact capacitance voltage (CV) techniques are current under development. In this theses work, terahertz time domain spectroscopy (THz-TDS) is utilized to achieve electrical doping profile in both destructive and non-contact manners. In recent years the Terahertz group at Rochester Institute Technology developed several techniques that use terahertz pulses to non-destructively map doping profiles. In this thesis, we study a destructive but potentially higher resolution version of the terahertz based approach to map the profile of activated dopants and augment the non-destructive approaches already developed. The basic idea of the profile mapping approach developed in this MS thesis is to anodize, and thus oxidize to silicon dioxide, thin layers (down to below 10 nm) of the wafer with the doping profile to be mapped. Since the dopants atoms and any free carriers in the silicon oxide thin

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.

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.

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

Supported Pd nanoclusters with enhanced hydrogen spillover for NOx removal via H2-SCR: the elimination of "volcano-type" behaviour.

PubMed

Peng, Zhezhe; Li, Zongyuan; Liu, Yun-Quan; Yan, Shuai; Tong, Jianing; Wang, Duo; Ye, Yueyuan; Li, Shuirong

2017-05-30

A rational design of a Pd catalyst with highly dispersed Pd nanoclusters on an Al doped ceria-based oxide for low temperature selective catalytic reduction of NO x by hydrogen with excess O 2 was achieved. The supported Pd nanocluster shows a high hydrogen spillover ability and a NO x conversion of >84% within 100-300 °C.

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.

Improving the optoelectronic properties of titanium-doped indium tin oxide thin films

NASA Astrophysics Data System (ADS)

Taha, Hatem; Jiang, Zhong-Tao; Henry, David J.; Amri, Amun; Yin, Chun-Yang; Mahbubur Rahman, M.

2017-06-01

The focus of this study is on a sol-gel method combined with spin-coating to prepare high-quality transparent conducting oxide (TCO) films. The structural, morphological, optical and electrical properties of sol-gel-derived pure and Ti-doped indium tin oxide (ITO) thin films were studied as a function of the concentration of the Ti (i.e. 0 at%, 2 at% and 4 at%) and annealing temperatures (150 °C-600 °C). FESEM measurements indicate that all the films are ˜350 nm thick. XRD analysis confirmed the cubic bixbyite structure of the polycrystalline indium oxide phase for all of the thin films. Increasing the Ti ratio, as well as the annealing temperature, improved the crystallinity of the films. Highly crystalline structures were obtained at 500 °C, with average grain sizes of about 50, 65 and 80 nm for Ti doping of 0 at%, 2 at% and 4 at%, respectively. The electrical and optical properties improved as the annealing temperature increased, with an enlarged electronic energy band gap and an optical absorption edge below 280 nm. In particular, the optical transmittance and electrical resistivity of the samples with a 4 at% Ti content improved from 87% and 7.10 × 10-4 Ω.cm to 92% and 1.6 × 10-4 Ω.cm, respectively. The conductivity, especially for the annealing temperature at 150 °C, is acceptable for many applications such as flexible electronics. These results demonstrate that unlike the more expensive and complex vacuum sputtering process, high-quality Ti-doped ITO films can be achieved by fast processing, simple wet-chemistry, and easy doping level control with the possibility of producing films with high scalability.

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.

The effect of cerium oxide argon-annealed coatings on the high temperature oxidation of a FeCrAl alloy

NASA Astrophysics Data System (ADS)

Nguyen, C. T.; Buscail, H.; Cueff, R.; Issartel, C.; Riffard, F.; Perrier, S.; Poble, O.

2009-09-01

Ceria coatings were applied in order to improve the adherence of alumina scales developed on a model Fe-20Cr-5Al alloy during oxidation at high temperature. These coatings were performed by argon annealing of a ceria sol-gel coating at temperatures ranging between 600 and 1000 °C. The influence of these coatings on the alloy oxidation behaviour was studied at 1100 °C. In situ X-ray diffraction (XRD) was performed to characterize the coating crystallographic nature after annealing and during the oxidation process. The alumina scale morphologies were studied by means of scanning electron microscopy (SEM) coupled with energy dispersive X-ray spectroscopy (EDS). The present work shows that the alumina scale morphology observed on cerium sol-gel coated alloy was very convoluted. On the cerium sol-gel coated alloy, argon annealing results in an increase of the oxidation rate in air, at 1100 °C. The 600 °C argon annealing temperature results in a good alumina scale adherence under thermal cycling conditions at 1100 °C.

Preparation of Cu-doped nickel oxide thin films and their properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gowthami, V.; Meenakshi, M.; Anandhan, N.

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.

Effects of the Physical Characteristics of Cerium Oxide on Plasma-Enhanced Tetraethylorthosiliate Removal Rate of Chemical Mechanical Polishing for Shallow Trench Isolation

NASA Astrophysics Data System (ADS)

Kim, Sang-Kyun; Paik, Ungyu; Oh, Seong-Geun; Park, Yong-Kook; Katoh, Takeo; Park, Jea-Gun

2003-03-01

Ceria powders were synthesized by two different methods, solid-state displacement reaction and wet chemical precipitation, and the influence of the physical characteristics of cerium oxide on the removal rate of plasma-enhanced tetraethylorthosilicate (PETEOS) and chemical vapor deposition (CVD) nitride films in chemical mechanical planarization (CMP) was investigated. The fundamental physicochemical property and electrokinetic behavior of ceria particles in aqueous suspending media were investigated to identify the correlation between the colloidal property of ceria and the CMP performance. The surface potentials of two different ceria particles are found to have different isoelectric point (pHiep) values and differences in physical properties of ceria particles such as porosity and density were found to be the key parameters in CMP of PETEOS films. Ceria powders synthesized by the solid-state displacement reaction method yielded a higher removal rate of PETEOS and higher selectivity than powders synthesized by the wet chemical precipitation method.

Photo-oxidative doping in π-conjugated zig-zag chain of carbon atoms with sulfur-functional group

NASA Astrophysics Data System (ADS)

Ikeura-Sekiguchi, Hiromi; Sekiguchi, Tetsuhiro

2017-12-01

Photo-oxidative doping processes were studied for the trans-polyacetylene backbone with the -SCH3 side group as a chemically representative of the precisely controlled S-functionalized zig-zag graphene nanoribbon edge. Sulfur K-edge X-ray absorption near edge structure (XANES) spectroscopy indicates that photochemical reaction of S-CH3 with atmospheric O2 forms selectively oxidized products such as -S(O)CH3 and -SO3- bound to the polyacetylene (PA) backbone. Using the correlation between the oxidation states of sulfur and the XANES peak positions, the partial charge distribution of CH3Sδ+-PAδ- has been estimated. Such positively charged sulfur atoms can attract higher electronegative oxygen atoms and expect to enhance the photooxidization capabilities. The formation of the -SO3- side group is evidently responsible for hole doping into the PA backbone. The results can provide some strategy for area-selective and controllable doping processes of atomic-scale molecular systems with the assistance of UV light.

Thermoelectric Properties of Hot-Pressed and PECS-Sintered Magnesium-Doped Copper Aluminum Oxide

NASA Astrophysics Data System (ADS)

Liu, Chang; Morelli, Donald T.

2011-05-01

Copper aluminum oxide (CuAlO2) is considered as a potential candidate for thermoelectric applications. Partially magnesium-doped CuAlO2 bulk pellets were fabricated using solid-state reactions, hot-pressing, and pulsed electric current sintering (PECS) techniques. X-ray diffraction and scanning electron microscopy were adopted for structural analysis. High-temperature transport property measurements were performed on hot-pressed samples. Electrical conductivity increased with Mg doping before secondary phases became significant, while the Seebeck coefficient displayed the opposite trend. Thermal conductivity was consistently reduced as the Mg concentration increased. Effects of Mg doping, preparation conditions, and future modification on this material's properties are discussed.

Defect Chemistry of Oxides for Energy Applications.

PubMed

Schweke, Danielle; Mordehovitz, Yuval; Halabi, Mahdi; Shelly, Lee; Hayun, Shmuel

2018-05-31

Oxides are widely used for energy applications, as solid electrolytes in various solid oxide fuel cell devices or as catalysts (often associated with noble metal particles) for numerous reactions involving oxidation or reduction. Defects are the major factors governing the efficiency of a given oxide for the above applications. In this paper, the common defects in oxide systems and external factors influencing the defect concentration and distribution are presented, with special emphasis on ceria (CeO 2 ) based materials. It is shown that the behavior of a variety of oxide systems with respect to properties relevant for energy applications (conductivity and catalytic activity) can be rationalized by general considerations about the type and concentration of defects in the specific system. A new method based on transmission electron microscopy (TEM), recently reported by the authors for mapping space charge defects and measuring space charge potentials, is shown to be of potential importance for understanding conductivity mechanisms in oxides. The influence of defects on gas-surface reactions is exemplified on the interaction of CO 2 and H 2 O with ceria, by correlating between the defect distribution in the material and its adsorption capacity or splitting efficiency. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Spray deposition of highly transparent fluorine doped cadmium oxide thin films

NASA Astrophysics Data System (ADS)

Deokate, R. J.; Pawar, S. M.; Moholkar, A. V.; Sawant, V. S.; Pawar, C. A.; Bhosale, C. H.; Rajpure, K. Y.

2008-01-01

The cadmium oxide (CdO) and F:CdO films have been deposited by spray pyrolysis method using cadmium acetate and ammonium fluoride as precursors for Cd and F ions, respectively. The effect of temperature and F doping on the structural, morphological, optical and Hall effect properties of sprayed CdO thin films was investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), optical absorption and electrical measurement techniques. TGA and DTA studies, indicates the formation of CdO by decomposition of cadmium acetate after 250 °C. XRD patterns reveal that samples are polycrystalline with cubic structure and exhibits (2 0 0) preferential orientation. Considerable broading of (2 0 0) peak, simultaneous shifting of corresponding Bragg's angle have been observed with respect to F doping level. SEM and AFM show the heterogeneous distribution of cubical grains all over the substrate, which are randomly distributed. F doping shifts the optical gap along with the increase in the transparency of CdO films. The Hall effect measurement indicates that the resistivity and mobility decrease up to 4% F doping.

Role of Zn doping in oxidative stress mediated cytotoxicity of TiO2 nanoparticles in human breast cancer MCF-7 cells

NASA Astrophysics Data System (ADS)

Ahamed, Maqusood; Khan, M. A. Majeed; Akhtar, Mohd Javed; Alhadlaq, Hisham A.; Alshamsan, Aws

2016-07-01

We investigated the effect of Zn-doping on structural and optical properties as well as cellular response of TiO2 nanoparticles (NPs) in human breast cancer MCF-7 cells. A library of Zn-doped (1-10 at wt%) TiO2 NPs was prepared. Characterization data indicated that dopant Zn was incorporated into the lattice of host TiO2. The average particle size of TiO2 NPs was decreases (38 to 28 nm) while the band gap energy was increases (3.35 eV-3.85 eV) with increasing the amount of Zn-doping. Cellular data demonstrated that Zn-doped TiO2 NPs induced cytotoxicity (cell viability reduction, membrane damage and cell cycle arrest) and oxidative stress (reactive oxygen species generation & glutathione depletion) in MCF-7 cells and toxic intensity was increases with increasing the concentration of Zn-doping. Molecular data revealed that Zn-doped TiO2 NPs induced the down-regulation of super oxide dismutase gene while the up-regulation of heme oxygenase-1 gene in MCF-7 cells. Cytotoxicity induced by Zn-doped TiO2 NPs was efficiently prevented by N-acetyl-cysteine suggesting that oxidative stress might be the primarily cause of toxicity. In conclusion, our data indicated that Zn-doping decreases the particle size and increases the band gap energy as well the oxidative stress-mediated toxicity of TiO2 NPs in MCF-7 cells.

Role of Zn doping in oxidative stress mediated cytotoxicity of TiO2 nanoparticles in human breast cancer MCF-7 cells

PubMed Central

Ahamed, Maqusood; Khan, M. A. Majeed; Akhtar, Mohd Javed; Alhadlaq, Hisham A.; Alshamsan, Aws

2016-01-01

We investigated the effect of Zn-doping on structural and optical properties as well as cellular response of TiO2 nanoparticles (NPs) in human breast cancer MCF-7 cells. A library of Zn-doped (1–10 at wt%) TiO2 NPs was prepared. Characterization data indicated that dopant Zn was incorporated into the lattice of host TiO2. The average particle size of TiO2 NPs was decreases (38 to 28 nm) while the band gap energy was increases (3.35 eV–3.85 eV) with increasing the amount of Zn-doping. Cellular data demonstrated that Zn-doped TiO2 NPs induced cytotoxicity (cell viability reduction, membrane damage and cell cycle arrest) and oxidative stress (reactive oxygen species generation & glutathione depletion) in MCF-7 cells and toxic intensity was increases with increasing the concentration of Zn-doping. Molecular data revealed that Zn-doped TiO2 NPs induced the down-regulation of super oxide dismutase gene while the up-regulation of heme oxygenase-1 gene in MCF-7 cells. Cytotoxicity induced by Zn-doped TiO2 NPs was efficiently prevented by N-acetyl-cysteine suggesting that oxidative stress might be the primarily cause of toxicity. In conclusion, our data indicated that Zn-doping decreases the particle size and increases the band gap energy as well the oxidative stress-mediated toxicity of TiO2 NPs in MCF-7 cells. PMID:27444578

Copper doping enhanced the oxidative stress-mediated cytotoxicity of TiO2 nanoparticles in A549 cells.

PubMed

Ahmad, J; Siddiqui, M A; Akhtar, M J; Alhadlaq, H A; Alshamsan, A; Khan, S T; Wahab, R; Al-Khedhairy, A A; Al-Salim, A; Musarrat, J; Saquib, Q; Fareed, M; Ahamed, M

2018-05-01

Physicochemical properties of titanium dioxide nanoparticles (TiO 2 NPs) can be tuned by doping with metals or nonmetals. Copper (Cu) doping improved the photocatalytic behavior of TiO 2 NPs that can be applied in various fields such as environmental remediation and nanomedicine. However, interaction of Cu-doped TiO 2 NPs with human cells is scarce. This study was designed to explore the role of Cu doping in cytotoxic response of TiO 2 NPs in human lung epithelial (A549) cells. Characterization data demonstrated the presence of both TiO 2 and Cu in Cu-doped TiO 2 NPs with high-quality lattice fringes without any distortion. The size of Cu-doped TiO 2 NPs (24 nm) was lower than pure TiO 2 NPs (30 nm). Biological results showed that both pure and Cu-doped TiO 2 NPs induced cytotoxicity and oxidative stress in a dose-dependent manner. Low mitochondrial membrane potential and higher caspase-3 enzyme (apoptotic markers) activity were also observed in A549 cells exposed to pure and Cu-doped TiO 2 NPs. We further observed that cytotoxicity caused by Cu-doped TiO 2 NPs was higher than pure TiO 2 NPs. Moreover, antioxidant N-acetyl cysteine effectively prevented the reactive oxygen species generation, glutathione depletion, and cell viability reduction caused by Cu-doped TiO 2 NPs. This is the first report showing that Cu-doped TiO 2 NPs induced cytotoxicity and oxidative stress in A549 cells. This study warranted further research to explore the role of Cu doping in toxicity mechanisms of TiO 2 NPs.

Charge distribution and transport properties in reduced ceria phases: A review

NASA Astrophysics Data System (ADS)

Shoko, E.; Smith, M. F.; McKenzie, Ross H.

2011-12-01

The question of the charge distribution in reduced ceria phases (CeO2-x) is important for understanding the microscopic physics of oxygen storage capacity, and the electronic and ionic conductivities in these materials. All these are key properties in the application of these materials in catalysis and electrochemical devices. Several approaches have been applied to study this problem, including ab initio methods. Recently [1], we applied the bond valence model (BVM) to discuss the charge distribution in several different crystallographic phases of reduced ceria. Here, we compare the BVM results to those from atomistic simulations to determine if there is consistency in the predictions of the two approaches. Our analysis shows that the two methods give a consistent picture of the charge distribution around oxygen vacancies in bulk reduced ceria phases. We then review the transport theory applicable to reduced ceria phases, providing useful relationships which enable comparison of experimental results obtained by different techniques. In particular, we compare transport parameters obtained from the observed optical absorption spectrum, α(ω), dc electrical conductivity with those predicted by small polaron theory and the Harrison method. The small polaron energy is comparable to that estimated from α(ω). However, we found a discrepancy between the value of the electron hopping matrix element, t, estimated from the Marcus-Hush formula and that obtained by the Harrison method. Part of this discrepancy could be attributed to the system lying in the crossover region between adiabatic and nonadiabatic whereas our calculations assumed the system to be nonadiabatic. Finally, by considering the relationship between the charge distribution and electronic conductivity, we suggest the possibility of low temperature metallic conductivity for intermediate phases, i.e., x˜0.3. This has not yet been experimentally observed.

Extended x-ray absorption fine structure spectroscopy and x-ray absorption near edge spectroscopy study of aliovalent doped ceria to correlate local structural changes with oxygen vacancies clustering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shirbhate, S. C.; Acharya, S. A., E-mail: saha275@yahoo.com; Yadav, A. K.

2016-04-04

This study provides atomic scale insight to understand the role of aliovalent dopants on oxygen vacancies clustering and dissociation mechanism in ceria system in order to enhance the performance of oxy-ion conductor. Dopants induced microscale changes in ceria are probed by extended X-ray absorption fine structure spectroscopy, X-ray absorption near edge spectra, and Raman spectroscopy. The results are explored to establish a correlation between atomic level structural changes (coordination number, interatomic spacing) → formation of dimer and trimer type cation-oxygen vacancies defect complex (intrinsic and extrinsic) → dissociation of oxygen vacancies from defect cluster → ionic conductivity temperature. It ismore » a strategic approach to understand key physics of ionic conductivity mechanism in order to reduce operating temperature of electrolytes for intermediate temperature (300–450 °C) electrochemical devices for the first time.« less

Structural and optical properties of pure and copper doped zinc oxide nanoparticles

NASA Astrophysics Data System (ADS)

Sajjad, Muhammad; Ullah, Inam; Khan, M. I.; Khan, Jamshid; Khan, M. Yaqoob; Qureshi, Muhammad Tauseef

2018-06-01

Pure and copper-doped zinc oxide nanoparticles (NPs) have been synthesized via chemical co-precipitation method where hydrazine is used as reducing agent and aqueous extract of Euphorbia milii plant as capping agent. Main objectives of the reported work are to investigate the effect of copper doping on crystal structure of ZnO nanoparticles; to study the effect of copper doping on optical band gap of ZnO nanoparticles and photoluminescence (PL) study of pure and copper-doped ZnO nanoparticles. To achieve the aforementioned objectives, XRD and SEM tests were performed for the identification and confirmation of crystal structure and morphology of the prepared samples. From XRD data the average grain size for pure ZnO was observed to be 24.62 nm which was first decreased to 18.95 nm for 5 wt% Cu-doped sample and then it was found to increase up to 37.80 nm as the Cu doping was increased to 7 wt%. Optical band gap of pure and Cu-doped ZnO nanoparticles was calculated from diffuse reflectance spectroscopy (DRS) spectra and was found to decrease from 3.13 eV to 2.94 eV as the amount of Cu increases up to 7 wt%. In photoluminescence study, PL technique was used and enhanced visible spectrum was observed. For further characterization FT-IR and EDX tests were also carried out.

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.

Nitrogen Doped Graphene Supported Pt Nanoflowers as Electrocatalysts for Oxidation of Formaldehyde.

PubMed

Xie, Aijuan; Zhou, Wenting; Luo, Shiping; Chen, Yu; Zhou, Xiaoqing; Chao, Yao

2017-02-01

A facile Pt nanoflowers/nitrogen-doped graphene (PtNFs/NG) electrocatalyst was prepared via depositing Pt nanoflowers (PtNFs) onto the nitrogen-doped graphene (NG) matrix with urea as the nitrogen source and PtNFs/NG modified glassy carbon electrode (GCE) was prepared by electro-chemical method. Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), Raman spectroscope, X-ray photoelectron spectroscopy (XPS) and Scanning electron microscope (SEM) were used to characterize the resulting composites. Also oxidation of formaldehyde on the resulting PtNFs/NG modified electrode was investigated. The influence of deposition time, electrodeposition potential and formaldehyde concentration on electrooxidation of formaldehyde was detected, the experimental results indicate the high performance of PtNFs/NG catalyst for formaldehyde oxidation is at electrodeposition time of 300 s with the applied potential of −0.3 V. Electrochemical process, electrocatalytic stability and chronoamperometry were also inspected, it was indicated that formalde-hyde oxidation reaction on the PtNFs/NG electrode is diffusion-controlled and PtNFs/NG exhibits a high catalytic activity, stability as well as excellent poisoning-tolerance towards formaldehyde oxidation, which is attributed to the synergistic effect of PtNFs and NG. It turns out that PtNFs/NG can be used in direct liquid-feed fuel cells as a promising alternative catalyst.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lim, K.; Schelhas, L. T.; Siah, S. C.

2016-10-03

There have been a number of studies on the fabrication of Sn-doped gallium oxide (Ga 2O 3: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 Ga 2O 3: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 Gamore » 2O 3: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 Ga 2O 3: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.« less

Physical Vapor Deposition and Defect Engineering of Europium Doped Lutetium Oxide

NASA Astrophysics Data System (ADS)

Gillard, Scott James

Lutetium oxide doped with europium (Lu2O3:Eu 3+) has been established as a promising scintillator material with properties that are advantageous when compared to other scintillators such as cesium iodide doped with thallium (CsI:Tl). Due to high X-ray attenuation characteristics, Lu2O3:Eu3+ is an attractive material for use in high resolution digital X-ray imaging systems. However, challenges still remain especially in the area of light output for Lu 2O3:Eu3+. Processing by physical vapor deposition (PVD) and manipulation of oxygen defect structure was explored in order to better understand the effect on the scintillation phenomena. PVD results were obtained using high temperature radio frequency sputtering (RF) and pulsed laser deposition (PLD) systems. Characterization of light output by radial noise power spectrum density measurements revealed that high temperature RF films were superior to those obtained using PLD. Optimization of sputtered films based on light output over a range of process parameters, namely temperature, power, pressure, and substrate orientation was investigated. Parameterization of deposition conditions revealed that: 75 watts, 10.00 mtorr, and 800°C were optimum conditions for Lu2O3:Eu 3+ films. Manipulation of anionic defect structure in similar material systems has been shown to improve scintillation response. Similar methods for Lu 2O3:Eu3+ were explored for hot pressed samples of Lu2O3:Eu3+; via controlled atmosphere annealing, and use of extrinsic co-doping with calcium. The controlled atmosphere experiments established the importance of oxygen defect structure within Lu 2O3:Eu3+ and showed that fully oxidized samples were preferred for light output. The second method utilized co-doping by the addition of calcium which induced oxygen vacancies and by Frenkel equilibrium changed the oxygen interstitial population within the Lu2O 3:Eu3+ structure. The addition of calcium was investigated and revealed that scintillation was improved

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

Structural and optical studies of Mg doped nanoparticles of chromium oxide (Cr2O3) synthesized by co-precipitation method

NASA Astrophysics Data System (ADS)

Singh, Jarnail; Verma, Vikram; Kumar, Ravi

2018-04-01

We present here the synthesization, structural and optical studies of Mg doped nanoparticles of Chromium oxide (Cr2O3) prepared using co-precipitation method. These samples were characterized using powder X-ray diffraction (XRD), Field emission scanning electron microscopy (FESEM), Raman spectroscopy and UV-Vis spectroscopy techniques. We have demonstrated that there is negligible change in optical band gap with the Mg doping. The prepared Cr2O3 nanoparticles are spherical in shape, but they are transformed into platelets when doped with Mg. The XRD studies reveal that the Mg doping in Cr2O3 doesn't affect the structure of Chromium oxide (Cr2O3).

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.

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.

Tuning the Electrical and Thermal Conductivities of Thermoelectric Oxides through Impurity Doping

NASA Astrophysics Data System (ADS)

Torres Arango, Maria A.

Waste heat and thermal gradients available at power plants can be harvested to power wireless networks and sensors by using thermoelectric (TE) generators that directly transform temperature differentials into electrical power. Oxide materials are promising for TE applications in harsh industrial environments for waste heat recovery at high temperatures in air, because they are lightweight, cheaply produced, highly efficient, and stable at high temperatures in air. Ca3Co4O9(CCO) with layered structure is a promising p-type thermoelectric oxide with extrapolated ZT value of 0.87 in single crystal form [1]. However the ZT values for the polycrystalline ceramics remain low of ˜0.1-0.3. In this research, nanostructure engineering approaches including doping and addition of nanoinclusions were applied to the polycrystalline CCO ceramic to improve the energy conversion efficiency. Polycrystalline CCO samples with various Bi doping levels were prepared through the sol-gel chemical route synthesis of powders, pressing and sintering of the pellets. Microstructure features of Bi doped ceramic bulk samples such as porosity, development of crystal texture, grain boundary dislocations and segregation of Bi dopants at various grain boundaries are investigated from microns to atomic scale. The results of the present study show that the Bi-doping is affecting both the electrical conductivity and thermal conductivity simultaneously, and the optimum Bi doping level is strongly correlated with the microstructure and the processing conditions of the ceramic samples. At the optimum doping level and processing conditions of the ceramic samples, the Bi substitution of Ca results in the increase of the electrical conductivity, decrease of the thermal conductivity, and improvement of the crystal texture. The atomic resolution Scanning Transmission Electron Microscopy (STEM) Z-contrast imaging and the chemistry analysis also reveal the Bi-segregation at grain boundaries of CCO

Cobalt Oxide on N-Doped Carbon for 1-Butene Oligomerization to Produce Linear Octenes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, Dongting; Xu, Zhuoran; Chada, Joseph P.

Cobalt oxide supported on N-doped carbon catalysts were investigated for 1-butene oligomerization. The materials were synthesized by treating activated carbon with nitric acid and subsequently with NH3 at 200, 400, 600, and 800 °C, followed by impregnation with cobalt. The 1-butene oligomerization selectivity increased with ammonia treatment temperature of the carbon support. The oligomerization selectivity of cobalt oxide on N-doped carbon synthesized at 800 °C (800A-CoOx/N-C) is 2.6 times higher than previously reported cobalt oxide on N-doped carbon synthesized with NH4OH (2A-CoOx/N-C). Over 70% of the butene dimers were linear C8 olefins for all catalysts. The oligomerization selectivity increased withmore » 1-butene conversion. The catalysts were characterized by elemental analysis, N2 adsorption, X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), and X-ray photoelectron spectroscopy (XPS). The nitrogen content of the catalysts increases with ammonia treatment temperature as confirmed by elemental analysis. The surface content of pyridinic nitrogen with a binding energy of 398.4 ± 0.1 eV increased with ammonia treatment temperature as evidenced by deconvolution of N 1s XPS spectra.« less

Structure and thermoelectric properties of Al-doped ZnO films prepared by thermal oxidization under high magnetic field

NASA Astrophysics Data System (ADS)

Liu, Shiying; Peng, Sunjuan; Ma, Jun; Li, Guojian; Qin, Xuesi; Li, Mengmeng; Wang, Qiang

2017-04-01

This paper studies the effects of high magnetic field (HMF) on the structure, optical and thermoelectric properties of the doped ZnO thin films. The results show that both Al dopant and application of HMF can affect the crystal structure, surface morphology, elemental distribution and so on. The particles of the thin films become small and regular by doping Al. The ZnO films oxidized from the Au/Zn bilayer have needle structure. The ZnO films oxidized from the Au/Zn-Al bilayer transform to spherical from hexagonal due to the application of HMF. The transmittance decreases with doping Al because of the opaque of Al element and decreases with the application of HMF due to the dense structure obtained under HMF. Electrical resistivity (ρ) of the ZnO films without Al decreases with increasing measurement temperature (T) and is about 1.5 × 10-3 Ω·m at 210 °C. However, the ρ of the Al-doped ZnO films is less than 10-5 Ω·m. The Seebeck coefficient (S) of the films oxidized from the Au/Zn-Al films reduces with increasing T. The S values oxidized under 0 T and 12 T conditions are 2.439 μV/K and -3.415 μV/K at 210 °C, respectively. Power factor reaches the maximum value (3.198 × 10-4 W/m·K2) at 210 °C for the film oxidized under 12 T condition. These results indicate that the Al dopant and the application of HMF can be used to control structure and thermoelectric properties of doped ZnO films.

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.

Microstructural and electrical characteristics of rare earth oxides doped ZnO varistor films

NASA Astrophysics Data System (ADS)

Jiao, Lei; Mei, Yunzhu; Xu, Dong; Zhong, Sujuan; Ma, Jia; Zhang, Lei; Bao, Li

2018-02-01

ZnO-Bi2O3 varistor films doped with two kinds of rare earth element oxides (Lu2O3 and Yb2O3) were prepared by the sol-gel method. The effects of Lu2O3/Yb2O3 doping on the microstructure and electrical characteristics of ZnO-Bi2O3 varistor films were investigated. All samples show a homogenized morphology and an improved nonlinear relationship between the electric field (E) and current density (I). Both Yb2O3 and Lu2O3 doping can decrease the grain size of ZnO-Bi2O3 varistor films and improve the electrical properties, which have a positive effect on the development of ZnO varistor ceramics. Yb2O3 doping significantly increases the dielectric constant at low frequency. 0.2 mol. % Yb2O3 doped ZnO-Bi2O3 varistor films exhibit the highest nonlinear coefficient (2.5) and the lowest leakage current (328 μA) among Lu2O3/Yb2O3 doped ZnO-Bi2O3 varistor films. Similarly, 0.1 mol. % Lu2O3 doping increases the nonlinear coefficient to 1.9 and decrease the leakage current to 462 μA.

Robust p-type doping of copper oxide using nitrogen implantation

NASA Astrophysics Data System (ADS)

Jorge, Marina; Polyakov, Stanislav M.; Cooil, Simon; Schenk, Alex K.; Edmonds, Mark; Thomsen, Lars; Mazzola, Federico; Wells, Justin W.

2017-07-01

We demonstrate robust p-type doping of Cu2O using low/medium energy ion implantation. Samples are made by controlled oxidation of annealed Cu metal foils, which results in Cu2O with levels of doping close to intrinsic. Samples are then implanted with nitrogen ions using a kinetic energy in the few keV range. Using this method, we are able to produce very high levels of doping, as evidenced by a 350 meV shift in the Fermi level towards the VB maximum. The robustness of the nitrogen implanted samples are tested by exposing them to atmospheric contaminants, and elevated temperatures. The samples are found to survive an increase in temperature of many hundreds of degrees. The robustness of the samples, combined with the fact that the materials used are safe, abundant and non-toxic and that the methods used for the growth of Cu2O and N+ implantation are simple and cheap to implement industrially, underlines the potential of Cu2O:N for affordable intermediate band photovoltaics.

Facile synthesis of antimony-doped tin oxide nanoparticles by a polymer-pyrolysis method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Yuan-Qing, E-mail: yqli@mail.ipc.ac.cn; Wang, Jian-Lei; Fu, Shao-Yun, E-mail: syfu@mail.ipc.ac.cn

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 themore » 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}.« less

Experimental Demonstration of the Thermochemical Reduction of Ceria in a Solar Aerosol Reactor

PubMed Central

2016-01-01

We report on the experimental demonstration of an aerosol solar reactor for the thermal reduction of ceria, as part of a thermochemical redox cycle for splitting H2O and CO2. The concept utilizes a cavity-receiver enclosing an array of alumina tubes, each containing a downward gravity-driven aerosol flow of ceria particles countercurrent to an inert sweep gas flow for intrinsic separation of reduced ceria and oxygen. A 2 kWth lab-scale prototype with a single tube was tested under radiative fluxes approaching 4000 suns, yielding reaction extents of up to 53% of the thermodynamic equilibrium at 1919 K within residence times below 1 s. Upon thermal redox cycling, fresh primary particles of 2.44 μm mean size initially formed large agglomerates of 1000 μm mean size, then sintered into stable particles of 150 μm mean size. The reaction extent was primarily limited by heat transfer for large particles/agglomerates (mean size > 200 μm) and by the gas phase advection of product O2 for smaller particles. PMID:27853339

Experimental Demonstration of the Thermochemical Reduction of Ceria in a Solar Aerosol Reactor.

PubMed

Welte, Michael; Barhoumi, Rafik; Zbinden, Adrian; Scheffe, Jonathan R; Steinfeld, Aldo

2016-10-12

We report on the experimental demonstration of an aerosol solar reactor for the thermal reduction of ceria, as part of a thermochemical redox cycle for splitting H 2 O and CO 2 . The concept utilizes a cavity-receiver enclosing an array of alumina tubes, each containing a downward gravity-driven aerosol flow of ceria particles countercurrent to an inert sweep gas flow for intrinsic separation of reduced ceria and oxygen. A 2 kW th lab-scale prototype with a single tube was tested under radiative fluxes approaching 4000 suns, yielding reaction extents of up to 53% of the thermodynamic equilibrium at 1919 K within residence times below 1 s. Upon thermal redox cycling, fresh primary particles of 2.44 μm mean size initially formed large agglomerates of 1000 μm mean size, then sintered into stable particles of 150 μm mean size. The reaction extent was primarily limited by heat transfer for large particles/agglomerates (mean size > 200 μm) and by the gas phase advection of product O 2 for smaller particles.

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.

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. Copyright © 2011 Elsevier B.V. All rights reserved.

Thermochemistry of rare earth doped uranium oxides LnxU1-xO2-0.5x+y (Ln = La, Y, Nd)

NASA Astrophysics Data System (ADS)

Zhang, Lei; Navrotsky, Alexandra

2015-10-01

Lanthanum, yttrium, and neodymium doped uranium dioxide samples in the fluorite structure have been synthesized, characterized in terms of metal ratio and oxygen content, and their enthalpies of formation measured by high temperature oxide melt solution calorimetry. For oxides doped with 10-50 mol % rare earth (Ln) cations, the formation enthalpies from constituent oxides (LnO1.5, UO2 and UO3 in a reaction not involving oxidation or reduction) become increasingly exothermic with increasing rare earth content, while showing no significant dependence on the varying uranium oxidation state. The oxidation enthalpy of LnxU1-xO2-0.5x+y is similar to that of UO2 to UO3 for all three rare earth doped systems. Though this may suggest that the oxidized uranium in these systems is energetically similar to that in the hexavalent state, thermochemical data alone can not constrain whether the uranium is present as U5+, U6+, or a mixture of oxidation states. The formation enthalpies from elements calculated from the calorimetric data are generally consistent with those from free energy measurements.

Reactivating the Ni-YSZ electrode in solid oxide cells and stacks by infiltration

NASA Astrophysics Data System (ADS)

Skafte, Theis Løye; Hjelm, Johan; Blennow, Peter; Graves, Christopher

2018-02-01

The solid oxide cell (SOC) could play a vital role in energy storage when the share of intermittent electricity production is high. However, large-scale commercialization of the technology is still hindered by the limited lifetime. Here, we address this issue by examining the potential for repairing various failure and degradation mechanisms occurring in the fuel electrode, thereby extending the potential lifetime of a SOC system. We successfully infiltrated the nickel and yttria-stabilized zirconia cermet electrode in commercial cells with Gd-doped ceria after operation. By this method we fully reactivated the fuel electrode after simulated reactant starvation and after carbon formation. Furthermore, by infiltrating after 900 h of operation, the degradation of the fuel electrode was reduced by a factor of two over the course of 2300 h. Lastly, the scalability of the concept is demonstrated by reactivating an 8-cell stack based on a commercial design.

Design, fabrication and characterization of a double layer solid oxide fuel cell (DLFC)

NASA Astrophysics Data System (ADS)

Wang, Guangjun; Wu, Xiangying; Cai, Yixiao; Ji, Yuan; Yaqub, Azra; Zhu, Bin

2016-11-01

A double layer solid oxide fuel cell (DLSOFC) without using the electrolyte (layer) has been designed by integrating advantages of positive electrode material of lithium ion battery(LiNi0.8Co0.15Al0.05O2) and oxygen-permeable membranes material (trace amount cobalt incorporated terbium doped ceria, TDC + Co) based on the semiconductor physics principle. Instead of using an electrolyte layer, the depletion layer between the anode and cathode served as an electronic insulator to block the electrons but to maintain the electrolyte function for ionic transport. Thus the device with two layers can realize the function of SOFC and at the same time avoids the electronic short circuiting problem. Such novel DLFC showed good performance at low temperatures, for instance, a maximum power density of 230 mWcm-2 was achieved at 500 °C. The working principle of the new device is presented.

RGO modified Ni doped FeOOH for enhanced electrochemical and photoelectrochemical water oxidation

NASA Astrophysics Data System (ADS)

Zhang, Xiaofan; Zhang, Bingyan; Liu, Shuangshuang; Kang, Hongwei; Kong, Weiqian; Zhang, Shouren; Shen, Yan; Yang, Baocheng

2018-04-01

Ni,Fe-based (oxy)hydroxides have been one of the most active catalysts for the oxygen evolution reaction. In this article, reduced graphene oxide supported Ni doped FeOOH (RGO/Ni:FeOOH) was prepared for electrochemical and photoelectrochemical (PEC) water oxidation. The RGO/Ni:FeOOH exhibited a lower over-potential (260 mV at 10 mA cm-2) and smaller Tafel slope (32.3 mV dec-1) than that of the FeOOH and Ni:FeOOH. Such significant enhancement is attributed to Ni doping and RGO, which reduce the over-potential, improve the conductivity and enlarge surface areas. Besides, RGO/Ni:FeOOH decorated the TiO2 nanorods (NRs) was also fabricated for photoelectrochemical (PEC) water oxidation, which exhibited a higher photocurrent density and lower onset potential than that of TiO2 NRs the bare under illumination due to the synergistic effect of RGO and Ni:FeOOH. These results demonstrate the RGO/Ni:FeOOH has great promising as a co-catalyst to improve the PEC performance.

Chemical compatibility and properties of suspension plasma-sprayed SrTiO3-based anodes for intermediate-temperature solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Zhang, Shan-Lin; Li, Cheng-Xin; Li, Chang-Jiu

2014-10-01

La-doped strontium titanate (LST) is a promising, redox-stable perovskite material for direct hydrocarbon oxidation anodes in intermediate-temperature solid oxide fuel cells (IT-SOFCs). In this study, nano-sized LST and Sm-doped ceria (SDC) powders are produced by the sol-gel and glycine-nitrate processes, respectively. The chemical compatibility between LST and electrolyte materials is studied. A LST-SDC composite anode is prepared by suspension plasma spraying (SPS). The effects of annealing conditions on the phase structure, microstructure, and chemical stability of the LST-SDC composite anode are investigated. The results indicate that the suspension plasma-sprayed LST-SDC anode has the same phase structure as the original powders. LST exhibits a good chemical compatibility with SDC and Mg/Sr-doped lanthanum gallate (LSGM). The anode has a porosity of ∼40% with a finely porous structure that provides high gas permeability and a long three-phase boundary for the anode reaction. Single cells assembled with the LST-SDC anode, La0.8Sr0.2Ga0.8Mg0.2O3 electrolyte, and La0.8Sr0.2CoO3-SDC cathode show a good performance at 650-800 °C. The annealing reduces the impedances due to the enhancement in the bonding between the particles in the anode and interface of anode and LSGM electrolyte, thus improving the output performance of the cell.

Au-Doped Indium Tin Oxide Ohmic Contacts to p-Type GaN

NASA Astrophysics Data System (ADS)

Guo, H.; Andagana, H. B.; Cao, X. A.

2010-05-01

Indium tin oxide (ITO) thin films doped with Au, Ni, or Pt (3.5 at.% to 10.5 at.%) were deposited on p-GaN epilayers (Mg ~4 × 1019 cm-3) using direct-current (DC) sputter codeposition. It was found that undoped ITO con- tacts to p-GaN exhibited leaky Schottky behavior, whereas the incorporation of a small amount of Au (3.5 at.% to 10.5 at.%) significantly improved their ohmic characteristics. Compared with standard Ni/ITO contacts, the Au-doped ITO contacts had a similar specific contact resistance in the low 10-2 Ω cm-2 range, but were more stable above 600°C and more transparent at blue wavelengths. These results provide support for the use of Au-doped ITO ohmic contact to p-type GaN in high-brightness blue light-emitting diodes.

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

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

DOE PAGES

Lim, K.; Schelhas, L. T.; Siah, S. C.; ...

2016-10-07

There have been a number of studies on the fabrication of Sn-doped gallium oxide (Ga 2O 3: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 Ga 2O 3: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 SnO x phases in themore » Ga 2O 3: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. Furthermore, these observations suggest that to obtain transparent Ga 2O 3: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.« less

Study of defects and vacancies in structural properties of Mn, co-doped oxides: ZnO

NASA Astrophysics Data System (ADS)

Kumar, Harish; Kaushik, A.; Alvi, P. A.; Dalela, B.; Dalela, S.

2018-05-01

The paper deals with the Structural properties on Mn, Co doped oxides ZnO samples using XRD, Positron Annihilation Lifetime (PAL) Spectra and Raman Spectra. The Mn, Co doped ZnO samples crystallize in a wurtzite structure without any impurity phases in XRD Spectra. The defect state of these samples has been investigated by using positron annihilation lifetime (PAL) spectroscopy technique in which all the relevant lifetime parameters are measured for all the spectra. The results are explained in the direction of doping concentration in these samples in terms of defects structure on Zn lattice site VZn and oxygen defects Vo.

Cu and Boron Doped Carbon Nitride for Highly Selective Oxidation of Toluene to Benzaldehyde.

PubMed

Han, Hongling; Ding, Guodong; Wu, Tianbin; Yang, Dexin; Jiang, Tao; Han, Buxing

2015-07-13

A novel Cu and boron doped graphitic carbon nitride catalyst (Cu-CNB) was synthesized using cheap precursors and systematically characterized. The selective oxidation of toluene proceeded very smoothly over the catalyst at 70 °C using tert-butyl hydroperoxide (TBHP) as the oxidant to exclusively afford benzaldehyde. The catalyst can be used for at least five cycles without decrease in activity and selectivity.

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.

A facile method to synthesize boron-doped Ni/Fe alloy nano-chains as electrocatalyst for water oxidation

NASA Astrophysics Data System (ADS)

Yang, Yisu; Zhuang, Linzhou; Lin, Rijia; Li, Mengran; Xu, Xiaoyong; Rufford, Thomas E.; Zhu, Zhonghua

2017-05-01

We report a novel magnetic field assisted chemical reduction method for the synthesis of boron-doped Ni/Fe nano-chains as promising catalysts for the oxygen evolution reaction (OER). The boron-doped Ni/Fe nano-chains were synthesised in a one step process at room temperature using NaBH4 as a reducing agent. The addition of boron reduced the magnetic moment of the intermediate synthesis products and produced nano-chains with a high specific surface area of 73.4 m2 g-1. The boron-doped Ni/Fe nano-chains exhibited catalytic performance superior to state-of-the-art Ba0.5Sr0.5Co0.8Fe0.2O3-δ perovskite and RuO2 noble metal oxide catalysts. The mass normalized activity of the boron-doped Ni/Fe nano-chains measured at an overpotential of 0.35 V was 64.0 A g-1, with a Tafel slope of only 40 mV dec-1. The excellent performance of the boron-doped Ni/Fe nano-chains can be attributed to the uniform elemental distribution and highly amorphous structure of the B-doped nano-chains. These results provide new insights into the effect of doping transition-metal based OER catalysts with non-metallic elements. The study demonstrates a facile approach to prepare transition metal nano-chains using magnetic field assisted chemical reduction method as cheap and highly active catalysts for electrochemical water oxidation.

Synthesis and characterization of cobalt doped nickel oxide thin films by spray pyrolysis method

NASA Astrophysics Data System (ADS)

Sathisha, D.; Naik, K. Gopalakrishna

2018-05-01

Cobalt (Co) doped nickel oxide (NiO) thin films were deposited on glass substrates at a temperature of about 400 °C by spray pyrolysis method. The effect of Co doping concentration on structural, optical and compositional properties of NiO thin films was investigated. X-ray diffraction result shows that the deposited thin films are polycrystalline in nature. Surface morphologies of the deposited thin films were observed by FESEM and AFM. EDS spectra showed the incorporation of Co dopants in NiO thin films. Optical properties of the grown thin films were characterized by UV-visible spectroscopy. It was found that the optical band gap energy and transmittance of the films decrease with increasing Co doping concentration.

Fabrication and characterization of novel transparent conducting oxide N-CNT doped ZnO for photovoltaic applications

NASA Astrophysics Data System (ADS)

Benyounes, Anas; Abbas, Naseem; Hammi, Maryama; Ziat, Younes; Slassi, Amine; Zahra, Nida

2018-02-01

The present research reports on the electrical and optical properties of N-CNT doped with ZnO, which is considered as wurtzite transparent and conducting oxide semiconductor structure. The thin films of N-doped carbon nanotubes/ZnO were prepared using sol-gel method, then we carried out investigations in optical and electrical point of view to extract their usefulness in photovoltaic applications. For this purpose, ZnO films were doped by several ratios of carbon nanotubes and N-doped carbon nanotubes. The electrical studies were performed over these two kinds of doped ZnO films, the electrical conductivity has found to be more important for ZnO films filled with N-CNTs. This finding is pretty explained by the electronic conduction hold by nitrogen as charge carriers within carbon nanotubes.

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.

Microstructure evolution of Al-doped zinc oxide and Sn-doped indium oxide deposited by radio-frequency magnetron sputtering: A comparison

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nie, Man; Bikowski, Andre; Ellmer, Klaus, E-mail: ellmer@helmholtz-berlin.de

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 AZOmore » 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.« less

First-principles theory of doping in layered oxide electrode materials

NASA Astrophysics Data System (ADS)

Hoang, Khang

2017-12-01

Doping lithium-ion battery electrode materials Li M O2 (M = Co, Ni, Mn) with impurities has been shown to be an effective way to optimize their electrochemical properties. Here, we report a detailed first-principles study of layered oxides LiCoO2, LiNiO2, and LiMnO2 lightly doped with transition-metal (Fe, Co, Ni, Mn) and non-transition-metal (Mg, Al) impurities using hybrid-density-functional defect calculations. We find that the lattice site preference is dependent on both the dopant's charge and spin states, which are coupled strongly to the local lattice environment and can be affected by the presence of codopant(s), and the relative abundance of the host compound's constituting elements in the synthesis environment. On the basis of the structure and energetics of the impurities and their complexes with intrinsic point defects, we determine all possible low-energy impurity-related defect complexes, thus providing defect models for further analyses of the materials. From a materials modeling perspective, these lightly doped compounds also serve as model systems for understanding the more complex, mixed-metal, Li M O2 -based battery cathode materials.

Microwave-assisted boron and nitrogen co-doped reduced graphene oxide as a transparent conductive electrode

NASA Astrophysics Data System (ADS)

Umrao, Sima; Mishra, Himanshu; Srivastava, Anchal; Lee, Sungjoo

2017-07-01

A crystalline Boron (B)- and Nitrogen (N)-co-doped microwave-assisted reduced graphene oxide (BNMRGO) film was investigated as a potential transparent conducting electrode (TCE) material. X-ray diffraction results revealed the good crystallinity of the BNMRGO film, and the presence of a (0004) reflection plane indicated the formation of a few small domains of hexagonal boron nitride in the microwave assisted reduced graphene oxide (MRGO) sheets under the co-doping process. Raman and X-ray photoelectron spectroscopic results indicated a reduction of sp3 carbon centers upon co-doping. The ID/IG ratio decreased after co-doping from 0.89 to 0.24, indicating a low average defect density of ˜1.01 × 1010 cm-2. Optoelectronic characterization of the BNMRGO film on a glass substrate revealed a high optical transparency of 82% at 550 nm and a low sheet resistance (Rsh) of 355 Ω/sq, which was lower than that observed from the MRGO sheets (Rsh = 719 Ω/sq). BNMRGO provided a ratio between the direct conductivity (σdc) to the optical conductivity (σoc), that is, the figure of merit of a TCE material, of 5.96. Overall, this work paves the way toward developing a manufacturable TCE.

Defect-mediated magnetism of transition metal doped zinc oxide thin films

NASA Astrophysics Data System (ADS)

Roberts, Bradley Kirk

Magnetism in transition metal doped wide band-gap materials is of interest to further the fundamental science of materials and future spintronics applications. Large inter-dopant separations require mediation of ferromagnetism by some method; carrier-mediated mechanisms are typically applicable to dilute magnetic semiconductors with low Curie temperatures. Dilute magnetic oxides, commonly with poor conductivity and TC above room temperature, cannot be described within this theory. Recent experiment and theory developments suggest that ferromagnetic exchange in these materials can be mediated by defects. This research includes experimental results justifying and developing this approach. Thin films of Cr doped ZnO (band gap ˜3.3 eV) were deposited with several processing variations to enhance the effects of either 0-dimensional (vacancy, hydrogen-related defect) or two-dimensional defects (surface/interface) and thereby affect magnetism and conductivity. We observe surface magnetism in dielectric thin films of oxygen-saturated ZnO:Cr with spontaneous magnetic moment and conductance dropping approximately exponentially with increasing thickness. Uniform defect concentrations would not result in such magnetic ordering behavior indicating that magnetism is mediated either by surface defects or differing concentrations of point defects near the surface. Polarized neutron reflectivity profiling confirms a magnetically active region of ˜8 nm at the film surface. Hydrogen is notoriously present as a defect and carrier dopant in ZnO, and artificial introduction of hydrogen in dielectric ZnO:Cr films results in varying electronic and magnetic behavior. Free carriers introduced with hydrogen doping are not spin-polarized requiring an alternative explanation for ferromagnetism. We find from positron annihilation spectroscopy measurements that hydrogen doping increases the concentration of an altered VZn-related defect (a preliminary interpretation) throughout the film, which

Preparation of Ru-doped SnO2-supported Pt catalysts and their electrocatalytic properties for methanol oxidation.

PubMed

Pang, H L; Zhang, X H; Zhong, X X; Liu, B; Wei, X G; Kuang, Y F; Chen, J H

2008-03-01

Ru-doped SnO2 nanoparticles were prepared by chemical precipitation and calcinations at 823 K. Due to high stability in diluted acidic solution, Ru-doped SnO2 nanoparticles were selected as the catalyst support and second catalyst for methanol electrooxidation. The micrograph, elemental composition, and structure of the Ru-doped SnO2 nanoparticles were characterized by scanning electron microscopy, energy dispersive X-ray spectroscopy, and X-ray diffraction, respectively. The electrocatalytic properties of the Ru-doped SnO2-supported Pt catalyst (Pt/Ru-doped SnO2) for methanol oxidation have been investigated by cyclic voltammetry. Under the same loading mass of Pt, the Pt/Ru-doped SnO2 catalyst shows better electrocatalytic performance than the Pt/SnO2 catalyst and the best atomic ratio of Ru to Sn in Ru-doped SnO2 is 1/75. Additionally, the Pt/Ru-doped SnO2 catalyst possesses good long-term cycle stability.

Solution-processed flexible fluorine-doped indium zinc oxide thin-film transistors fabricated on plastic film at low temperature.

PubMed

Seo, Jin-Suk; Jeon, Jun-Hyuck; Hwang, Young Hwan; Park, Hyungjin; Ryu, Minki; Park, Sang-Hee Ko; Bae, Byeong-Soo

2013-01-01

Transparent flexible fluorine-doped indium zinc oxide (IZO:F) thin-film transistors (TFTs) were demonstrated using the spin-coating method of the metal fluoride precursor aqueous solution with annealing at 200°C for 2 hrs on polyethylene naphthalate films. The proposed thermal evolution mechanism of metal fluoride aqueous precursor solution examined by thermogravimetric analysis and Raman spectroscopy can easily explain oxide formation. The chemical composition analysed by XPS confirms that the fluorine was doped in the thin films annealed below 250°C. In the IZO:F thin films, a doped fluorine atom substitutes for an oxygen atom generating a free electron or occupies an oxygen vacancy site eliminating an electron trap site. These dual roles of the doped fluorine can enhance the mobility and improve the gate bias stability of the TFTs. Therefore, the transparent flexible IZO:F TFT shows a high mobility of up to 4.1 cm(2)/V·s and stable characteristics under the various gate bias and temperature stresses.

Intra- and interparticle magnetism of cobalt-doped iron-oxide nanoparticles encapsulated in a synthetic ferritin cage

NASA Astrophysics Data System (ADS)

Skoropata, E.; Desautels, R. D.; Falvo, E.; Ceci, P.; Kasyutich, O.; Freeland, J. W.; van Lierop, J.

2014-11-01

We present an in-depth examination of the composition and magnetism of cobalt (Co2 +)-doped iron-oxide nanoparticles encapsulated in Pyrococcus furiosus ferritin shells. We show that the Co2 + dopant ions were incorporated into the γ -Fe2O3/Fe3O4 core, with small paramagnetic-like clusters likely residing on the surface of the nanoparticle that were observed for all cobalt-doped samples. In addition, element-specific characterization using Mössbauer spectroscopy and polarized x-ray absorption indicated that Co2 + was incorporated exclusively into the octahedral B sites of the spinel-oxide nanoparticle. Comparable superparamagnetic blocking temperatures, coercivities, and effective anisotropies were obtained for 7%, 10%, and 12% cobalt-doped nanoparticles, and were only slightly reduced for 3% cobalt, indicating a strong effect of cobalt incorporation, with a lesser effect of cobalt content. Due to the regular particle size and separation that result from the use of the ferritin cage, a comparison of the effects of interparticle interactions on the disordered assembly of nanoparticles was also obtained that indicated significantly different behaviors between undoped and cobalt-doped nanoparticles.

Effect of doping with nickel ions on the structural state of a zinc oxide crystal

NASA Astrophysics Data System (ADS)

Dubinin, S. F.; Sokolov, V. I.; Parkhomenko, V. D.; Maksimov, V. I.; Gruzdev, N. B.

2009-10-01

The fine structure of a hexagonal zinc oxide crystal doped with nickel ions of the composition Zn1 - x Ni x O has been studied using neutron diffraction and magnetic measurements. It is established that even at very low doping levels ( x = 0.0004), the crystal undergoes local distortions in basal planes of the initial hexagonal lattice. The local distortions are assumed to be sources of the formation of ferromagnetism in compounds of this class.

Influence of defect luminescence and structural modification on the electrical properties of Magnesium Doped Zinc Oxide Nanorods

NASA Astrophysics Data System (ADS)

Santoshkumar, B.; Biswas, Amrita; Kalyanaraman, S.; Thangavel, R.; Udayabhanu, G.; Annadurai, G.; Velumani, S.

2017-06-01

Magnesium doped zinc oxide nanorod arrays on zinc oxide seed layers were grown by hydrothermal method. X-ray diffraction (XRD) patterns revealed the growth orientation along the preferential (002) direction. The hexagonal morphology was revealed from the field emission scanning electron microscope (FESEM) images. The elemental composition of the samples was confirmed by energy dispersive x-ray analysis spectra (EDS) and mapping dots. Carrier concentration, resistivity and mobility of the samples were obtained by Hall measurements. I-V characteristic curve confirmed the increase in resistivity upon doping. Photoluminescence (PL) spectra exposed the characteristic of UV emission along with defect mediated visible emission in the samples. Electrochemical impedance spectroscopy and cyclic voltammetry were undertaken to study the charge transport property. Owing to the change in the structural parameters and defect concentration the electrical properties of the doped samples were altered.

Characterization of swift heavy ion irradiation damage in ceria

DOE PAGES

Yablinsky, Clarissa A.; Devanathan, Ram; Pakarinen, Janne; ...

2015-03-04

Swift heavy ion induced radiation damage is investigated for ceria (CeO 2), which serves as a UO 2 fuel surrogate. Microstructural changes resulting from an irradiation with 940 MeV gold ions of 42 keV/nm electronic energy loss are investigated by means of electron microscopy accompanied by electron energy loss spectroscopy showing that there exists a small density reduction in the ion track core. While chemical changes in the ion track are not precluded, evidence of them was not observed. Classical molecular dynamics simulations of thermal spikes in CeO 2 with an energy deposition of 12 and 36 keV/nm show damagemore » consisting of isolated point defects at 12 keV/nm, and defect clusters at 36 keV/nm, with no amorphization at either energy. Furthermore, inferences are drawn from modeling about density changes in the ion track and the formation of interstitial loops that shed light on features observed by electron microscopy of swift heavy ion irradiated ceria.« less

Atomic Layer-Deposited Titanium-Doped Vanadium Oxide Thin Films and Their Thermistor Applications

DOE PAGES

Wang, Shuyu; Yu, Shifeng; Lu, Ming; ...

2016-11-30

In this paper, 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.

Highly concentrated, stable nitrogen-doped graphene for supercapacitors: Simultaneous doping and reduction

NASA Astrophysics Data System (ADS)

Jiang, Baojiang; Tian, Chungui; Wang, Lei; Sun, Li; Chen, Chen; Nong, Xiaozhen; Qiao, Yingjie; Fu, Honggang

2012-02-01

In this work, we developed a concentrated ammonia-assisted hydrothermal method to obtain N-doped graphene sheets by simultaneous N-doping and reduction of graphene oxide (GO) sheets. The effects of hydrothermal temperature on the surface chemistry and the structure of N-doped graphene sheets were also investigated. X-ray photoelectron spectroscopy (XPS) study of N-doped graphene reveals that the highest doping level of 7.2% N is achieved at 180 °C for 12 h. N binding configurations of sample consist of pyridine N, quaternary N, and pyridine-N oxides. N doping is accompanied by the reduction of GO with decreases in oxygen levels from 34.8% in GO down to 8.5% in that of N-doped graphene. Meanwhile, the sample exhibits excellent N-doped thermal stability. Electrical measurements demonstrate that products have higher capacitive performance than that of pure graphene, the maximum specific capacitance of 144.6 F/g can be obtained which ascribe the pseudocapacitive effect from the N-doping. The samples also show excellent long-term cycle stability of capacitive performance.

Boron doped ZnO embedded into reduced graphene oxide for electrochemical supercapacitors

NASA Astrophysics Data System (ADS)

Alver, Ü.; Tanrıverdi, A.

2016-08-01

In this work, reduced graphene oxide/boron doped zinc oxide (RGO/ZnO:B) composites were fabricated by a hydrothermal process and their electrochemical properties were investigated as a function of dopant concentration. First, boron doped ZnO (ZnO:B) particles was fabricated with different boron concentrations (5, 10, 15 and 20 wt%) and then ZnO:B particles were embedded into RGO sheets. The physical properties of sensitized composites were characterized by XRD and SEM. Characterization indicated that the ZnO:B particles with plate-like structure in the composite were dispersed on graphene sheets. The electrochemical properties of the RGO/ZnO:B composite were investigated through cyclic voltammetry, galvanostatic charge/discharge measurements in a 6 M KOH electrolyte. Electrochemical measurements show that the specific capacitance values of RGO/ZnO:B electrodes increase with increasing boron concentration. RGO/ZnO:B composite electrodes (20 wt% B) display the specific capacitance as high as 230.50 F/g at 5 mV/s, which is almost five times higher than that of RGO/ZnO (52.71 F/g).

Zn2+-Doped Polyaniline/Graphene Oxide as Electrode Material for Electrochemical Supercapacitors

NASA Astrophysics Data System (ADS)

Xu, Hui; Tang, Jing; Chen, Yong; Liu, Jian; Pu, Jinjuan; Li, Qi

2017-10-01

Electrodes based on Zn2+-doped polyaniline/graphene oxide (Zn2+/PANI/GO) were synthesized on stainless steel mesh substrates in H2SO4 solution via electrochemical codeposition. Different concentrations of graphene oxide (GO) were incorporated into the films to improve the electrochemical performance of the electrodes. Electrochemical properties of the films were tested by cyclic voltammetry, galvanostatic charge-discharge tests, and electrochemical impedance spectroscopy, in a three-electrode system. The maximum specific capacitance of the Zn2+/PANI/GO film with a GO concentration of 15 mg L-1 was found to be 1266 F g-1 at a scan rate of 3 mV s-1. This value was higher than that of a Zn2+ doped polyaniline (Zn2+/PANI) film (814 F g-1). The Zn2+/PANI/GO film also showed good cycling stability, retaining over 86% of its initial capacitance after 1000 cycles. These results indicate that the Zn2+/PANI/GO composites can be applied as high performance supercapacitor electrodes.

On Defect Cluster Aggregation and Non-Reducibilty in Tin-Doped Indium Oxide

NASA Astrophysics Data System (ADS)

Warschkow, Oliver; Ellis, Donald E.; Gonzalez, Gabriela; Mason, Thomas O.

2003-03-01

The conductivity of tin-doped indium oxide (ITO), a transparent conductor, is critically dependent on the amount of tin-doping and oxygen partial pressure during preparation and annealing. Frank and Kostlin (Appl. Phys. A 27 (1982) 197-206) rationalized the carrier concentration dependence by postulating the formation of two types of neutral defect clusters at medium tin-doping levels: "Reducible" and "non-reducible" defect clusters; so named to indicate their ability to create carriers under reduction. According to Frank and Kostlin, both are composed of a single oxygen interstitial and two tin atoms substituting for indium, positioned in non-nearest and nearest coordination, respectively. This present work, seeking to distinguish reducible and non-reducible clusters by use of an atomistic model, finds only a weak correlation of oxygen interstitial binding energies with the relative positioning of dopants. Instead, the number of tin-dopants in the vicinity of the interstitial has a much larger effect on how strongly it is bound, a simple consequence of Coulomb interactions. We postulate that oxygen interstitials become non-reducible when clustered with three or more Sn_In. This occurs at higher doping levels as reducible clusters aggregate and share tin atoms. A simple probabilistic model, estimating the average number of clusters so aggregated, provides a qualitatively correct description of the carrier density in reduced ITO as a function of Sn doping level.

Well-dispersed NiO nanoparticles supported on nitrogen-doped carbon nanotube for methanol electrocatalytic oxidation in alkaline media

NASA Astrophysics Data System (ADS)

Wang, Pengcheng; Zhou, Yingke; Hu, Min; Chen, Jian

2017-01-01

Nitrogen-doped carbon nanotube supporting NiO nanoparticles were synthesized by a chemical precipitation process coupled with subsequent calcination. The morphology and structure of the composites were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), and the electrochemical performance was evaluated using cyclic voltammetry and chronoamperometric technique. The effects of nitrogen doping, calcination temperature and content of NiO nanoparticles on the electrocatalytic activity toward methanol oxidation were systematically studied. The results show that the uniformly dispersed ultrafine NiO nanoparticles supported on nitrogen-doped carbon nanotube are obtained after calcination at 400 °C. The optimized composite catalysts present high electrocatalytic activity, fast charge-transfer process, excellent accessibility and stability for methanol oxidation reaction, which are promising for application in the alkaline direct methanol fuel cells.

Alcohol vapor sensing by cadmium-doped zinc oxide thick films based chemical sensor

NASA Astrophysics Data System (ADS)

Zargar, R. A.; Arora, M.; Chackrabarti, S.; Ahmad, S.; Kumar, J.; Hafiz, A. K.

2016-04-01

Cadmium-doped zinc oxide nanoparticles were derived by simple chemical co-precipitation route using zinc acetate dihydrate and cadmium acetate dihydrate as precursor materials. The thick films were casted from chemical co-precipitation route prepared nanoparticles by economic facile screen printing method. The structural, morphological, optical and electrical properties of the film were characterized relevant to alcohol vapor sensing application by powder XRD, SEM, UV-VIS and DC conductivity techniques. The response and sensitivity of alcohol (ethanol) vapor sensor are obtained from the recovery curves at optimum working temperature range from 20∘C to 50∘C. The result shows that maximum sensitivity of the sensor is observed at 25∘C operating temperature. On varying alcohol vapor concentration, minor variation in resistance has been observed. The sensing mechanism of sensor has been described in terms of physical adsorption and chemical absorption of alcohol vapors on cadmium-doped zinc oxide film surface and inside film lattice network through weak hydrogen bonding, respectively.

Pyroelectricity of silicon-doped hafnium oxide thin films

NASA Astrophysics Data System (ADS)

Jachalke, Sven; Schenk, Tony; Park, Min Hyuk; Schroeder, Uwe; Mikolajick, Thomas; Stöcker, Hartmut; Mehner, Erik; Meyer, Dirk C.

2018-04-01

Ferroelectricity in hafnium oxide thin films is known to be induced by various doping elements and in solid-solution with zirconia. While a wealth of studies is focused on their basic ferroelectric properties and memory applications, thorough studies of the related pyroelectric properties and their application potential are only rarely found. This work investigates the impact of Si doping on the phase composition and ferro- as well as pyroelectric properties of thin film capacitors. Dynamic hysteresis measurements and the field-free Sharp-Garn method were used to correlate the reported orthorhombic phase fractions with the remanent polarization and pyroelectric coefficient. Maximum values of 8.21 µC cm-2 and -46.2 µC K-1 m-2 for remanent polarization and pyroelectric coefficient were found for a Si content of 2.0 at%, respectively. Moreover, temperature-dependent measurements reveal nearly constant values for the pyroelectric coefficient and remanent polarization over the temperature range of 0 ° C to 170 ° C , which make the material a promising candidate for IR sensor and energy conversion applications beyond the commonly discussed use in memory applications.

Investigation of fluorine-doped tin oxide based optically transparent E-shaped patch antenna for terahertz communications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Anand, S., E-mail: anand.s.krishna@gmail.com, E-mail: darak.mayur@gmail.com, E-mail: srk@nitt.edu; Darak, Mayur Sudesh, E-mail: anand.s.krishna@gmail.com, E-mail: darak.mayur@gmail.com, E-mail: srk@nitt.edu; Kumar, D. Sriram, E-mail: anand.s.krishna@gmail.com, E-mail: darak.mayur@gmail.com, E-mail: srk@nitt.edu

2014-10-15

In this paper, a fluorine-doped tin oxide based optically transparent E-shaped patch antenna is designed and its radiation performance is analyzed in the 705 – 804 GHz band. As optically transparent antennas can be mounted on optical display, they facilitate the reduction of overall system size. The proposed antenna design is simulated using electromagnetic solver - Ansys HFSS and its characteristics such as impedance bandwidth, directivity, radiation efficiency and gain are observed. Results show that the fluorine-doped tin oxide based optically transparent patch antenna overcomes the conventional patch antenna limitations and thus the same can be used for solar cellmore » antenna used in satellite systems.« less

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 cm 2 V –1 s –1 for carrier densities above 10 20 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

Dysprosium-doped cadmium oxide as a gateway material for mid-infrared plasmonics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sachet, Edward; Shelton, Christopher T.; Harris, Joshua S.

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 cm 2 V –1 s –1 for carrier densities above 10 20 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

Comparison of iron and copper doped manganese cobalt spinel oxides as protective coatings for solid oxide fuel cell interconnects

NASA Astrophysics Data System (ADS)

Talic, Belma; Molin, Sebastian; Wiik, Kjell; Hendriksen, Peter Vang; Lein, Hilde Lea

2017-12-01

MnCo2O4, MnCo1.7Cu0.3O4 and MnCo1.7Fe0.3O4 are investigated as coatings for corrosion protection of metallic interconnects in solid oxide fuel cell stacks. Electrophoretic deposition is used to deposit the coatings on Crofer 22 APU alloy. All three coating materials reduce the parabolic oxidation rate in air at 900 °C and 800 °C. At 700 °C there is no significant difference in oxidation rate between coated samples and uncoated pre-oxidized Crofer 22 APU. The cross-scale area specific resistance (ASR) is measured in air at 800 °C using La0.85Sr0.1Mn1.1O3 (LSM) contact plates to simulate the interaction with the cathode in a SOFC stack. All coated samples have three times lower ASR than uncoated Crofer 22 APU after 4370 h aging. The ASR increase with time is lowest with the MnCo2O4 coating, followed by the MnCo1.7Fe0.3O4 and MnCo1.7Cu0.3O4 coatings. LSM plates contacted to uncoated Crofer 22 APU contain significant amounts of Cr after aging, while all three coatings effectively prevent Cr diffusion into the LSM. A complex Cr-rich reaction layer develops at the coating-alloy interface during oxidation. Cu and Fe doping reduce the extent of this reaction layer at 900 °C, while at 800 °C the effect of doping is insignificant.

Investigation of photoluminescence and dielectric properties of pure and Fe doped nickel oxide nanoparticles

NASA Astrophysics Data System (ADS)

Gupta, Jhalak; Ahmad, Arham S.

2018-05-01

The nanocrystallites of pure and Fe doped Nickel Oxide (NiO) were synthesized by the cost effective co-precipitation method using nickel nitrate as the initial precursor. The synthesized nickel oxide nanoparticles were characterized by X-Ray Diffraction (XRD), Photoluminiscence Spectroscopy (PL), LCR meter. The crystallite size of synthesized pure Nickel Oxide nanoparticles obtained by XRD using Debye Scherer's formula was found to be 21.8nm and the size decreases on increasing the dopant concentration. The optical properties were analyzed by PL and dielectric ones by using LCR meter.

Morphology and Doping Engineering of Sn-Doped Hematite Nanowire Photoanodes.

PubMed

Li, Mingyang; Yang, Yi; Ling, Yichuan; Qiu, Weitao; Wang, Fuxin; Liu, Tianyu; Song, Yu; Liu, Xiaoxia; Fang, Pingping; Tong, Yexiang; Li, Yat

2017-04-12

High-temperature activation has been commonly used to boost the photoelectrochemical (PEC) performance of hematite nanowires for water oxidation, by inducing Sn diffusion from fluorine-doped tin oxide (FTO) substrate into hematite. Yet, hematite nanowires thermally annealed at high temperature suffer from two major drawbacks that negatively affect their performance. First, the structural deformation reduces light absorption capability of nanowire. Second, this "passive" doping method leads to nonuniform distribution of Sn dopant in nanowire and limits the Sn doping concentration. Both factors impair the electrochemical properties of hematite nanowire. Here we demonstrate a silica encapsulation method that is able to simultaneously retain the hematite nanowire morphology even after high-temperature calcination at 800 °C and improve the concentration and uniformity of dopant distribution along the nanowire growth axis. The capability of retaining nanowire morphology allows tuning the nanowire length for optimal light absorption. Uniform distribution of Sn doping enhances the donor density and charge transport of hematite nanowire. The morphology and doping engineered hematite nanowire photoanode decorated with a cobalt oxide-based oxygen evolution reaction (OER) catalyst achieves an outstanding photocurrent density of 2.2 mA cm -2 at 0.23 V vs Ag/AgCl. This work provides important insights on how the morphology and doping uniformity of hematite photoanodes affect their PEC performance.

Different threshold and bipolar resistive switching mechanisms in reactively sputtered amorphous undoped and Cr-doped vanadium oxide thin films

NASA Astrophysics Data System (ADS)

Rupp, Jonathan A. J.; Querré, Madec; Kindsmüller, Andreas; Besland, Marie-Paule; Janod, Etienne; Dittmann, Regina; Waser, Rainer; Wouters, Dirk J.

2018-01-01

This study investigates resistive switching in amorphous undoped and Cr-doped vanadium oxide thin films synthesized by sputtering deposition at low oxygen partial pressure. Two different volatile threshold switching characteristics can occur as well as a non-volatile bipolar switching mechanism, depending on device stack symmetry and Cr-doping. The two threshold switching types are associated with different crystalline phases in the conduction filament created during an initial forming step. The first kind of threshold switching, observed for undoped vanadium oxide films, was, by its temperature dependence, proven to be associated with a thermally triggered insulator-to-metal transition in a crystalline VO2 phase, whereas the threshold switch observed in chromium doped films is stable up to 90 °C and shows characteristics of an electronically induced Mott transition. This different behaviour for undoped versus doped films has been attributed to an increased stability of V3+ due to the Cr3+ doping (as evidenced by X-ray photoelectron spectroscopy analysis), probably favouring the creation of a crystalline Cr-doped V2O3 phase (rather than a Cr-doped VO2 phase) during the energetic forming step. The symmetric Pt/a-(VCr)Ox/Pt device showing high temperature stable threshold switching may find interesting applications as a possible new selector device for resistive switching memory (ReRAM) crossbar arrays.

Performance evaluation of Mn and Fe doped SrCo0.9Nb0.1O3-δ cathode for IT-SOFC application

NASA Astrophysics Data System (ADS)

Bele, Lokesh; Lenka, R. K.; Patro, P. K.; Muhmood, L.; Mahata, T.; Sinha, P. K.

2018-02-01

Cathode materials of Mn and Fe doped SrCo0.9Nb0.1O3-δ, are synthesized by solid state route for intermediate temperature fuel cell applications. Phase pure material is obtained after calcining the precursors at 1100 °C. Phase compatibility is observed between this novel cathode material with gadolinia doped ceria (GDC) electrolyte material as reflected in the diffraction pattern. The state of art YSZ electrolyte is not compatible with this cathode material. Average thermal expansion coefficient of the material varies between 17 to 22 X 10-6 K-1 on doping, from room temperature to 800 °C. Increase in thermal expansion coefficient is observed with Mn and Fe doping associated with the loss of oxygen from the crystal. The electrical conductivity of the cathode material decreases with Fe and Mn doping. Mn doped samples show lowest conductivity. From the symmetric cell measurement lower area specific resistance (0.16 Ω-cm2) is obtained for un-doped samples, at 850 °C. From the initial results it can be inferred that Mn/Fe doping improves neither the thermal expansion co-efficient nor the electrochemical activity.

Conversion of ethanol to 1,3-butadiene over Na doped ZnxZryOz mixed metal oxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baylon, Rebecca A.; Sun, Junming; Wang, Yong

2016-01-01

Despite numerous studies on different oxide catalysts for the ethanol to 1,3-butadiene reaction, few have identified active sites (i.e., type of acidity) correlated to the catalytic performances. In this work, the type of acidity needed for ethanol to 1,3-butadiene conversion has been studied over Zn/Zr mixed oxide catalysts. Specifically, synthesis method, Zn/Zr ratio, and Na doping have been used to control the surface acid-base properties, as confirmed by characterizations such as NH3-TPD and IR-Py techniques. The 2000 ppm Na doped Zn1Zr10Oz-H with balanced base and weak Bronsted acid sites was found to give not only high selectivity to 1,3-butadiene (47%)more » at near complete ethanol conversion (97%), but also exhibited a much higher 1,3-butadiene productivity than other mixed oxides studied.« less

Electrochemically assisted photocatalysis: Highly efficient treatment using thermal titanium oxides doped and non-doped electrodes for water disinfection.

PubMed

Dos Santos, Andreia Betina Kreuser; Claro, Elis Marina Turini; Montagnolli, Renato Nallin; Cruz, Jaqueline Matos; Lopes, Paulo Renato Matos; Bidoia, Ederio Dino

2017-12-15

Electrochemically assisted photocatalysis (by electronic drainage) is a highly promising method for disinfection of water. In this research, the efficiency of photolytic oxidation using UV-A radiation and electrochemically assisted photocatalysis (with electric potential of 1.5 V) was studied by using electrodes prepared by thermal treatment and doped with silver, for inactivation of Escherichia coli and Staphylococcus aureus. The Chick-Watson microorganism inactivation model was applied and the electrical energy consumption of the process was calculated. It was observed no significant inactivation of microorganisms when UV-A light or electric potential were applied separately. However, the electrochemically assisted photocatalytic process, with Ag-doped electrode completely inactivated the microbial population after 10 (E. coli) and 60 min (S. aureus). The best performing non-doped electrodes achieved 52.74% (E. coli) and 44.09% (S. aureus) inactivation rates after 60 min. Thus, electrochemically assisted photocatalytic activity was not only effective for the inactivation of microorganisms, but also notably low on electrical energy consumption during the treatment due to small current and low electric potential applied. Copyright © 2017 Elsevier Ltd. All rights reserved.

Final-state effect on x-ray photoelectron spectrum of nominally d1 and n -doped d0 transition-metal oxides

NASA Astrophysics Data System (ADS)

Lin, Chungwei; Posadas, Agham; Hadamek, Tobias; Demkov, Alexander A.

2015-07-01

We investigate the x-ray photoelectron spectroscopy (XPS) of nominally d1 and n -doped d0 transition-metal oxides including NbO2,SrVO3, and LaTiO3 (nominally d1), as well as n -doped SrTiO3 (nominally d0). In the case of single phase d1 oxides, we find that the XPS spectra (specifically photoelectrons from Nb 3 d , V 2 p , Ti 2 p core levels) all display at least two, and sometimes three distinct components, which can be consistently identified as d0,d1, and d2 oxidation states (with decreasing order in binding energy). Electron doping increases the d2 component but decreases the d0 component, whereas hole doping reverses this trend; a single d1 peak is never observed, and the d0 peak is always present even in phase-pure samples. In the case of n -doped SrTiO3, the d1 component appears as a weak shoulder with respect to the main d0 peak. We argue that these multiple peaks should be understood as being due to the final-state effect and are intrinsic to the materials. Their presence does not necessarily imply the existence of spatially localized ions of different oxidation states nor of separate phases. A simple model is provided to illustrate this interpretation, and several experiments are discussed accordingly. The key parameter to determine the relative importance between the initial-state and final-state effects is also pointed out.

Solution-Processed Flexible Fluorine-doped Indium Zinc Oxide Thin-Film Transistors Fabricated on Plastic Film at Low Temperature

PubMed Central

Seo, Jin-Suk; Jeon, Jun-Hyuck; Hwang, Young Hwan; Park, Hyungjin; Ryu, Minki; Park, Sang-Hee Ko; Bae, Byeong-Soo

2013-01-01

Transparent flexible fluorine-doped indium zinc oxide (IZO:F) thin-film transistors (TFTs) were demonstrated using the spin-coating method of the metal fluoride precursor aqueous solution with annealing at 200°C for 2 hrs on polyethylene naphthalate films. The proposed thermal evolution mechanism of metal fluoride aqueous precursor solution examined by thermogravimetric analysis and Raman spectroscopy can easily explain oxide formation. The chemical composition analysed by XPS confirms that the fluorine was doped in the thin films annealed below 250°C. In the IZO:F thin films, a doped fluorine atom substitutes for an oxygen atom generating a free electron or occupies an oxygen vacancy site eliminating an electron trap site. These dual roles of the doped fluorine can enhance the mobility and improve the gate bias stability of the TFTs. Therefore, the transparent flexible IZO:F TFT shows a high mobility of up to 4.1 cm2/V·s and stable characteristics under the various gate bias and temperature stresses. PMID:23803977

Interfacial control of oxygen vacancy doping and electrical conduction in thin film oxide heterostructures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Veal, Boyd W.; Kim, Seong Keun; Zapol, Peter

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 filmmore » 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.« less

Interfacial control of oxygen vacancy doping and electrical conduction in thin film oxide heterostructures

DOE PAGES

Veal, Boyd W.; Kim, Seong Keun; Zapol, Peter; ...

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 behavior, large changes in metal-insulator transition temperatures, or enhanced catalytic activity. Here in this paper, we report the discovery of a means of reversibly controlling the oxygen vacancy concentration and distribution in oxide heterostructures consisting of electronically conducting In 2O 3 films grown on ionically conducting Y 2O 3-stabilized ZrO 2 substrates. Oxygen ion redistribution across the heterointerface is induced using an applied electric field oriented in the plane of the interface, resulting in controlled oxygenmore » vacancy (and hence electron) doping of the film and possible orders-of-magnitude enhancement of the film's electrical conduction. The reversible modified behavior is dependent on interface properties and is attained without cation doping or changes in the gas environment.« less

Al-doped TiO{sub 2} mesoporous material supported Pd with enhanced catalytic activity for complete oxidation of ethanol

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu, Jing, E-mail: mlczjsls123@163.com; Mu, Wentao, E-mail: mwt15035687833@163.com; Su, Liqing, E-mail: suliqing0163@163.com

Pd catalysts supported on Al-doped TiO{sub 2} mesoporous materials were evaluated in complete oxidation of ethanol. The catalysts synthesized by wet impregnation based on evaporation-induced self-assembly were characterized by X-ray diffraction, measurement of pore structure, XPS, FT-IR, temperature programmed reduction and TEM. Characteristic results showed that the aluminium was doped into the lattice of mesoporous anatase TiO{sub 2} to form Al-O-Ti defect structure. Catalytic results revealed that Al-doped catalysts were much more active than the pristine one, especially at low temperature (≤200 °C). This should be ascribed to the introduction of aluminium ions that suppressed the strong metal-support interaction andmore » increased the active sites of Pd oxides, enhanced the stabilized anatase TiO{sub 2}, improved well dispersed high valence palladium species with high reducibility and enriched chemisorption oxygen. - Graphical abstract: Al-doped Pd/TiO{sub 2} exhibited optimal catalytic performance for ethanol oxidation and CO{sub 2} yield by the suppression of SMSI. - Highlights: • Palladium catalysts supported on Al-doped TiO{sub 2} mesoporous materials were studied. • The introduction of Al can enhance anatase stabilization and increase defect TiO{sub 2}. • The Pd/Al-TiO{sub 2} catalysts show higher ethanol conversion and CO{sub 2} yield than Pd/TiO{sub 2}. • The influence of Al on SMSI and catalytic performance were evaluated by TPR and XPS.« less

Jellyfish-like few-layer graphene nanoflakes: Synthesis, oxidation, and hydrothermal N-doping

NASA Astrophysics Data System (ADS)

Chernyak, Sergei A.; Podgornova, Angelina M.; Arkhipova, Ekaterina A.; Novotortsev, Roman O.; Egorova, Tolganay B.; Ivanov, Anton S.; Maslakov, Konstantin I.; Savilov, Serguei V.; Lunin, Valery V.

2018-05-01

Few-layer graphene nanoflakes with the bent edges, diameter of 15-40 nm and thickness of 6-7 graphene layers have been synthesized using MgO-templated CVD growth. Their oxidation by nitric acid led to the high oxygen content of 18 at.%, a third of which was attributed to carboxylic groups. Oxidized nanoflakes were post-doped by nitrogen groups using hydrothermal treatment at 220 °C with ammonia and urea water solutions resulting in corresponding nitrogen content of 7 and 5 at.%. Synthesized and treated materials were characterized by XPS, Raman spectroscopy and electron microscopy.

Nanostructured cerium oxide: preparation, characterization, and application in energy and environmental catalysis

DOE PAGES

Tang, Wen-Xiang; Gao, Pu-Xian

2016-11-10

Nanostructured cerium oxide (CeO 2) with outstanding physical and chemical properties has attracted extensive interests over the past few decades in environment and energy-related applications. With controllable synthesis of nanostructured CeO 2, much more features were technologically brought out from defect chemistry to structure-derived effects. This paper highlights recent progress on the synthesis and characterization of nanostructured ceria-based materials as well as the traditional and new applications. Specifically, several typical applications based on the desired ceria nanostructures are focused to showcase the importance of nanostructure-derived effects. Moreover, some challenges and perspectives on the nanostructured ceria are presented, such as defectsmore » controlling and retainment, scale-up fabrication, and monolithic devices. Hopefully, this paper can provide an improved understanding of nanostructured CeO 2 and offer new opportunities to promote the further research and applications in the future.« less

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.

High performance of SDC and GDC core shell type composite electrolytes using methane as a fuel for low temperature SOFC

DOE Office of Scientific and Technical Information (OSTI.GOV)

Irshad, Muneeb; Siraj, Khurram, E-mail: razahussaini786@gmail.com, E-mail: khurram.uet@gmail.com; Javed, Fayyaz

Nanocomposites Samarium doped Ceria (SDC), Gadolinium doped Ceria (GDC), core shell SDC amorphous Na{sub 2}CO{sub 3} (SDCC) and GDC amorphous Na{sub 2}CO{sub 3} (GDCC) were synthesized using co-precipitation method and then compared to obtain better solid oxide electrolytes materials for low temperature Solid Oxide Fuel Cell (SOFCs). The comparison is done in terms of structure, crystallanity, thermal stability, conductivity and cell performance. In present work, XRD analysis confirmed proper doping of Sm and Gd in both single phase (SDC, GDC) and dual phase core shell (SDCC, GDCC) electrolyte materials. EDX analysis validated the presence of Sm and Gd in bothmore » single and dual phase electrolyte materials; also confirming the presence of amorphous Na{sub 2}CO{sub 3} in SDCC and GDCC. From TGA analysis a steep weight loss is observed in case of SDCC and GDCC when temperature rises above 725 °C while SDC and GDC do not show any loss. The ionic conductivity and cell performance of single phase SDC and GDC nanocomposite were compared with core shell GDC/amorphous Na{sub 2}CO{sub 3} and SDC/ amorphous Na{sub 2}CO{sub 3} nanocomposites using methane fuel. It is observed that dual phase core shell electrolytes materials (SDCC, GDCC) show better performance in low temperature range than their corresponding single phase electrolyte materials (SDC, GDC) with methane fuel.« less

Water–gas shift reaction over gold nanoparticles dispersed on nanostructured CeO x–TiO 2(110) surfaces: Effects of high ceria coverage

DOE PAGES

Grinter, D. C.; Park, J. B.; Agnoli, S.; ...

2016-08-01

We used scanning tunnelling microscopy to study the morphology of an overlayer of ceria in contact with a TiO 2(110) substrate. Two types of domains were observed after ceria deposition. An ordered ceria film covered half of the surface and high-resolution imaging suggested a near-c(6 × 2) relationship to the underlying TiO 2(110)-(1 × 1). For the other half of the surface, it comprised CeO x nanoparticles and reconstructed TiOx supported on TiO 2(110)-(1 × 1). Exposure to a small amount of gold resulted in the formation of isolated gold atoms and small clusters on the ordered ceria film andmore » TiO 2(110)-(1 × 1) areas, which exhibited significant sintering at 500 K and showed strong interaction between the sintered gold clusters and the domain boundaries of the ceria film. The Au/CeO x/TiO 2(110) model system proved to be a good catalyst for the water–gas shift (WGS) exhibiting much higher turnover frequencies (TOFs) than Cu(111) and Pt(111) benchmarks, or the individual Au/TiO 2(110) and Au/CeO 2(111) systems. Finally, for Au/CeO x/TiO 2(110) catalysts, there was a decrease in catalytic activity with increasing ceria coverage that correlates with a reduction in the concentration of Ce 3 + formed during WGS reaction conditions.« less

Water–gas shift reaction over gold nanoparticles dispersed on nanostructured CeO x–TiO 2(110) surfaces: Effects of high ceria coverage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Grinter, D. C.; Park, J. B.; Agnoli, S.

We used scanning tunnelling microscopy to study the morphology of an overlayer of ceria in contact with a TiO 2(110) substrate. Two types of domains were observed after ceria deposition. An ordered ceria film covered half of the surface and high-resolution imaging suggested a near-c(6 × 2) relationship to the underlying TiO 2(110)-(1 × 1). For the other half of the surface, it comprised CeO x nanoparticles and reconstructed TiOx supported on TiO 2(110)-(1 × 1). Exposure to a small amount of gold resulted in the formation of isolated gold atoms and small clusters on the ordered ceria film andmore » TiO 2(110)-(1 × 1) areas, which exhibited significant sintering at 500 K and showed strong interaction between the sintered gold clusters and the domain boundaries of the ceria film. The Au/CeO x/TiO 2(110) model system proved to be a good catalyst for the water–gas shift (WGS) exhibiting much higher turnover frequencies (TOFs) than Cu(111) and Pt(111) benchmarks, or the individual Au/TiO 2(110) and Au/CeO 2(111) systems. Finally, for Au/CeO x/TiO 2(110) catalysts, there was a decrease in catalytic activity with increasing ceria coverage that correlates with a reduction in the concentration of Ce 3 + formed during WGS reaction conditions.« less

Actinide oxide photodiode and nuclear battery

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sykora, Milan; Usov, Igor

Photodiodes and nuclear batteries may utilize actinide oxides, such a uranium oxide. An actinide oxide photodiode may include a first actinide oxide layer and a second actinide oxide layer deposited on the first actinide oxide layer. The first actinide oxide layer may be n-doped or p-doped. The second actinide oxide layer may be p-doped when the first actinide oxide layer is n-doped, and the second actinide oxide layer may be n-doped when the first actinide oxide layer is p-doped. The first actinide oxide layer and the second actinide oxide layer may form a p/n junction therebetween. Photodiodes including actinide oxidesmore » are better light absorbers, can be used in thinner films, and are more thermally stable than silicon, germanium, and gallium arsenide.« less

Atomically Dispersed Pd–O Species on CeO 2(111) as Highly Active Sites for Low-Temperature CO Oxidation

DOE PAGES

Spezzati, Giulia; Su, Yaqiong; Hofmann, Jan P.; ...

2017-09-07

Ceria-supported Pd is a promising heterogeneous catalyst for CO oxidation relevant to environmental cleanup reactions. Pd loaded onto a nanorod form of ceria exposing predominantly (111) facets is already active at 50 °C. Here we report a combination of CO-FTIR spectroscopy and theoretical calculations that allows assigning different forms of Pd on the CeO 2(111) surface during reaction conditions. Single Pd atoms stabilized in the form of PdO and PdO 2 in a CO/O 2 atmosphere participate in a catalytic cycle involving very low activation barriers for CO oxidation. In conclusion, the presence of single Pd atoms on the Pd/CeOmore » 2-nanorod, corroborated by aberration-corrected TEM and CO-FTIR spectroscopy, is considered pivotal to its high CO oxidation activity.« less

Atomically Dispersed Pd–O Species on CeO 2(111) as Highly Active Sites for Low-Temperature CO Oxidation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Spezzati, Giulia; Su, Yaqiong; Hofmann, Jan P.

Ceria-supported Pd is a promising heterogeneous catalyst for CO oxidation relevant to environmental cleanup reactions. Pd loaded onto a nanorod form of ceria exposing predominantly (111) facets is already active at 50 °C. Here we report a combination of CO-FTIR spectroscopy and theoretical calculations that allows assigning different forms of Pd on the CeO 2(111) surface during reaction conditions. Single Pd atoms stabilized in the form of PdO and PdO 2 in a CO/O 2 atmosphere participate in a catalytic cycle involving very low activation barriers for CO oxidation. In conclusion, the presence of single Pd atoms on the Pd/CeOmore » 2-nanorod, corroborated by aberration-corrected TEM and CO-FTIR spectroscopy, is considered pivotal to its high CO oxidation activity.« less

Spectroscopic Study of Local Interactions of Platinum in Small [CexOy]Ptx' - Clusters

NASA Astrophysics Data System (ADS)

Ray, Manisha; Kafader, Jared O.; Chick Jarrold, Caroline

2016-06-01

Cerium oxide is a good ionic conductor, and the conductivity can be enhanced with oxygen vacancies and doping. This conductivity may play an important role in the enhancement of noble or coinage metal toward the water-gas shift reaction when supported by cerium oxide. The ceria-supported platinum catalyst in particular has received much attention because of higher activity at lower temperatures (LT) compared to the most common commercial LT-WGS catalyst. We have used a combination of anion photoelectron spectroscopy and density functional theory calculations to study the interesting molecular and electronic structures and properties of cluster models of ceria-supported platinum. [CexOy]Ptx' - (x,x'=1,2 ; y≤2x') clusters exhibit evidence of ionic bonding possible because of the high electron affinity of Pt and the low ionization potential of cerium oxide clusters. In addition, Pt- is a common daughter ion resulting from photodissociation of [CexOy]Ptx' - clusters. Finally, several of the anion and neutral clusters have profoundly different structures. These features may play a role in the enhancement of catalytic activity toward the water-gas shift reaction.

Manganese oxide nanowires wrapped with nitrogen doped carbon layers for high performance supercapacitors.

PubMed

Li, Ying; Mei, Yuan; Zhang, Lin-Qun; Wang, Jian-Hai; Liu, An-Ran; Zhang, Yuan-Jian; Liu, Song-Qin

2015-10-01

In this study, manganese oxide nanowires wrapped by nitrogen-doped carbon layers (MnO(x)@NCs) were prepared by carbonization of poly(o-phenylenediamine) layer coated onto MnO2 nanowires for high performance supercapacitors. The component and structure of the MnO(x)@NCs were controlled through carbonization procedure under different temperatures. Results demonstrated that this composite combined the high conductivity and high specific surface area of nitrogen-doped carbon layers with the high pseudo-capacitance of manganese oxide nanowires. The as-prepared MnO(x)@NCs exhibited superior capacitive properties in 1 M Na2SO4 aqueous solution, such as high conductivity (4.167×10(-3) S cm(-1)), high specific capacitance (269 F g(-1) at 10 mV s(-1)) and long cycle life (134 F g(-1) after 1200 cycles at a scan rate of 50 mV s(-1)). It is reckoned that the present novel hybrid nanowires can serve as a promising electrode material for supercapacitors and other electrochemical devices. Copyright © 2015 Elsevier Inc. All rights reserved.

Performance and properties of anodes reinforced with metal oxide nanoparticles for molten carbonate fuel cells

NASA Astrophysics Data System (ADS)

Accardo, Grazia; Frattini, Domenico; Yoon, Sung Pil; Ham, Hyung Chul; Nam, Suk Woo

2017-12-01

Development of electrode materials for molten carbonate fuel cells is a fundamental issue as a balance between mechanical and electrochemical properties is required due to the particular operating environments of these cells. As concern the anode, a viable strategy is to use nano-reinforced particles during electrodes' fabrication. Candidate nanomaterials comprise, but are not limited to, ZrO2, CeO2, TiO2, Ti, Mg, Al, etc. This work deals with the characterization and test of two different types of hard oxide nanoparticles as reinforce for NiAl-based anodes in molten carbonate fuel cells. Nano ceria and nano zirconia are compared each other and single cell test performances are presented. Compared to literature, the use of hard metal oxide nanoparticles allows good performance and promising perspectives with respect to the use a third alloying metal. However, nano zirconia performed slightly better than nano ceria as polarization and power curves are higher even if nano ceria has the highest mechanical properties. This means that the choice of nanoparticles to obtain improved anodes performance and properties is not trivial and a trade-off between relevant properties plays a key role.

Optimization of Uranium-Doped Americium Oxide Synthesis for Space Application.

PubMed

Vigier, Jean-François; Freis, Daniel; Pöml, Philipp; Prieur, Damien; Lajarge, Patrick; Gardeur, Sébastien; Guiot, Antony; Bouëxière, Daniel; Konings, Rudy J M

2018-04-16

Americium 241 is a potential alternative to plutonium 238 as an energy source for missions into deep space or to the dark side of planetary bodies. In order to use the 241 Am isotope for radioisotope thermoelectric generator or radioisotope heating unit (RHU) production, americium materials need to be developed. This study focuses on the stabilization of a cubic americium oxide phase using uranium as the dopant. After optimization of the material preparation, (Am 0.80 U 0.12 Np 0.06 Pu 0.02 )O 1.8 has been successfully synthesized to prepare a 2.96 g pellet containing 2.13 g of 241 Am for fabrication of a small scale RHU prototype. Compared to the use of pure americium oxide, the use of uranium-doped americium oxide leads to a number of improvements from a material properties and safety point of view, such as good behavior under sintering conditions or under alpha self-irradiation. The mixed oxide is a good host for neptunium (i.e., the 241 Am daughter element), and it has improved safety against radioactive material dispersion in the case of accidental conditions.

Segregation and Migration of the Oxygen Vacancies in the 3 (111) Tilt Grain Boundaries of Ceria

DOE PAGES

Yuan, Fenglin; Liu, Bin; Zhang, Yanwen; ...

2016-03-01

In nanocrystalline materials, defect-grain boundary (GB) interaction plays a key role in determining the structure stability, as well as size-dependent ionic, electronic, magnetic and chemical properties. In this study, we systematically investigated using density functional theory segregation and migration of oxygen vacancies at the Σ3 [110] / (111) grain boundary of ceria. Three oxygen layers near the GB are predicted to be segregation sites for oxygen vacancies. Moreover, the presence of oxygen vacancies stabilizes this tilt GB at a low Fermi level and/or oxygen poor conditions. An atomic strain model was proposed to rationalize layer dependency of the relaxation energymore » for +2 charged oxygen vacancy. The structural origin of large relaxation energies at layers 1 and 2 was determined to be free-volume space that induces ion relaxation towards the GB. Our results not only pave the way for improving the oxygen transport near GBs of ceria, but also provide important insights into engineering the GB structure for better ionic, magnetic and chemical properties of nanocrystalline ceria.« less

Improved thermal stability of methylsilicone resins by compositing with N-doped graphene oxide/Co3O4 nanoparticles

NASA Astrophysics Data System (ADS)

Jiang, Bo; Zhao, Liwei; Guo, Jiang; Yan, Xingru; Ding, Daowei; Zhu, Changcheng; Huang, Yudong; Guo, Zhanhu

2016-06-01

Nanoparticles play important roles in enhancing the thermal-resistance of hosting polymer resins. Despite tremendous efforts, developing thermally stable methylsilicone resin at high temperatures is still a challenge. Herein, we report a strategy to increase the activation energy to slow down the decomposition/degradation of methylsilicone resin using synergistic effects between the Co3O4 nanoparticles and the nitrogen doped graphene oxide. The N-doped graphene oxides composited with Co3O4 nanoparticles were prepared by hydrolysis of cobalt nitrate hexahydrate in the presence of graphene oxide and were incorporated into the methylsilicone resin. Two-stage decompositions were observed, i.e., 200-300 and 400-500 °C. The activation energy for the low temperature region was enhanced by 47.117 kJ/mol (vs. 57.76 kJ/mol for pure resin). The enhanced thermal stability was due to the fact that the nanofillers prevented the silicone hydroxyl chain ends ``biting'' to delay the degradation. The activation energy for high-temperature region was enhanced by 11.585 kJ/mol (vs. 171.95 kJ/mol for pure resin). The nanofillers formed a protective layer to isolate oxygen from the hosting resin. The mechanism for the enhanced thermal stability through prohibited degradation with synergism of these nitrogen-doped graphene oxide nanocomposites was proposed as well.

Facile fabrication of palladium-ionic liquids-nitrogen-doped graphene nanocomposites as enhanced electro-catalyst for ethanol oxidation

NASA Astrophysics Data System (ADS)

Li, Shuwen; Yang, Honglei; Ren, Ren; Ma, Jianxin; Jin, Jun; Ma, Jiantai

2015-10-01

The palladium-ionic liquids-nitrogen-doped graphene nanocomposites are facile fabricated as enhanced electro-catalyst for ethanol oxidation. First, the ionic liquids functionalized nitrogen-doping graphene nanosheets (PDIL-NGS) with few layers is synthesized through a facile and effective one-pot hydrothermal method with graphene oxide as raw material, urea as reducing-doping agents and ionic liquids (ILs) derived from 3,4,9,10-perylene tetracarboxylic acid as functional molecules. The results of systematic characterization reveal that the PDIL molecules not only can functionalize NGS by π-π stacking with no affecting the nitrogen doping but also prevent the agglomeration of NGS. More importantly, the processing performance and the property of electron transfer are remarkably enhanced duo to introducing a large number of ILs groups. Then, the enhanced electrocatalytic Pd nanoparticles are successfully anchored on PDIL-NGS by a facile and surfactant-free synthetic technique. As an anode catalyst, the novel catalyst exhibits better kinetics, more superior electrocatalytic performance, higher tolerance and electrochemical stability than the other catalysts toward ethanol electrooxidation, owing to the role of PDIL molecules. Therefore, the new catalyst is believed to have the potential use for direct alcohol fuel cells in the future and the functionalized NGS is promising useful materials applied in other fields.

Visible-light driven nitrogen-doped petal-morphological ceria nanosheets for water splitting

NASA Astrophysics Data System (ADS)

Qian, Junchao; Zhang, Wenya; Wang, Yaping; Chen, Zhigang; Chen, Feng; Liu, Chengbao; Lu, Xiaowang; Li, Ping; Wang, Kaiyuan; Chen, Ailian

2018-06-01

Water splitting is a promising sustainable technology for solar-to-chemical energy conversion. Herein, we successfully fabricated nitrogen-doped ultrathin CeO2 nanosheets by using field poppy petals as templates, which exhibit an efficiently catalytic activity for water splitting. Abundant oxygen vacancies and substitutional N atoms were experimentally observed in the film due to its unique biomorphic texture. In view of high efficiency and long durability of the as-prepared photocatalyst, this biotemplate method may provide an alternative technique for using biomolecules to assemble 2D nanomaterials.

Effects of rare earth doping on multi-core iron oxide nanoparticles properties

NASA Astrophysics Data System (ADS)

Petran, Anca; Radu, Teodora; Borodi, Gheorghe; Nan, Alexandrina; Suciu, Maria; Turcu, Rodica

2018-01-01

New multi-core iron oxide magnetic nanoparticles doped with rare earth metals (Gd, Eu) were obtained by a one step synthesis procedure using a solvothermal method for potential biomedical applications. The obtained clusters were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), energy-dispersive X-ray microanalysis (EDX), X-ray photoelectron spectroscopy (XPS) and magnetization measurements. They possess high colloidal stability, a saturation magnetization of up to 52 emu/g, and nearly spherical shape. The presence of rare earth ions in the obtained samples was confirmed by EDX and XPS. XRD analysis proved the homogeneous distribution of the trivalent rare earth ions in the inverse-spinel structure of magnetite and the increase of crystal strain upon doping the samples. XPS study reveals the valence state and the cation distribution on the octahedral and tetrahedral sites of the analysed samples. The observed shift of the XPS valence band spectra maximum in the direction of higher binding energies after rare earth doping, as well as theoretical valence band calculations prove the presence of Gd and Eu ions in octahedral sites. The blood protein adsorption ability of the obtained samples surface, the most important factor of the interaction between biomaterials and body fluids, was assessed by interaction with bovine serum albumin (BSA). The rare earth doped clusters surface show higher afinity for binding BSA. In vitro cytotoxicity test results for the studied samples showed no cytotoxicity in low and medium doses, establishing a potential perspective for rare earth doped MNC to facilitate multiple therapies in a single formulation for cancer theranostics.

Oxidation of Sn doped Cu cluster: A first principle study

NASA Astrophysics Data System (ADS)

Parida, Ganesh; Majumder, Chiranjib

2017-05-01

Bimetallic clusters have immense potential to exhibit tunable properties in the emerging field of nano catalysis. Using plane wave based pseudopotential approach we have investigated the oxidation behavior of pure and Sn doped Cu13 clusters. The results showed significant modification of the cluster geometry upon interaction with oxygen molecule. The interaction of oxygen with Cu13, Cu12Sn1 and Cu11Sn2 clusters show dissociative chemisorption is more favorable than molecular adsorption. In addition, the adsorption energy is found to decrease with the increase in Sn concentration.

Systematic Doping of Cobalt into Layered Manganese Oxide Sheets Substantially Enhances Water Oxidation Catalysis.

PubMed

McKendry, Ian G; Thenuwara, Akila C; Shumlas, Samantha L; Peng, Haowei; Aulin, Yaroslav V; Chinnam, Parameswara Rao; Borguet, Eric; Strongin, Daniel R; Zdilla, Michael J

2018-01-16

The effect on the electrocatalytic oxygen evolution reaction (OER) of cobalt incorporation into the metal oxide sheets of the layered manganese oxide birnessite was investigated. Birnessite and cobalt-doped birnessite were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and conductivity measurements. A cobalt:manganese ratio of 1:2 resulted in the most active catalyst for the OER. In particular, the overpotential (η) for the OER was 420 mV, significantly lower than the η = 780 mV associated with birnessite in the absence of Co. Furthermore, the Tafel slope for Co/birnessite was 81 mV/dec, in comparison to a Tafel slope of greater than 200 mV/dec for birnessite. For chemical water oxidation catalysis, an 8-fold turnover number (TON) was achieved (h = 70 mmol of O 2 /mol of metal). Density functional theory (DFT) calculations predict that cobalt modification of birnessite resulted in a raising of the valence band edge and occupation of that edge by holes with enhanced mobility during catalysis. Inclusion of extra cobalt beyond the ideal 1:2 ratio was detrimental to catalysis due to disruption of the layered structure of the birnessite phase.

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

EPA Science Inventory

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

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

PubMed

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

2016-10-01

We report the synthesis of high quality CeO2-CdO binary metal oxide nanocomposites were synthesized by a simple chemical precipitation and hydrothermal method. Cerium nitrate and cadmium nitrate were used as precursors. Composition, structure and morphology of the nanocomposites were analyzed by X-ray diffraction (XRD) and high resolution transmission electron microscopy (HRTEM). XRD pattern proves that the final product has cubic phase and the particle size diameter of the nanocomposites are 27nm, XRD results also indicated that the crystalline properties of the nanocomposite were improved without affecting the parent lattice, FESEM analysis indicates that the product is composed of spherical particles in clusters. The morphological and optical properties of CeO2-CdO nanosamples were characterized by HRTEM and DRS spectroscopy. The IR results showed high purity of products and indicated that the nanocomposites are made up of CeO2 and CdO bonds. Absorption spectra exhibited an upward shift in characteristic peaks caused by the addition of transition metal oxide, suggesting that crystallinity of both the metal oxide is improved due to specific doping level. TGA plots further confirmed the purity and stability of nanomaterials prepared. Hence the nanocomposite has cubic crystal lattice and form a homogeneous solid structure. From the result, Cd(2+) ions are embedded in the cubic crystal lattice of ceria. The growth rate increases which are ascribed to the cationic doping with a lower valence cation. Ce-Cd binary metal oxide nanocomposites showed antibacterial activity, it showed the better growth inhibition towards p.aeruginosa. Exploit of photodegradation and photocatalytic activity of large scale synthesis of CeO2-CdO binary metal oxide nanocomposites was reported. Copyright © 2016 Elsevier B.V. All rights reserved.

Characterization of cubic ceria?zirconia powders by X-ray diffraction and vibrational and electronic spectroscopy

NASA Astrophysics Data System (ADS)

Sánchez Escribano, Vicente; Fernández López, Enrique; Panizza, Marta; Resini, Carlo; Gallardo Amores, José Manuel; Busca, Guido

2003-10-01

The X-ray diffraction (XRD) patterns and the Infrared, Raman and UV-visible spectra of CeO 2ZrO 2 powders prepared by co-precipitation are presented. Raman spectra provide evidence for the largely predominant cubic structure of the powders with CeO 2 molar composition higher than 25%. Also skeletal IR spectra allow to distinguish cubic from tetragonal phases which are instead not easily distinguished on the basis of the XRD patterns. All mixed oxides including pure ceria are strong UV absorbers although also absorb in the violet visible region. By carefully selecting their composition and treatment temperature, the onset of the radiation that they cut off can be chosen in the 425-475 nm interval. Although they are likely metastable, the cubic phases are still pure even after heating at 1173 K for 4 h.

Bipolar charge storage characteristics in copper and cobalt co-doped zinc oxide (ZnO) thin film.

PubMed

Kumar, Amit; Herng, Tun Seng; Zeng, Kaiyang; Ding, Jun

2012-10-24

The bipolar charge phenomenon in Cu and Co co-doped zinc oxide (ZnO) film samples has been studied using scanning probe microscopy (SPM) techniques. Those ZnO samples are made using a pulsed laser deposition (PLD) technique. It is found that the addition of Cu and Co dopants suppresses the electron density in ZnO and causes a significant change in the work function (Fermi level) value of the ZnO film; this results in the ohmic nature of the contact between the electrode (probe tip) and codoped sample, whereas this contact exhibits a Schottky nature in the undoped and single-element-doped samples. These results are verified by Kelvin probe force microscopy (KPFM) and ultraviolet photoelectron spectroscopy (UPS) measurements. It is also found that the co-doping (Cu and Co) can stabilize the bipolar charge, whereas Cu doping only stabilizes the positive charge in ZnO thin films.

Low-Concentration Indium Doping in Solution-Processed Zinc Oxide Films for Thin-Film Transistors.

PubMed

Zhang, Xue; Lee, Hyeonju; Kwon, Jung-Hyok; Kim, Eui-Jik; Park, Jaehoon

2017-07-31

We investigated the influence of low-concentration indium (In) doping on the chemical and structural properties of solution-processed zinc oxide (ZnO) films and the electrical characteristics of bottom-gate/top-contact In-doped ZnO thin-film transistors (TFTs). The thermogravimetry and differential scanning calorimetry analysis results showed that thermal annealing at 400 °C for 40 min produces In-doped ZnO films. As the In content of ZnO films was increased from 1% to 9%, the metal-oxygen bonding increased from 5.56% to 71.33%, while the metal-hydroxyl bonding decreased from 72.03% to 9.63%. The X-ray diffraction peaks and field-emission scanning microscope images of the ZnO films with different In concentrations revealed a better crystalline quality and reduced grain size of the solution-processed ZnO thin films. The thickness of the In-doped ZnO films also increased when the In content was increased up to 5%; however, the thickness decreased on further increasing the In content. The field-effect mobility and on/off current ratio of In-doped ZnO TFTs were notably affected by any change in the In concentration. Considering the overall TFT performance, the optimal In doping concentration in the solution-processed ZnO semiconductor was determined to be 5% in this study. These results suggest that low-concentration In incorporation is crucial for modulating the morphological characteristics of solution-processed ZnO thin films and the TFT performance.

Plasmon resonance and perfect light absorption in subwavelength trench arrays etched in gallium-doped zinc oxide film

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hendrickson, Joshua R., E-mail: joshua.hendrickson.4@us.af.mil; Leedy, Kevin; Cleary, Justin W.

Near-perfect light absorption in subwavelength trench arrays etched in highly conductive gallium-doped zinc oxide films was experimentally observed in the mid infrared regime. At wavelengths corresponding to the resonant excitation of surface plasmons, up to 99% of impinging light is efficiently trapped and absorbed in the periodic trenches. Scattering cross sectional calculations reveal that each individual trench acts like a vertical split ring resonator with a broad plasmon resonance spectrum. The coupling of these individual plasmon resonators in the grating structure leads to enhanced photon absorption and significant resonant spectral linewidth narrowing. Ellipsometry measurements taken before and after device fabricationmore » result in different permittivity values for the doped zinc oxide material, indicating that localized annealing occurred during the plasma etching process due to surface heating. Simulations, which incorporate a 50 nm annealed region at the zinc oxide surface, are in a good agreement with the experimental results.« less

Influence of Cr doping on the stability and structure of small cobalt oxide clusters.

PubMed

Tung, Nguyen Thanh; Tam, Nguyen Minh; Nguyen, Minh Tho; Lievens, Peter; Janssens, Ewald

2014-07-28

The stability of mass-selected pure cobalt oxide and chromium doped cobalt oxide cluster cations, ConO+m and Con-1CrO+m (n = 2, 3; m = 2-6 and n = 4; m = 3-8), has been investigated using photodissociation mass spectrometry. Oxygen-rich ConO+m clusters (m ≥ n + 1 for n = 2, 4 and m ≥ n + 2 for n = 3) prefer to photodissociate via the loss of an oxygen molecule, whereas oxygen poorer clusters favor the evaporation of oxygen atoms. Substituting a single Co atom by a single Cr atom alters the dissociation behavior. All investigated Con-1 CrO+m clusters, except CoCrO+2 and CoCrO+3, prefer to decay by eliminating a neutral oxygen molecule. Co2O+2, Co4O+3, Co4O+4, and CoCrO+2 are found to be relatively difficult to dissociate and appear as fragmentation product of several larger clusters, suggesting that they are particularly stable. The geometric structures of pure and Cr doped cobalt oxide species are studied using density functional theory calculations. Dissociation energies for different evaporation channels are calculated and compared with the experimental observations. The influence of the dopant atom on the structure and the stability of the clusters is discussed.

Synthesis and controllable oxidation of monodisperse cobalt-doped wüstite nanoparticles and their core-shell stability and exchange-bias stabilization.

PubMed

Chen, Chih-Jung; Chiang, Ray-Kuang; Kamali, Saeed; Wang, Sue-Lein

2015-09-14

Cobalt-doped wüstite (CWT), Co0.33Fe0.67O, nanoparticles were prepared via the thermal decomposition of CoFe2-oleate complexes in organic solvents. A controllable oxidation process was then performed to obtain Co0.33Fe0.67O/CoFe2O4 core-shell structures with different core-to-shell volume ratios and exchange bias properties. The oxidized core-shell samples with a ∼4 nm CoFe2O4 shell showed good resistance to oxygen transmission. Thus, it is inferred that the cobalt ferrite shell provides a better oxidation barrier performance than magnetite in the un-doped case. The hysteresis loops of the oxidized 19 nm samples exhibited a high exchange bias field (H(E)), an enhanced coercivity field (H(C)), and a pronounced vertical shift, thus indicating the presence of a strong exchange bias coupling effect. More importantly, the onset temperature of H(E) was found to be higher than 200 K, which suggests that cobalt doping increases the Néel temperature (T(N)) of the CWT core. In general, the results show that the homogeneous dispersion of Co in iron precursors improves the stability of the final CWT nanoparticles. Moreover, the CoFe2O4 shells formed following oxidation increase the oxidation resistance of the CWT cores and enhance their anisotropy energy.

One-step electrochemical synthesis of nitrogen and sulfur co-doped, high-quality graphene oxide.

PubMed

Parvez, Khaled; Rincón, Rosalba A; Weber, Nils-Eike; Cha, Kitty C; Venkataraman, Shyam S

2016-04-28

High-quality graphene oxide (GO) with high crystallinity and electrical conductivity as well as in situ doped with nitrogen and sulfur is obtained via the electrochemical exfoliation of graphite. Furthermore, iron incorporated GO sheets show promising catalytic activity and stable methanol tolerance durability when used as electrocatalysts for the oxygen reduction reaction.

Interplay of dopant, defects and electronic structure in driving ferromagnetism in Co-doped oxides: TiO(2), CeO(2) and ZnO.

PubMed

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

2009-11-11

A comprehensive study of the defects and impurity (Co)-driven ferromagnetism is undertaken in the oxide semiconductors: TiO(2), ZnO and CeO(2). The effect of magnetic (Co(2+)) and non-magnetic (Cu(2+)) impurities in conjunction with defects, such as oxygen vacancies (V(o)), have been thoroughly investigated. Analyses of the x-ray diffraction (XRD) and x-ray photoelectron spectroscopy (XPS) data reveal the incorporation of cobalt in the lattice, with no signature of cobalt segregation. It is shown that oxygen vacancies are necessary for the ferromagnetic coupling in the Co-doped oxides mentioned above. The possible exchange mechanisms responsible for the ferromagnetism are discussed in light of the energy levels of dopants in the host oxides. In addition, Co and Cu co-doped TiO(2) samples are studied in order to understand the role of point defects in establishing room temperature ferromagnetism. The parameters calculated from the bound magnetic polaron (BMP) and Jorgensen's optical electronegativity models offer a satisfactory explanation of the defect-driven ferromagnetism in the doped/co-doped samples.

Acetone Sensing Properties of a Gas Sensor Composed of Carbon Nanotubes Doped With Iron Oxide Nanopowder.

PubMed

Tan, Qiulin; Fang, Jiahua; Liu, Wenyi; Xiong, Jijun; Zhang, Wendong

2015-11-11

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.

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

Plasmonic Properties of Silicon Nanocrystals Doped with Boron and Phosphorus.

PubMed

Kramer, Nicolaas J; Schramke, Katelyn S; Kortshagen, Uwe R

2015-08-12

Degenerately doped silicon nanocrystals are appealing plasmonic materials due to silicon's low cost and low toxicity. While surface plasmonic resonances of boron-doped and phosphorus-doped silicon nanocrystals were recently observed, there currently is poor understanding of the effect of surface conditions on their plasmonic behavior. Here, we demonstrate that phosphorus-doped silicon nanocrystals exhibit a plasmon resonance immediately after their synthesis but may lose their plasmonic response with oxidation. In contrast, boron-doped nanocrystals initially do not exhibit plasmonic response but become plasmonically active through postsynthesis oxidation or annealing. We interpret these results in terms of substitutional doping being the dominant doping mechanism for phosphorus-doped silicon nanocrystals, with oxidation-induced defects trapping free electrons. The behavior of boron-doped silicon nanocrystals is more consistent with a strong contribution of surface doping. Importantly, boron-doped silicon nanocrystals exhibit air-stable plasmonic behavior over periods of more than a year.

Low-temperature CO oxidation over Cu/Pt co-doped ZrO2 nanoparticles synthesized by solution combustion.

PubMed

Singhania, Amit; Gupta, Shipra Mital

2017-01-01

Zirconia (ZrO 2 ) nanoparticles co-doped with Cu and Pt were applied as catalysts for carbon monoxide (CO) oxidation. These materials were prepared through solution combustion in order to obtain highly active and stable catalytic nanomaterials. This method allows Pt 2+ and Cu 2+ ions to dissolve into the ZrO 2 lattice and thus creates oxygen vacancies due to lattice distortion and charge imbalance. High-resolution transmission electron microscopy (HRTEM) results showed Cu/Pt co-doped ZrO 2 nanoparticles with a size of ca. 10 nm. X-ray diffraction (XRD) and Raman spectra confirmed cubic structure and larger oxygen vacancies. The nanoparticles showed excellent activity for CO oxidation. The temperature T 50 (the temperature at which 50% of CO are converted) was lowered by 175 °C in comparison to bare ZrO 2 . Further, they exhibited very high stability for CO reaction (time-on-stream ≈ 70 h). This is due to combined effect of smaller particle size, large oxygen vacancies, high specific surface area and better thermal stability of the Cu/Pt co-doped ZrO 2 nanoparticles. The apparent activation energy for CO oxidation is found to be 45.6 kJ·mol -1 . The CO conversion decreases with increase in gas hourly space velocity (GHSV) and initial CO concentration.

The Structure and Properties of Plasma Sprayed Iron Oxide Doped Manganese Cobalt Oxide Spinel Coatings for SOFC Metallic Interconnectors

NASA Astrophysics Data System (ADS)

Puranen, Jouni; Lagerbom, Juha; Hyvärinen, Leo; Kylmälahti, Mikko; Himanen, Olli; Pihlatie, Mikko; Kiviaho, Jari; Vuoristo, Petri

2011-01-01

Manganese cobalt oxide spinel doped with Fe2O3 was studied as a protective coating on ferritic stainless steel interconnects. Chromium alloying causes problems at high operation temperatures in such oxidizing conditions where chromium compounds evaporate and poison the cathode active area, causing the degradation of the solid oxide fuel cell. In order to prevent chromium evaporation, these interconnectors need a protective coating to block the chromium evaporation and to maintain an adequate electrical conductivity. Thermal spraying is regarded as a promising way to produce dense and protective layers. In the present work, the ceramic Mn-Co-Fe oxide spinel coatings were produced by using the atmospheric plasma spray process. Coatings with low thickness and low amount of porosity were produced by optimizing deposition conditions. The original spinel structure decomposed because of the fast transformation of solid-liquid-solid states but was partially restored by using post-annealing treatment.

Transparent indium-tin oxide/indium-gallium-zinc oxide Schottky diodes formed by gradient oxygen doping

NASA Astrophysics Data System (ADS)

Ho, Szuheng; Yu, Hyeonggeun; So, Franky

2017-11-01

Amorphous InGaZnO (a-IGZO) is promising for transparent electronics due to its high carrier mobility and optical transparency. However, most metal/a-IGZO junctions are ohmic due to the Fermi-level pinning at the interface, restricting their device applications. Here, we report that indium-tin oxide/a-IGZO Schottky diodes can be formed by gradient oxygen doping in the a-IGZO layer that would otherwise form an ohmic contact. Making use of back-to-back a-IGZO Schottky junctions, a transparent IGZO permeable metal-base transistor is also demonstrated with a high common-base gain.

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.

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.

Liquid Phase Plasma Synthesis of Iron Oxide Nanoparticles on Nitrogen-Doped Activated Carbon Resulting in Nanocomposite for Supercapacitor Applications.

PubMed

Lee, Heon; Lee, Won-June; Park, Young-Kwon; Ki, Seo Jin; Kim, Byung-Joo; Jung, Sang-Chul

2018-03-25

Iron oxide nanoparticles supported on nitrogen-doped activated carbon powder were synthesized using an innovative plasma-in-liquid method, called the liquid phase plasma (LPP) method. Nitrogen-doped carbon (NC) was prepared by a primary LPP reaction using an ammonium chloride reactant solution, and an iron oxide/NC composite (IONCC) was prepared by a secondary LPP reaction using an iron chloride reactant solution. The nitrogen component at 3.77 at. % formed uniformly over the activated carbon (AC) surface after a 1 h LPP reaction. Iron oxide nanoparticles, 40~100 nm in size, were impregnated homogeneously over the NC surface after the LPP reaction, and were identified as Fe₃O₄ by X-ray photoelectron spectroscopy and X-ray diffraction. NC and IONCCs exhibited pseudo-capacitive characteristics, and their specific capacitance and cycling stability were superior to those of bare AC. The nitrogen content on the NC surface increased the compatibility and charge transfer rate, and the composites containing iron oxide exhibited a lower equivalent series resistance.

Three-dimensional Nitrogen-Doped Reduced Graphene Oxide/Carbon Nanotube Composite Catalysts for Vanadium Flow Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fu, Shaofang; Zhu, Chengzhou; Song, Junhua

The development of vanadium redox flow battery is limited by the sluggish kinetics of the reaction, especially the cathodic VO2+/VO2+ redox couples. Therefore, it is vital to develop new electrocatalyst with enhanced activity to improve the battery performance. Herein, we first synthesized the hydrogel precursor by a facile hydrothermal method. After the following carbonization, nitrogen-doped reduced graphene oxide/carbon nanotube composite was obtained. By virtue of the large surface area and good conductivey, which are ensured by the unique hybrid structure, as well as the proper nitrogen doping, the as-prepared composite presents enhanced catalytic performance toward the VO2+/VO2+ redox reaction. Wemore » also demonstrated the composite with carbon nanotube loading of 2 mg/mL exhibits the highest activity and remarkable stability in aqueous solution due to the strong synergy between reduced graphene oxide and carbon nanotubes, indicating that this composite might show promising applications in vanadium redox flow battery.« less

Metal/metal oxide doped oxide catalysts having high deNOx selectivity for lean NOx exhaust aftertreatment systems

DOEpatents

Park, Paul W.

2004-03-16

A lean NOx catalyst and method of preparing the same is disclosed. The lean NOx catalyst includes a ceramic substrate, an oxide support material, preferably .gamma.-alumina, deposited on the substrate and a metal 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, vanadium, oxides thereof, and 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 about 80 to 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 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.

Enhancement of the catalytic activity of Pt nanoparticles toward methanol electro-oxidation using doped-SnO2 supporting materials

NASA Astrophysics Data System (ADS)

Merati, Zohreh; Basiri Parsa, Jalal

2018-03-01

Catalyst supports play important role in governing overall catalyst activity and durability. In this study metal oxides (SnO2, Sb and Nb doped SnO2) were electrochemically deposited on titanium substrate (Ti) as a new support material for Pt catalyst in order to electro-oxidation of methanol. Afterward platinum nanoparticles were deposited on metal oxide film via electro reduction of platinum salt in an acidic solution. The surface morphology of modified electrodes were evaluated by field-emission scanning electron microscopy (FESEM) and energy dispersive X-ray analysis (EDX) techniques. The electro-catalytic activities of prepared electrodes for methanol oxidation reaction (MOR) and oxidation of carbon monoxide (CO) absorbed on Pt was considered with cyclic voltammetry. The results showed high catalytic activity for Pt/Nb-SnO2/Ti electrode. The electrochemical surface area (ECSA) of a platinum electro-catalyst was determined by hydrogen adsorption. Pt/Nb-SnO2/Ti electrode has highest ECSA compared to other electrode resulting in high activity toward methanol electro-oxidation and CO stripping experiments. The doping of SnO2 with Sb and Nb improved ECSA and MOR activity, which act as electronic donors to increase electronic conductivity.

Photocatalytic and electrochemical performance of three-Dimensional reduced graphene Oxide/WS2/Mg-doped ZnO composites

NASA Astrophysics Data System (ADS)

Yu, Weiwei; Chen, Xi'an; Mei, Wei; Chen, Chuansheng; Tsang, Yuenhong

2017-04-01

To improve the dispersion of reduced graphene oxide and enhance the photocatalytic property of reduced graphene oxide/Mg-doped ZnO composites (rGMZ), the reduced graphene oxide/WS2/Mg-doped ZnO composites (rGWMZ) were prepared by electrostatic self-assembly and coprecipitation methods. The effects of mass ratio of WS2 nanosheets to reduced graphene oxide (WS2/rGO wt.%) and calcination temperature on the photocatalytic and electrochemical property of rGWMZ composites were investigated. Experimental results showed that the photocatalytic efficiency of rGWMZ composites is three-fold compared with that of rGMZ composites when the WS2/rGO wt.% is 20.8% and calcination temperature is 500 °C, in which the degradation ratio Rhodamin B (RhB) can reach 95% within 15 min under the UV light and 90% within 90 min under simulated solar light. In addition, the rGWMZ show larger capacitance and smaller resistance than rGMZ. The enhancement for photocatalytic activity and electrochemical performance of rGWMZ is ascribed to improving the specific surface area, electrical conductivity and electronic storage capability because of the synergistic effect of rGO and WS2 nanosheets.

Rare-Earth Oxide Ion (Tm3+, Ho3+, and U3+) Doped Glasses and Fibres for 1.8 to 4 Micrometer Coherent and Broadband Sources

DTIC Science & Technology

2006-07-24

oxide ( TeO2 ) , fluorine- containing silicate (SiOF2) and germanate (GeOF2) glass hosts for each dopant by characterising the spectroscopic properties...Earth Oxide Ion (Tm3+, Ho3+, And U3+) Doped Glasses And Fibres For 1.8 To 4 Micrometer Coherent And Broadband Sources 5c. PROGRAM ELEMENT NUMBER 5d...Rare-earth oxide ion (Tm3+, Ho3+, and U3+) doped glasses and fibres for 1.8 to 4 micrometer coherent and broadband sources Report prepared

Low-Concentration Indium Doping in Solution-Processed Zinc Oxide Films for Thin-Film Transistors

PubMed Central

Zhang, Xue; Lee, Hyeonju; Kim, Eui-Jik; Park, Jaehoon

2017-01-01

We investigated the influence of low-concentration indium (In) doping on the chemical and structural properties of solution-processed zinc oxide (ZnO) films and the electrical characteristics of bottom-gate/top-contact In-doped ZnO thin-film transistors (TFTs). The thermogravimetry and differential scanning calorimetry analysis results showed that thermal annealing at 400 °C for 40 min produces In-doped ZnO films. As the In content of ZnO films was increased from 1% to 9%, the metal-oxygen bonding increased from 5.56% to 71.33%, while the metal-hydroxyl bonding decreased from 72.03% to 9.63%. The X-ray diffraction peaks and field-emission scanning microscope images of the ZnO films with different In concentrations revealed a better crystalline quality and reduced grain size of the solution-processed ZnO thin films. The thickness of the In-doped ZnO films also increased when the In content was increased up to 5%; however, the thickness decreased on further increasing the In content. The field-effect mobility and on/off current ratio of In-doped ZnO TFTs were notably affected by any change in the In concentration. Considering the overall TFT performance, the optimal In doping concentration in the solution-processed ZnO semiconductor was determined to be 5% in this study. These results suggest that low-concentration In incorporation is crucial for modulating the morphological characteristics of solution-processed ZnO thin films and the TFT performance. PMID:28773242

Effect of Cr doping on the structural, morphological, optical and electrical properties of indium tin oxide films

NASA Astrophysics Data System (ADS)

Mirzaee, Majid; Dolati, Abolghasem

2015-03-01

We report on the preparation and characterization of high-purity chromium (0.5-2.5 at.%)-doped indium tin oxide (ITO, In:Sn = 90:10) films deposited by sol-gel-mediated dip coating. The effects of different Cr-doping contents on structural, morphological, optical and electrical properties of the films were characterized by means of X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM), UV-Vis spectroscopy and four-point probe methods. XRD showed high phase purity cubic In2O3 and indicated a contraction of the lattice with Cr doping. FESEM micrographs show that grain size decreased with increasing the Cr-doping content. A method to determine chromium species in the sample was developed through the decomposition of the Cr 2 p XPS spectrum in Cr6+ and Cr3+ standard spectra. Optical and electrical studies revealed that optimum opto-electronic properties, including minimum sheet resistance of 4,300 Ω/Sq and an average optical transmittance of 85 % in the visible region with a band gap of 3.421 eV, were achieved for the films doped with Cr-doping content of 2 at.%.

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 LaAlO 3 and SrTiO 3 supports a 2D electron gas1 with high mobility of >1,000 cm 2 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). Ifmore » 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 BiFeO 3 down to the nanoscale.« less

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

Erbium-doped zinc-oxide waveguide amplifiers for hybrid photonic integrated circuits

NASA Astrophysics Data System (ADS)

O'Neal, Lawrence; Anthony, Deion; Bonner, Carl; Geddis, Demetris

2016-02-01

CMOS logic circuits have entered the sub-100nm regime, and research is on-going to investigate the quantum effects that are apparent at this dimension. To avoid some of the constraints imposed by fabrication, entropy, energy, and interference considerations for nano-scale devices, many have begun designing hybrid and/or photonic integrated circuits. These circuits consist of transistors, light emitters, photodetectors, and electrical and optical waveguides. As attenuation is a limiting factor in any communications system, it is advantageous to integrate a signal amplifier. There are numerous examples of electrical amplifiers, but in order to take advantage of the benefits provided by optically integrated systems, optical amplifiers are necessary. The erbium doped fiber amplifier is an example of an optical amplifier which is commercially available now, but the distance between the amplifier and the device benefitting from amplification can be decreased and provide greater functionality by providing local, on-chip amplification. Zinc oxide is an attractive material due to its electrical and optical properties. Its wide bandgap (≍3.4 eV) and high refractive index (≍2) make it an excellent choice for integrated optics systems. Moreover, erbium doped zinc oxide (Er:ZnO) is a suitable candidate for optical waveguide amplifiers because of its compatibility with semiconductor processing technology, 1.54 μm luminescence, transparency, low resistivity, and amplification characteristics. This research presents the characterization of radio frequency magnetron sputtered Er:ZnO, the design and fabrication of integrated waveguide amplifiers, and device analysis.

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.

Investigation of thermodynamic properties of metal-oxide catalysts

NASA Astrophysics Data System (ADS)

Shah, Parag Rasiklal

An apparatus for Coulometric Titration was developed and used to measure the redox isotherms (i.e. oxygen fugacity P(O2) vs oxygen stoichiometry) of ceria-zirconia solid solutions, mixed oxides of vanadia, and vanadia supported on ZrO2. This data was used to correlate the redox thermodynamics of these oxides to their structure and catalytic properties. From the redox isotherms measured between 873 K and 973 K, the differential enthalpies of oxidation (DeltaH) for Ce0.81Zr0.19O 2.0 and Ce0.25Zr0.75O2.0 were determined, and they were found to be independent of extent of reduction or composition of the solid solution. They were also lower than DeltaH for ceria, which explains the better redox properties of ceria-zirconia solid solutions. The oxidation was driven by entropy in the low reduction region, and a structural model was proposed to explain the observed entropy effects. Redox isotherms were also measured for a number of bulk vanadates between 823 K and 973 K. DeltaG, DeltaH and DeltaS were reported for V 2O5, Mg3(VO4)2, CeVO 4 and ZrV2O7 along with DeltaG values for AlVO 4, LaVO4, CrVO4. V2O5 and ZrV2O7, which were the only oxides having V-O-V bonds, showed a two-step transition of vanadium for V+3↔V +4 and V+4↔V+5 equilibrium in the redox isotherms. The other oxides, all of which have only M-O-V (M=cation other than V), showed a direct one-step transition, V+3↔V +5. The nature of the M-atom also influenced the P(O2) at which the V+3↔V+5 transition occurs. Redox isotherms at 748 K were measured for vanadia supported on ZrO 2; with two different vanadia loadings corresponding to isolated vanadyls and polymeric vanadyls. The isotherm for the sample with isolated vanadyls showed a single-step transition, similar to the one seen in bulk vanadates with M-O-V linkages, while no such one-step transition was observed in the isotherm of the other sample. To study the affect of the varying redox properties of the vanadium-based catalysts on oxidation rates

Structural, optical, and magnetic studies of manganese-doped zinc oxide hierarchical microspheres by self-assembly of nanoparticles.

PubMed

Hao, Yao-Ming; Lou, Shi-Yun; Zhou, Shao-Min; Yuan, Rui-Jian; Zhu, Gong-Yu; Li, Ning

2012-02-02

In this study, a series of manganese [Mn]-doped zinc oxide [ZnO] hierarchical microspheres [HMSs] are prepared by hydrothermal method only using zinc acetate and manganese acetate as precursors and ethylene glycol as solvent. X-ray diffraction indicates that all of the as-obtained samples including the highest Mn (7 mol%) in the crystal lattice of ZnO have a pure phase (hexagonal wurtzite structure). A broad Raman spectrum from as-synthesized doping samples ranges from 500 to 600 cm-1, revealing the successful doping of paramagnetic Mn2+ ions in the host ZnO. Optical absorption analysis of the samples exhibits a blueshift in the absorption band edge with increasing dopant concentration, and corresponding photoluminescence spectra show that Mn doping suppresses both near-band edge UV emission and defect-related blue emission. In particular, magnetic measurements confirm robust room-temperature ferromagnetic behavior with a high Curie temperature exceeding 400 K, signifying that the as-formed Mn-doped ZnO HMSs will have immense potential in spintronic devices and spin-based electronic technologies.

High Performance, Low Temperature Solution-Processed Barium and Strontium Doped Oxide Thin Film Transistors.

PubMed

Banger, Kulbinder K; Peterson, Rebecca L; Mori, Kiyotaka; Yamashita, Yoshihisa; Leedham, Timothy; Sirringhaus, Henning

2014-01-28

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 cm 2 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 cm 2 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.

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

Communication: Towards catalytic nitric oxide reduction via oligomerization on boron doped graphene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cantatore, Valentina, E-mail: valcan@chalmers.se; Panas, Itai

We use density functional theory to describe a novel way for metal free catalytic reduction of nitric oxide NO utilizing boron doped graphene. The present study is based on the observation that boron doped graphene and O—N=N—O{sup −} act as Lewis acid-base pair allowing the graphene surface to act as a catalyst. The process implies electron assisted N=N bond formation prior to N—O dissociation. Two N{sub 2} + O{sub 2} product channels, one of which favoring N{sub 2}O formation, are envisaged as outcome of the catalytic process. Besides, we show also that the N{sub 2} + O{sub 2} formation pathwaysmore » are contrasted by a side reaction that brings to N{sub 3}O{sub 3}{sup −} formation and decomposition into N{sub 2}O + NO{sub 2}{sup −}.« less

Hierarchical Heterogeneity at the CeO x –TiO 2 Interface: Electronic and Geometric Structural Influence on the Photocatalytic Activity of Oxide on Oxide Nanostructures

DOE PAGES

Luo, Si; Nguyen-Phan, Thuy-Duong; Johnston-Peck, Aaron C.; ...

2015-01-13

Mixed oxide interfaces are critical for delivering active components of demanding catalytic processes such as the photo-catalytic splitting of water. We have studied CeO xTiO₂ catalysts with low ceria loadings of 1 wt%, 3 wt% and 6 wt% that were prepared with wet impregnation methods to favor a strong interaction between CeO x and TiO₂. In these materials the interfaces between CeO x-TiO₂ have been sequentially loaded (1%, 3% and 6%), with and without Pt (0.5 wt%). The structure and properties of the catalysts were characterized using several X-ray and electron based techniques including XRD, XPS, UPS, NEXAFS, UV-Vis andmore » HR-STEM/STEM-EELS, to unravel the local morphology, bulk structure, surface states and electronic structure. The combination of all these techniques allow us to analyze in a systematic way the complete structural and electronic properties that prevail at the CeO x-TiO₂ interface. Fluorite structured nano crystallites of ceria on anatase-structured titania were identified by both XRD and NEXAFS. A sequential increasing of the CeO x loading led to the formation of clusters, then plates and finally nano particles in a hierarchical manner on the TiO₂ support. The electronic structures of these catalysts indicate that the interaction between TiO₂ and CeO₂ is closely related to the local morphology of nanostructured CeO₂. Ce³⁺ cations were detected at the surface of CeO₂ and at the interface of the two oxides. In addition, the titania is perturbed by the interaction with ceria and also with Pt. The photocatalytic activity for the splitting of H₂O using UV light was measured for these materials and correlated with our understanding of the electronic and structural properties. Optimal catalytic performance and photo response results were found for the 1 wt% CeO x-TiO₂ catalyst where low dimensional geometry of the ceria provided ideal electronic and geometrical properties. The structural and electronic properties of the

Physico-chemical effects of supercritical carbon dioxide post polymerization treatment on HCl-doped polyaniline prepared via oxidative chemical polymerization

NASA Astrophysics Data System (ADS)

Fernando, J. G.; Vequizo, R. M.; Odarve, M. K. G.; Sambo, B. R. B.; Alguno, A. C.; Malaluan, R. M.; Candidato, R. T., Jr.; Gambe, J. E.; Jabian, M.; Paylaga, G. J.; Bagsican, F. R. G.; Miyata, H.

2015-06-01

Polyanilinefilms doped with varying HClconcentrations (0.2 M, 0.6 M and 1.0 M) were synthesized on glass substrates via oxidative polymerization of aniline. The films were treated with supercritical carbon dioxide (SC-CO2) at 30 MPa and 40°C for 30 minutes. Their structural, optical and morphological properties were studied and compared to conventionally prepared polyanilinefilms using FTIR analysis, UVVisspectroscopy and scanning electron microscopy. It was observed that supercritical carbon dioxide (SC-CO2) could interact with PANI films that consequently altered the bandgapsand changed the film thickness. SC-CO2 treatment also increased the oxidation level of polyanilinefilms and modified the morphology of polyanilinefilm doped with 1M HCl.

Extreme mobility enhancement of two-dimensional electron gases at oxide interfaces by charge-transfer-induced modulation doping

NASA Astrophysics Data System (ADS)

Chen, Y. Z.; Trier, F.; Wijnands, T.; Green, R. J.; Gauquelin, N.; Egoavil, R.; Christensen, D. V.; Koster, G.; Huijben, M.; Bovet, N.; Macke, S.; He, F.; Sutarto, R.; Andersen, N. H.; Sulpizio, J. A.; Honig, M.; Prawiroatmodjo, G. E. D. K.; Jespersen, T. S.; Linderoth, S.; Ilani, S.; Verbeeck, J.; van Tendeloo, G.; Rijnders, G.; Sawatzky, G. A.; Pryds, N.

2015-08-01

Two-dimensional electron gases (2DEGs) formed at the interface of insulating complex oxides promise the development of all-oxide electronic devices. These 2DEGs involve many-body interactions that give rise to a variety of physical phenomena such as superconductivity, magnetism, tunable metal-insulator transitions and phase separation. Increasing the mobility of the 2DEG, however, remains a major challenge. Here, we show that the electron mobility is enhanced by more than two orders of magnitude by inserting a single-unit-cell insulating layer of polar La1-xSrxMnO3 (x = 0, 1/8, and 1/3) at the interface between disordered LaAlO3 and crystalline SrTiO3 produced at room temperature. Resonant X-ray spectroscopy and transmission electron microscopy show that the manganite layer undergoes unambiguous electronic reconstruction, leading to modulation doping of such atomically engineered complex oxide heterointerfaces. At low temperatures, the modulation-doped 2DEG exhibits Shubnikov-de Haas oscillations and fingerprints of the quantum Hall effect, demonstrating unprecedented high mobility and low electron density.

Solid solutions of gadolinium doped zinc oxide nanorods by combined microwave-ultrasonic irradiation assisted crystallization

NASA Astrophysics Data System (ADS)

Kiani, Armin; Dastafkan, Kamran; Obeydavi, Ali; Rahimi, Mohammad

2017-12-01

Nanocrystalline solid solutions consisting of un-doped and gadolinium doped zinc oxide nanorods were fabricated by a modified sol-gel process utilizing combined ultrasonic-microwave irradiations. Polyvinylpyrrolidone, diethylene glycol, and triethylenetetramine respectively as capping, structure directing, and complexing agents were used under ultrasound dynamic aging and microwave heating to obtain crystalline nanorods. Crystalline phase monitoring, lattice parameters and variation, morphology and shape, elemental analysis, functional groups, reducibility, and the oxidation state of emerged species were examined by PXRD, FESEM, TEM, EDX, FTIR, micro Raman, H2-TPR, and EPR techniques. Results have verified that irradiation mechanism of gelation and crystallization reduces the reaction time, augments the crystal quality, and formation of hexagonal close pack structure of Wurtzite morphology. Besides, dissolution of gadolinium within host lattice involves lattice deformation, unit cell distortion, and angular position variation. Structure related shape and growth along with compositional purity were observed through microscopic and spectroscopic surveys. Furthermore, TPR and EPR studies elucidated more detailed behavior upon exposure to the exerted irradiations and subsequent air-annealing including the formed oxidation states and electron trapping centers, presence of gadolinium, zinc, and oxygen disarrays and defects, as well as alteration in the host unit cell via gadolinium addition.

Activation of Molecular Oxygen Using Durable Cobalt Encapsulated with Nitrogen-Doped Graphitic Carbon Shells for Aerobic Oxidation of Lignin-Derived Alcohols.

PubMed

Sun, Yuxia; Ma, Hong; Luo, Yang; Zhang, Shujing; Gao, Jin; Xu, Jie

2018-03-26

It has long been a challenge for activating O 2 by transition-metal nanocatalysts, which might lose activity due to strong tendency for oxidation. Herein, O 2 could be activated by durable encapsulated cobalt nanoparticles (NPs) with N-doped graphitic carbon shells (Co@N-C), but not by encapsulated cobalt NPs with graphitic carbon, exposed cobalt NPs supported on activated carbon, or N-doped carbon. Electron paramagnetic resonance, real-time in situ FTIR spectroscopy, and mass spectrometry measurements demonstrated the generation of the highly active superoxide radical, O 2 .- . This unique ability enables Co@N-C to afford an excellent catalytic performance in model aerobic oxidation of monomeric lignin-derived alcohols. Further analysis elucidated that encapsulated cobalt and nitrogen-doped graphitic carbon might contribute to the capacity through influencing the electronic properties of outer layers. Moreover, through isolation by N-doped graphitic carbon shells, the inner metallic cobalt NPs are inaccessible in term of either alcohols or oxygenated products, and a distinctive resistance to leaching and agglomeration has been achieved. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structural and optical properties of Ag-doped copper oxide thin films on polyethylene napthalate substrate prepared by low temperature microwave annealing

NASA Astrophysics Data System (ADS)

Das, Sayantan; Alford, T. L.

2013-06-01

Silver doped cupric oxide thin films are prepared on polyethylene naphthalate (flexible polymer) substrates. Thin films Ag-doped CuO are deposited on the substrate by co-sputtering followed by microwave assisted oxidation of the metal films. The low temperature tolerance of the polymer substrates led to the search for innovative low temperature processing techniques. Cupric oxide is a p-type semiconductor with an indirect band gap and is used as selective absorption layer solar cells. X-ray diffraction identifies the CuO phases. Rutherford backscattering spectrometry measurements confirm the stoichiometry of each copper oxide formed. The surface morphology is determined by atomic force microscopy. The microstructural properties such as crystallite size and the microstrain for (-111) and (111) planes are calculated and discussed. Incorporation of Ag led to the lowering of band gap in CuO. Consequently, it is determined that Ag addition has a strong effect on the structural, morphological, surface, and optical properties of CuO grown on flexible substrates by microwave annealing. Tauc's plot is used to determine the optical band gap of CuO and Ag doped CuO films. The values of the indirect and direct band gap for CuO are found to be 2.02 eV and 3.19 eV, respectively.

Paramagnetic dysprosium-doped zinc oxide thin films grown by pulsed-laser deposition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lo, Fang-Yuh, E-mail: fangyuhlo@ntnu.edu.tw; Ting, Yi-Chieh; Chou, Kai-Chieh

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 photoluminescencemore » 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.« less

Nanocerium oxide increases the survival of adult rod and cone photoreceptor in culture by abrogating hydrogen peroxide-induced oxidative stress.

PubMed

Bhargava, Neelima; Shanmugaiah, Vellasamy; Saxena, Manav; Sharma, Manish; Sethy, Niroj Kumar; Singh, Sushil Kumar; Balakrishnan, Karuppiah; Bhargava, Kalpana; Das, Mainak

2016-09-16

In vitro cell culture system for adult rod and cone photoreceptor (PR) is an effective and economical model for screening drug candidates against all kinds of age related retinal blindness. Interestingly, adult PR cells have a limited survival in the culture system, thus preventing full exploitation of this in vitro approach for drug screening applications. The limited survival of the adult PR cells in culture is due to their inherently high oxidative stress and photic injury. Mixed valence-state ceria nanoparticles have the ability to scavenge free radicals and reduce oxidative stress. Here, ceria nanoparticles of 5-10 nm dimensions have been synthesized, possessing dual oxidation state (+3 and +4) as evident from x-ray photoelectron spectroscopy and exhibiting real time reduction of hydrogen peroxide (H 2 O 2 ) as quantified by absorbance spectroscopy and cyclic voltammogram analysis. Using flow cytometry and cell culture assay, it has been shown that, upon one time addition of 10 nM of nanoceria in the PR culture of the 18 months old adult common carp (Cyprinus carpio) at the time of plating the cells, the oxidative stress caused due to hydrogen peroxide assault could be abrogated. A further single application of nanoceria significantly increases the survival of these fragile cells in the culture, thus paving way for developing a more robust photoreceptor culture model to study the aging photoreceptor cells in a defined condition.

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

Investigation of the properties of Sb doping on tin oxide SNO2 materials for technological applications

NASA Astrophysics Data System (ADS)

Hachoun, Z.; Ouerdane, A.; Bouslama, M.; Ghaffour, M.; Abdellaoui, A.; Caudano, Y.; benamara, A. Ali

2016-04-01

The conductivities of the oxide SnO2 is dependent on the nature of the surrounding gas. This property stems from the adsorption or desorption on the surface of oxide grains. These phenomena are usually accompanied by electronic transfer between the adsorbed molecule and the semiconductor material, changing its conductivity. Tin oxidation and Sb doping were realized without and with heating process. The XPS technique and the TEM microscopy showed the synthesized nanocrystals. Simulated Monte Carlo program Casino is used for a scanning its profile. The surface characteristics are highlighted in the aim to be used as spatial gas sensors.

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

NASA Astrophysics Data System (ADS)

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

2017-02-01

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

Water Adsorption and Dissociation on Ceria-Supported Single-Atom Catalysts: A First-Principles DFT+U Investigation.

PubMed

Han, Zhong-Kang; Gao, Yi

2016-02-01

Single-atom catalysts have attracted wide attention owing to their extremely high atom efficiency and activities. In this paper, we applied density functional theory with the inclusion of the on-site Coulomb interaction (DFT+U) to investigate water adsorption and dissociation on clean CeO 2 (111) surfaces and single transition metal atoms (STMAs) adsorbed on the CeO 2 (111) surface. It is found that the most stable water configuration is molecular adsorption on the clean CeO 2 (111) surface and dissociative adsorption on STMA/CeO 2 (111) surfaces, respectively. In addition, our results indicate that the more the electrons that transfer from STMA to the ceria substrate, the stronger the binding energies between the STMA and ceria surfaces. A linear relationship is identified between the water dissociation barriers and the d band centers of STMA, known as the generalized Brønsted-Evans-Polanyi principle. By combining the oxygen spillovers, single-atom dispersion stabilities, and water dissociation barriers, Zn, Cr, and V are identified as potential candidates for the future design of ceria-supported single-atom catalysts for reactions in which the dissociation of water plays an important role, such as the water-gas shift reaction. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Highly improved ethanol gas-sensing performance of mesoporous nickel oxides nanowires with the stannum donor doping.

PubMed

Wei, Junqi; Li, Xiaoqing; Han, Yanbing; Xu, Jingcai; Jin, Hongxiao; Jin, Dingfeng; Peng, Xiaoling; Hong, Bo; Li, Jing; Yang, Yanting; Ge, Hongliang; Wang, Xinqing

2018-06-15

Mesoporous nickel oxides (NiO) and stannum(Sn)-doped NiO nanowires (NWs) were synthesized by using SBA-15 templates with the nanocasting method. X-ray diffraction, transmission electron microscope, energy dispersive spectrometry, nitrogen adsorption/desorption isotherm and UV-vis spectrum were used to characterize the phase structure, components and microstructure of the as-prepared samples. The gas-sensing analysis indicated that the Sn-doping could greatly improve the ethanol sensitivity for mesoporous NiO NWs. With the increasing Sn content, the ethanol sensitivity increased from 2.16 for NiO NWs up to the maximum of 15.60 for Ni 0.962 Sn 0.038 O 1.038 , and then decreased to 12.24 for Ni 0.946 Sn 0.054 O 1.054 to 100 ppm ethanol gas at 340 °C. The high surface area from the Sn-doping improved the adsorption of oxygen on the surface of NiO NWs, resulting in the smaller surface resistance in air. Furthermore, owing to the recombination of the holes in hole-accumulation lay with the electrons from the donor impurity level and the increasing the body defects for Sn-doping, the total resistance in ethanol gas enhanced greatly. It was concluded that the sensitivity of Sn-doped NiO NWs based sensor could be greatly improved by the higher surface area and high-valence donor substitution from Sn-doping.

Highly improved ethanol gas-sensing performance of mesoporous nickel oxides nanowires with the stannum donor doping

NASA Astrophysics Data System (ADS)

Wei, Junqi; Li, Xiaoqing; Han, Yanbing; Xu, Jingcai; Jin, Hongxiao; Jin, Dingfeng; Peng, Xiaoling; Hong, Bo; Li, Jing; Yang, Yanting; Ge, Hongliang; Wang, Xinqing

2018-06-01

Mesoporous nickel oxides (NiO) and stannum(Sn)-doped NiO nanowires (NWs) were synthesized by using SBA-15 templates with the nanocasting method. X-ray diffraction, transmission electron microscope, energy dispersive spectrometry, nitrogen adsorption/desorption isotherm and UV–vis spectrum were used to characterize the phase structure, components and microstructure of the as-prepared samples. The gas-sensing analysis indicated that the Sn-doping could greatly improve the ethanol sensitivity for mesoporous NiO NWs. With the increasing Sn content, the ethanol sensitivity increased from 2.16 for NiO NWs up to the maximum of 15.60 for Ni0.962Sn0.038O1.038, and then decreased to 12.24 for Ni0.946Sn0.054O1.054 to 100 ppm ethanol gas at 340 °C. The high surface area from the Sn-doping improved the adsorption of oxygen on the surface of NiO NWs, resulting in the smaller surface resistance in air. Furthermore, owing to the recombination of the holes in hole-accumulation lay with the electrons from the donor impurity level and the increasing the body defects for Sn-doping, the total resistance in ethanol gas enhanced greatly. It was concluded that the sensitivity of Sn-doped NiO NWs based sensor could be greatly improved by the higher surface area and high-valence donor substitution from Sn-doping.

Synthesis of samarium doped gadolinium oxide nanorods, its spectroscopic and physical properties

NASA Astrophysics Data System (ADS)

Boopathi, G.; Gokul Raj, S.; Ramesh Kumar, G.; Mohan, R.; Mohan, S.

2018-06-01

One-dimensional samarium doped gadolinium oxide [Sm:Gd2O3] nanorods have been synthesized successfully through co-precipitation technique in aqueous solution. The as-synthesized and calcined products were characterized by using powder X-ray diffraction pattern, Fourier transform Raman spectroscopy, thermogravimetric/differential thermal analysis, scanning electron microscopy with energy-dispersive X-ray analysis, transmission electron microscopy, Fourier transform infrared spectroscopy, Ultraviolet-Visible spectrometry, photoluminescence spectrophotometer and X-ray photoelectron spectroscopy techniques. The obtained results are discussed in detailed manner.

Synergetic antibacterial activity of reduced graphene oxide and boron doped diamond anode in three dimensional electrochemical oxidation system

PubMed Central

Qi, Xiujuan; Wang, Ting; Long, Yujiao; Ni, Jinren

2015-01-01

A 100% increment of antibacterial ability has been achieved due to significant synergic effects of boron-doped diamond (BDD) anode and reduced graphene oxide (rGO) coupled in a three dimensional electrochemical oxidation system. The rGO, greatly enhanced by BDD driven electric field, demonstrated strong antibacterial ability and even sustained its excellent performance during a reasonable period after complete power cut in the BDD-rGO system. Cell damage experiments and TEM observation confirmed much stronger membrane stress in the BDD-rGO system, due to the faster bacterial migration and charge transfer by the expanded electro field and current-carrying efficiency by quantum tunnel. Reciprocally the hydroxyl-radical production was eminently promoted with expanded area of electrodes and delayed recombination of the electron–hole pairs in presence of the rGO in the system. This implied a huge potential for practical disinfection with integration of the promising rGO and the advanced electrochemical oxidation systems. PMID:25994309

Nitrogen-doped hierarchical porous carbon with high surface area derived from graphene oxide/pitch oxide composite for supercapacitors.

PubMed

Ma, Yuan; Ma, Chang; Sheng, Jie; Zhang, Haixia; Wang, Ranran; Xie, Zhenyu; Shi, Jingli

2016-01-01

A nitrogen-doped hierarchical porous carbon has been prepared through one-step KOH activation of pitch oxide/graphene oxide composite. At a low weight ratio of KOH/composite (1:1), the as-prepared carbon possesses high specific surface area, rich nitrogen and oxygen, appropriate mesopore/micropore ratio and considerable small-sized mesopores. The addition of graphene oxide plays a key role in forming 4 nm mesopores. The sample PO-GO-16 presents the characteristics of large surface area (2196 m(2) g(-1)), high mesoporosity (47.6%), as well as rich nitrogen (1.52 at.%) and oxygen (6.9 at.%). As a result, PO-GO-16 electrode shows an outstanding capacitive behavior: high capacitance (296 F g(-1)) and ultrahigh-rate performance (192 F g(-1) at 10 A g(-1)) in 6 M KOH aqueous electrolyte. The balanced structure characteristic, low-cost and high performance, make the porous carbon a promising electrode material for supercapacitors. Copyright © 2015 Elsevier Inc. All rights reserved.