Effects of oxide distributed in grain boundaries on microstructure stability of nanocrystalline metals

NASA Astrophysics Data System (ADS)

Zhou, Kai; Li, Hui; Biao Pang, Jin; Wang, Zhu

2013-06-01

Nanocrystalline copper and zinc prepared by high-pressure compaction method have been studied by positron lifetime spectroscopy associated with X-ray diffraction. For nanocrystalline Cu, mean grain sizes of the samples decrease after being annealed at 900 °C and increase during aging at 180 °C, revealing that the atoms exchange between the two regions. The positron lifetime results indicate that the vacancy clusters formed in the annealing process are unstable and decomposed at the aging time below 6 hours. In addition, the partially oxidized surfaces of the nanoparticles hinder the grain growth during the ageing at 180 °C, and the vacancy clusters inside the disorder regions which are related to Cu2O need longer aging time to decompose. In the case of nanocrystalline Zn, the open volume defect (not larger than divacancy) is dominant according to the high relative intensity for the short positron lifetime (τ1). The oxide (ZnO) inside the grain boundaries has been found having an effect to hinder the decrease of average positron lifetime (τav) during the annealing, which probably indicates that the oxide stabilizes the microstructure of the grain boundaries. For both nanocrystalline copper and zinc, the oxides in grain boundaries enhance the thermal stability of the microstucture, in spite of their different crystal structures. This effect is very important for the nanocrystalline materials using as radiation resistant materials.

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.

Arsenate Adsorption On Ruthenium Oxides: A Spectroscopic And Kinetic Investigation

EPA Science Inventory

Arsenate adsorption on amorphous (RuO₂•1.1H₂O) and crystalline (RuO₂) ruthenium oxides was evaluated using spectroscopic and kinetic methods to elucidate the adsorption mechanism. Extended X-ray absorption fine structure spectroscopy (EXAFS) was ...

In-situ XPS analysis of oxidized and reduced plasma deposited ruthenium-based thin catalytic films

NASA Astrophysics Data System (ADS)

Balcerzak, Jacek; Redzynia, Wiktor; Tyczkowski, Jacek

2017-12-01

A novel in-situ study of the surface molecular structure of catalytically active ruthenium-based films subjected to the oxidation (in oxygen) and reduction (in hydrogen) was performed in a Cat-Cell reactor combined with a XPS spectrometer. The films were produced by the plasma deposition method (PEMOCVD). It was found that the films contained ruthenium at different oxidation states: metallic (Ru0), RuO2 (Ru+4), and other RuOx (Ru+x), of which content could be changed by the oxidation or reduction, depending on the process temperature. These results allow to predict the behavior of the Ru-based catalysts in different redox environments.

Preparation of olefins from synthesis gas using ruthenium supported on ceric oxide

DOEpatents

Pierantozzi, Ronald

1985-01-01

A catalyst comprising a ruthenium carbonyl compound deposited on a cerium oxide-containing support material provides for the selective synthesis of low molecular weight olefinic hydrocarbons from mixtures of hydrogen and carbon monoxide.

Preparation of olefins from synthesis gas using ruthenium supported on ceric oxide

DOEpatents

Pierantozzi, R.

1985-04-09

A catalyst comprising a ruthenium carbonyl compound deposited on a cerium oxide-containing support material provides for the selective synthesis of low molecular weight olefinic hydrocarbons from mixtures of hydrogen and carbon monoxide.

Ruthenium or osmium complexes and their uses as catalysts for water oxidation

DOEpatents

Corbea, Javier Jesus Concepcion; Chen, Zuofeng; Jurss, Jonah Wesley; Templeton, Joseph L.; Hoertz, Paul; Meyer, Thomas J.

2013-09-03

The present invention provides ruthenium or osmium complexes and their uses as a catalyst for catalytic water oxidation. Another aspect of the invention provides an electrode and photo-electrochemical cells for electrolysis of water molecules.

Ruthenium or osmium complexes and their uses as catalysts for water oxidation

DOEpatents

Concepcion Corbea, Javier Jesus; Chen, Zuofeng; Jurss, Jonah Wesley; Templeton, Joseph L; Hoertz, Paul; Meyer, Thomas J

2014-10-28

The present invention provides ruthenium or osmium complexes and their uses as a catalyst for catalytic water oxidation. Another aspect of the invention provides an electrode and photo-electrochemical cells for electrolysis of water molecules.

Understanding the low temperature electrical properties of nanocrystalline tin oxide for gas sensor applications

NASA Astrophysics Data System (ADS)

Drake, Christina Hartsell

Nanocrystalline metal/metal oxide is an important class of transparent and electronic materials due to its potential use in many applications, including gas sensors. At the nanoscale, many of the phenomena observed that give nanocrystalline semiconducting oxide enhanced performance as a gas sensor material over other conventional engineering materials is still poorly understood. This study is aimed at understanding the low temperature electrical and chemical properties of nanocrystalline SnO2 that makes it suitable for room temperature gas detectors. Studies were carried out in order to understand how various synthesis methods affect the surfaces on the nano-oxides, interactions of a target gas (in this study hydrogen) with different surface species, and changes in the electrical properties as a function of dopants and grain size. A correlation between the surface reactions and the electrical response of doped nanocrystalline metal-oxide-semiconductors exposed to a reducing gas is established using Fourier Transform Infrared (FTIR) Spectroscopy attached to a specially built custom designed catalytic cell. First principle calculations of oxygen vacancy concentrations from absorbance spectra are presented. FTIR is used for effectively screening of these nanostructures for gas sensing applications. The effect of processing temperature on the microstructural evolution and on the electronic properties of nanocrystalline trivalent doped-SnO 2 is also presented. This study includes the effect of dopants (In and Ce) on the growth of nano-SnO2, as well as their effects on the electronic properties and gas sensor behavior of the nanomaterial at room temperature. Band bending affects are also investigated for this system and are related to enhanced low temperature gas sensing. The role and importance of oxygen vacancies in the electronic and chemical behavior of surface modified nanocrystalline SnO2 are explored in this study. A generalized explanation for the low temperature

Ruthenium-catalyzed aerobic oxidative decarboxylation of amino acids: a green, zero-waste route to biobased nitriles.

PubMed

Claes, Laurens; Verduyckt, Jasper; Stassen, Ivo; Lagrain, Bert; De Vos, Dirk E

2015-04-18

Oxidative decarboxylation of amino acids into nitriles was performed using molecular oxygen as terminal oxidant and a heterogeneous ruthenium hydroxide-based catalyst. A range of amino acids was oxidized in very good yield, using water as the solvent.

Subtractive Plasma-Assisted-Etch Process for Developing High Performance Nanocrystalline Zinc-Oxide Thin-Film-Transistors

DTIC Science & Technology

2015-03-26

THIN - FILM - TRANSISTORS THESIS Thomas M. Donigan, First Lieutenant, USAF AFIT-ENG-MS-15-M-027 DEPARTMENT OF THE AIR FORCE AIR UNIVERSITY AIR...DEVELOPING HIGH PERFORMANCE NANOCRYSTALLINE ZINC-OXIDE THIN - FILM - TRANSISTORS THESIS Presented to the Faculty Department of Electrical and...15-M-027 SUBTRACTIVE PLASMA-ASSISTED-ETCH PROCESS FOR DEVELOPING HIGH PERFORMANCE NANOCRYSTALLINE ZINC-OXIDE THIN - FILM - TRANSISTORS

Ruthenium carbonyl catalyst supported on ceric oxide for preparation of olefins from synthesis gas

DOEpatents

Pierantozzi, R.

1985-04-02

A catalyst comprising a ruthenium carbonyl compound deposited on a cerium oxide-containing support material provides for the selective synthesis of low molecular weight olefinic hydrocarbons from mixtures of hydrogen and carbon monoxide.

Ruthenium carbonyl catalyst supported on ceric oxide for preparation of olefins from synthesis gas

DOEpatents

Pierantozzi, Ronald

1985-01-01

A catalyst comprising a ruthenium carbonyl compound deposited on a cerium oxide-containing support material provides for the selective synthesis of low molecular weight olefinic hydrocarbons from mixtures of hydrogen and carbon monoxide.

C-H functionalization of phenols using combined ruthenium and photoredox catalysis: in situ generation of the oxidant.

PubMed

Fabry, David C; Ronge, Meria A; Zoller, Jochen; Rueping, Magnus

2015-02-23

A combination of ruthenium and photoredox catalysis allowed the ortho olefination of phenols. Using visible light, the direct C-H functionalization of o-(2-pyridyl)phenols occurred, and diverse phenol ethers were obtained in good yields. The regeneration of the ruthenium catalyst was accomplished by a photoredox-catalyzed oxidative process. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Graphene Oxide/ Ruthenium Oxide Composites for Supercapacitors Electrodes

NASA Astrophysics Data System (ADS)

Amir, Fatima

Supercapacitors are electrical energy storage devices with high power density, high rate capability, low maintenance cost, and long life cycle. They complement or replace batteries in harvesting applications when high power delivery is needed. An important improvement in performance of supercapacitors has been achieved through recent advances in the development of new nanostructured materials. Here we will discuss the fabrication of graphene oxide/ ruthenium oxide supercacitors electrodes including electrophoretic deposition. The morphology and structure of the fabricated electrodes were investigated and will be discussed. The electrochemical properties were determined using cyclic voltammetry and galvanostatic charge/discharge techniques and the experiments that demonstrate the excellent capacitive properties of the obtained supercapacitors will also be discussed. The fabrication and characterization of the samples were performed at the Center of Functional Nanomaterials at Brookhaven National Lab. The developed approaches in our study represent an exciting direction for designing the next generation of energy storage devices. This work was supported in part by the U.S. Department of Energy through the Visiting Faculty Program and the research used resources of the Center for Functional Nanomaterials at Brookhaven National Laboratory.

Oxidation resistant nanocrystalline MCrAl(Y) coatings and methods of forming such coatings

DOEpatents

Cheruvu, Narayana S.; Wei, Ronghua

2014-07-29

The present disclosure relates to an oxidation resistant nanocrystalline coating and a method of forming an oxidation resistant nanocrystalline coating. An oxidation resistant coating comprising an MCrAl(Y) alloy may be deposited on a substrate, wherein M, includes iron, nickel, cobalt, or combinations thereof present greater than 50 wt % of the MCrAl(Y) alloy, chromium is present in the range of 15 wt % to 30 wt % of the MCrAl(Y) alloy, aluminum is present in the range of 6 wt % to 12 wt % of the MCrAl(Y) alloy and yttrium, is optionally present in the range of 0.1 wt % to 0.5 wt % of the MCrAl(Y) alloy. In addition, the coating may exhibit a grain size of 200 nm or less as deposited.

Surface grafting of reduced graphene oxide using nanocrystalline cellulose via click reaction

NASA Astrophysics Data System (ADS)

Kabiri, Roya; Namazi, Hassan

2014-07-01

Reduced graphene oxide (RGO) sheet was functionalized with nanocrystalline cellulose (NCC) via click coupling between azide-functionalized graphene oxide (GO-N3) and terminal propargyl-functionalized nanocrystalline cellulose (PG-NCC). First, the reactive azide groups were introduced on the surface of GO with azidation of 2-chloroethyl isocyanate-treated graphene oxide (GO-Cl). Then, the resulted compounds were reacted with PG-NCC utilizing copper-catalyzed azide-alkyne cycloaddition. During the click reaction, GO was simultaneously reduced to graphene. The coupling was confirmed by Fourier transform infrared, Raman, DEPT135, and 13C NMR spectroscopy, and the complete exfoliation of graphene in the NCC matrix was confirmed with X-ray diffraction measurement. The degree of functionalization from the gradual mass loss of RGO-NCC suggests that around 23 mass % has been functionalized covalently. The size of both NCC and GO was found to be in nanometric range, which decreased after click reaction.

In situ chemical synthesis of ruthenium oxide/reduced graphene oxide nanocomposites for electrochemical capacitor applications.

PubMed

Kim, Ji-Young; Kim, Kwang-Heon; Yoon, Seung-Beom; Kim, Hyun-Kyung; Park, Sang-Hoon; Kim, Kwang-Bum

2013-08-07

An in situ chemical synthesis approach has been developed to prepare ruthenium oxide/reduced graphene oxide (RGO) nanocomposites. It is found that as the C/O ratio increases, the number density of RuO2 nanoparticles decreases, because the chemical interaction between the Ru ions and the oxygen-containing functional groups provides anchoring sites where the nucleation of particles takes place. For electrochemical capacitor applications, the microwave-hydrothermal process was carried out to improve the conductivity of RGO in RuO2/RGO nanocomposites. The significant improvement in capacitance and high rate capability might result from the RuO2 nanoparticles used as spacers that make the interior layers of the reduced graphene oxide electrode available for electrolyte access.

Mononuclear ruthenium polypyridine complexes that catalyze water oxidation

DOE PAGES

Tong, Lianpeng; Thummel, Randolph P.

2016-08-05

Over the past decade, significant advances have been made in the development of molecular water oxidation catalysts (WOCs) in the context of developing a system that would accomplish artificial photosynthesis. Mononuclear ruthenium complexes with polypyridine ligands have drawn considerable attention in this regard, due to their high catalytic activity and relatively simple structure. In this perspective review, we will discuss mononuclear Ru polypyridine WOCs by organizing them into four groups according to their ligand environments. Each group will be discussed with regard to three fundamental questions: first, how does the catalyst initiate O–O bond formation? Second, which step in themore » catalytic cycle is rate-determining? Third, how efficient is the catalyst according to the specific descriptors such as turnover frequency? All discussion is based on the high-valent ruthenium intermediates that are proposed in the catalytic cycle according to experimental observation and theoretical simulation. Two fundamental mechanisms are set forth. An acid–base mechanism that involves the attack of a water molecule on the oxo of a high valent Ru=O species to form the O–O bond. Subsequent steps lead to dissociation of O 2 and rehydration of the metal center. A second mechanism involves the formation of a Ru–O˙ radical species, two of which then couple to form a Ru–O–O–Ru species that can release O 2 afterwards. The acid–base mechanism appears to be more common and mechanistic differences could result from variation directly related to polypyridine ligand structures. Thus, understanding how electronic, steric, and conformational properties can effect catalyst performance will lead to the rational design of more effective WOCs with not only ruthenium but also other transition metals.« less

Synthesis of nanocrystalline rare earth oxides by glycothermal method

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

Hosokawa, Saburo; Iwamoto, Shinji; Inoue, Masashi

2008-11-03

The reaction of yttrium acetate hydrate in 1,2-propanediol at 300 deg. C yielded a product containing acetate groups and glycol moieties. From this product, Y{sub 2}O{sub 3} was directly crystallized at 400 deg. C without the formation of a carbonate oxide phase. The thus-obtained Y{sub 2}O{sub 3} samples had a small crystallite size (2.2 nm) and significantly large surface area (280 m{sup 2}/g). Other nanocrystalline rare earth (Gd-Yb) oxides were also obtained by this method.

Platinum-ruthenium nanotubes and platinum-ruthenium coated copper nanowires as efficient catalysts for electro-oxidation of methanol

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

Zheng, Jie; Cullen, David A.; Forest, Robert V.

2015-01-15

The sluggish kinetics of methanol oxidation reaction (MOR) is a major barrier to the commercialization of direct methanol fuel cells (DMFCs). In this study, we report a facile synthesis of platinum–ruthenium nanotubes (PtRuNTs) and platinum–ruthenium-coated copper nanowires (PtRu/CuNWs) by galvanic displacement reaction using copper nanowires as a template. The PtRu compositional effect on MOR is investigated; the optimum Pt/Ru bulk atomic ratio is about 4 and surface atomic ratio about 1 for both PtRuNTs and PtRu/CuNWs. Enhanced specific MOR activities are observed on both PtRuNTs and PtRu/CuNWs compared with the benchmark commercial carbon-supported PtRu catalyst (PtRu/C, Hispec 12100). Finally, x-raymore » photoelectron spectroscopy (XPS) reveals a larger extent of electron transfer from Ru to Pt on PtRu/CuNWs, which may lead to a modification of the d-band center of Pt and consequently a weaker bonding of CO (the poisoning intermediate) on Pt and a higher MOR activity on PtRu/CuNWs.« less

O–O bond formation in ruthenium-catalyzed water oxidation: single-site nucleophilic attack vs. O–O radical coupling

DOE PAGES

Shaffer, David W.; Xie, Yan; Concepcion, Javier J.

2017-09-01

In this review we discuss at the mechanistic level the different steps involved in water oxidation catalysis with ruthenium-based molecular catalysts. We have chosen to focus on ruthenium-based catalysts to provide a more coherent discussion and because of the availability of detailed mechanistic studies for these systems but many of the aspects presented in this review are applicable to other systems as well. The water oxidation cycle has been divided in four major steps: water oxidative activation, O–O bond formation, oxidative activation of peroxide intermediates, and O 2 evolution. A significant portion of the review is dedicated to the O–Omore » bond formation step as the key step in water oxidation catalysis. As a result, the two main pathways to accomplish this step, single-site water nucleophilic attack and O–O radical coupling, are discussed in detail and compared in terms of their potential use in photoelectrochemical cells for solar fuels generation.« less

O–O bond formation in ruthenium-catalyzed water oxidation: single-site nucleophilic attack vs. O–O radical coupling

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

Shaffer, David W.; Xie, Yan; Concepcion, Javier J.

In this review we discuss at the mechanistic level the different steps involved in water oxidation catalysis with ruthenium-based molecular catalysts. We have chosen to focus on ruthenium-based catalysts to provide a more coherent discussion and because of the availability of detailed mechanistic studies for these systems but many of the aspects presented in this review are applicable to other systems as well. The water oxidation cycle has been divided in four major steps: water oxidative activation, O–O bond formation, oxidative activation of peroxide intermediates, and O 2 evolution. A significant portion of the review is dedicated to the O–Omore » bond formation step as the key step in water oxidation catalysis. As a result, the two main pathways to accomplish this step, single-site water nucleophilic attack and O–O radical coupling, are discussed in detail and compared in terms of their potential use in photoelectrochemical cells for solar fuels generation.« less

O-O bond formation in ruthenium-catalyzed water oxidation: single-site nucleophilic attack vs. O-O radical coupling.

PubMed

Shaffer, David W; Xie, Yan; Concepcion, Javier J

2017-10-16

In this review we discuss at the mechanistic level the different steps involved in water oxidation catalysis with ruthenium-based molecular catalysts. We have chosen to focus on ruthenium-based catalysts to provide a more coherent discussion and because of the availability of detailed mechanistic studies for these systems but many of the aspects presented in this review are applicable to other systems as well. The water oxidation cycle has been divided in four major steps: water oxidative activation, O-O bond formation, oxidative activation of peroxide intermediates, and O 2 evolution. A significant portion of the review is dedicated to the O-O bond formation step as the key step in water oxidation catalysis. The two main pathways to accomplish this step, single-site water nucleophilic attack and O-O radical coupling, are discussed in detail and compared in terms of their potential use in photoelectrochemical cells for solar fuels generation.

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

Thiolate-bridged dinuclear ruthenium and iron complexes as robust and efficient catalysts toward oxidation of molecular dihydrogen in protic solvents.

PubMed

Yuki, Masahiro; Sakata, Ken; Hirao, Yoshifumi; Nonoyama, Nobuaki; Nakajima, Kazunari; Nishibayashi, Yoshiaki

2015-04-01

Thiolate-bridged dinuclear ruthenium and iron complexes are found to work as efficient catalysts toward oxidation of molecular dihydrogen in protic solvents such as water and methanol under ambient reaction conditions. Heterolytic cleavage of the coordinated molecular dihydrogen at the dinuclear complexes and the sequential oxidation of the produced hydride complexes are involved as key steps to promote the present catalytic reaction. The catalytic activity of the dinuclear complexes toward the chemical oxidation of molecular dihydrogen achieves up to 10000 TON (turnover number), and electrooxidation of molecular dihydrogen proceeds quite rapidly. The result of the density functional theory (DFT) calculation on the reaction pathway indicates that a synergistic effect between the two ruthenium atoms plays an important role to realize the catalytic oxidation of molecular dihydrogen efficiently. The present dinuclear ruthenium complex is found to work as an efficient organometallic anode catalyst for the fuel cell. It is noteworthy that the present dinuclear complex worked not only as an effective catalyst toward chemical and electrochemical oxidation of molecular dihydrogen but also as a good anode catalyst for the fuel cell. We consider that the result described in this paper provides useful and valuable information to develop highly efficient and low-cost transition metal complexes as anode catalysts in the fuel cell.

Water oxidation by Ruthenium complexes incorporating multifunctional biipyridyl diphosphonate ligands

DOE PAGES

Xie, Yan; Shaffer, David W.; Lewandowska-Andralojc, Anna; ...

2016-05-11

Here, we describe herein the synthesis and characterization of ruthenium complexes with multifunctional bipyridyl diphosphonate ligands as well as initial water oxidation studies. In these complexes, the phosphonate groups provide redox-potential leveling through charge compensation and σ donation to allow facile access to high oxidation states. These complexes display unique pH-dependent electrochemistry associated with deprotonation of the phosphonic acid groups. The position of these groups allows them to shuttle protons in and out of the catalytic site and reduce activation barriers. A mechanism for water oxidation by these catalysts is proposed on the basis of experimental results and DFT calculations.more » The unprecedented attack of water at a neutral six-coordinate [Ru IV] center to yield an anionic seven-coordinate [Ru IV–OH] – intermediate is one of the key steps of a single-site mechanism in which all species are anionic or neutral. These complexes are among the fastest single-site catalysts reported to date.« less

Highly efficient and robust molecular ruthenium catalysts for water oxidation.

PubMed

Duan, Lele; Araujo, Carlos Moyses; Ahlquist, Mårten S G; Sun, Licheng

2012-09-25

Water oxidation catalysts are essential components of light-driven water splitting systems, which could convert water to H(2) driven by solar radiation (H(2)O + hν → 1/2O(2) + H(2)). The oxidation of water (H(2)O → 1/2O(2) + 2H(+) + 2e(-)) provides protons and electrons for the production of dihydrogen (2H(+) + 2e(-) → H(2)), a clean-burning and high-capacity energy carrier. One of the obstacles now is the lack of effective and robust water oxidation catalysts. Aiming at developing robust molecular Ru-bda (H(2)bda = 2,2'-bipyridine-6,6'-dicarboxylic acid) water oxidation catalysts, we carried out density functional theory studies, correlated the robustness of catalysts against hydration with the highest occupied molecular orbital levels of a set of ligands, and successfully directed the synthesis of robust Ru-bda water oxidation catalysts. A series of mononuclear ruthenium complexes [Ru(bda)L(2)] (L = pyridazine, pyrimidine, and phthalazine) were subsequently synthesized and shown to effectively catalyze Ce(IV)-driven [Ce(IV) = Ce(NH(4))(2)(NO(3))(6)] water oxidation with high oxygen production rates up to 286 s(-1) and high turnover numbers up to 55,400.

Highly efficient and robust molecular ruthenium catalysts for water oxidation

PubMed Central

Duan, Lele; Araujo, Carlos Moyses; Ahlquist, Mårten S.G.; Sun, Licheng

2012-01-01

Water oxidation catalysts are essential components of light-driven water splitting systems, which could convert water to H2 driven by solar radiation (H2O + hν → 1/2O2 + H2). The oxidation of water (H2O → 1/2O2 + 2H+ + 2e-) provides protons and electrons for the production of dihydrogen (2H+ + 2e- → H2), a clean-burning and high-capacity energy carrier. One of the obstacles now is the lack of effective and robust water oxidation catalysts. Aiming at developing robust molecular Ru-bda (H2bda = 2,2′-bipyridine-6,6′-dicarboxylic acid) water oxidation catalysts, we carried out density functional theory studies, correlated the robustness of catalysts against hydration with the highest occupied molecular orbital levels of a set of ligands, and successfully directed the synthesis of robust Ru-bda water oxidation catalysts. A series of mononuclear ruthenium complexes [Ru(bda)L2] (L = pyridazine, pyrimidine, and phthalazine) were subsequently synthesized and shown to effectively catalyze CeIV-driven [CeIV = Ce(NH4)2(NO3)6] water oxidation with high oxygen production rates up to 286 s-1 and high turnover numbers up to 55,400. PMID:22753518

Fabrication of a symmetric micro supercapacitor based on tubular ruthenium oxide on silicon 3D microstructures

NASA Astrophysics Data System (ADS)

Wang, Xiaofeng; Yin, Yajiang; Li, Xiangyu; You, Zheng

2014-04-01

A micro-supercapacitor with a three-dimensional configuration has been fabricated using an ICP etching technique. Hydrous ruthenium oxide with a tubular morphology is successfully synthesized using a cathodic deposition technique with a Si micro prominence as a template. The desired tubular RuO2·xH2O architecture facilitates electrolyte penetration and proton exchange/diffusion. A single MEMS electrode is studied using cyclic voltammetry, and a specific capacitance of 99.3 mF cm-2 and 70 F g-1 is presented at 5 mV s-1 in neutral Na2SO4 solution. The accelerated cycle life is tested at 80 mV s-1, and satisfactory cyclability is observed. When placed on a chip, the symmetric cell exhibits good supercapacitor properties, and a specific capacitance as high as 23 mF cm-2 is achieved at 10 mA cm-2. Therefore, 3D MEMS microelectrode arrays with electrochemically deposited ruthenium oxide films are promising candidates for on-chip electrochemical micro-capacitor applications.

Benzene oxidation at diamond electrodes: comparison of microcrystalline and nanocrystalline diamonds.

PubMed

Pleskov, Yu V; Krotova, M D; Elkin, V V; Varnin, V P; Teremetskaya, I G; Saveliev, A V; Ralchenko, V G

2012-08-27

A comparative study of benzene oxidation at boron-doped diamond (BDD) and nitrogenated nanocrystalline diamond (NCD) anodes in 0.5 M K(2)SO(4) aqueous solution is conducted by using cyclic voltammetry and electrochemical impedance spectroscopy. It is shown by measurements of differential capacitance and anodic current that during the benzene oxidation at the BDD electrode, adsorption of a reaction intermediate occurs, which partially blocks the electrode surface and lowers the anodic current. At the NCD electrode, benzene is oxidized concurrently with oxygen evolution, a (quinoid) intermediate being adsorbed at the electrode. The adsorption and the electrode surface blocking are reflected in the impedance-frequency and impedance-potential complex-plane plots. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Alternating current transport and dielectric relaxation of nanocrystalline graphene oxide

NASA Astrophysics Data System (ADS)

Zedan, I. T.; El-Menyawy, E. M.

2018-07-01

Graphene oxide (GO) has been synthesized from natural graphite using modified Hummer's method and is subjected to sonication for 1 h. X-ray diffraction (XRD) showed that the prepared GO has nanocrystalline structure with particle size of about 5 nm and high-resolution transmission electron microscope showed that it had a layered structure. The nanocrystalline GO powder was pressed as a disk and the alternating current (AC) electrical conductivity, σAC, and dielectric properties have been investigated in the frequency range 50Hz-5 MHz and temperature range 298-523K using parallel plate spectroscopic technique. Analysis of σ AC as a function of frequency shows that the relation follows Jonscher's universal law with frequency exponent decreases with increasing temperature in which the correlated barrier hopping model is applicable to describe the behavior. The dielectric constant and dielectric loss are studied as functions of frequency and temperature. The dielectric modulus formalism is used for describing the relaxation process in which the relaxation time and its activation energy were evaluated.

Nano-crystalline porous tin oxide film for carbon monoxide sensing

NASA Technical Reports Server (NTRS)

Liu, Chung-Chiun (Inventor); Savinell, Robert F. (Inventor); Jin, Zhihong (Inventor)

2000-01-01

A tin oxide sol is deposited on platinum electrodes (12) of a sensor (10). The sol is calcined at a temperature of 500 to 800.degree. C. to produce a thin film of tin oxide with a thickness of about 150 nm to 2 .mu. and having a nano-crystalline structure with good stability. The sensor rapidly detects reducing gases, such as carbon monoxide, or hydrocarbons and organic vapors. Sensors using films calcined at around 700.degree. C. have high carbon monoxide selectivity with a response time of around 4 minutes and a recovery time of 1 minute, and therefore provide good detection systems for detection of trace amounts of pollutants such as toxic and flammable gases in homes, industrial settings, and hospitals.

Initial stage corrosion of nanocrystalline copper particles and thin films

NASA Astrophysics Data System (ADS)

Tao, Weimin

1997-12-01

Corrosion behavior is an important issue in nanocrystalline materials research and development. A very fine grain size is expected to have significant effects on the corrosion resistance of these novel materials. However, both the macroscopic corrosion properties and the corresponding structure evolution during corrosion have not been fully studied. Under such circumstances, conducting fundamental research in this area is important and necessary. In this study, high purity nanocrystalline and coarse-grained copper were selected as our sample material, sodium nitrite aqueous solution at room temperature and air at a high temperature were employed as corrosive environments. The weight loss testing and electrochemical methods were used to obtain the macroscopic corrosion properties, whereas the high resolution transmission electron microscope was employed for the structure analysis. The weight loss tests indicate that the corrosion rate of nanocrystalline copper is about 5 times higher than that of coarse-grained copper at the initial stage of corrosion. The electrochemical measurements show that the corrosion potential of the nanocrystalline copper has a 230 mV negative shift in comparison with that of the coarse-grained copper. The nanocrystalline copper also exhibits a significantly higher exchange current density than the coarse-grained copper. High resolution TEM revealed that the surface structure changes at the initial stage of corrosion. It was found that the first copper oxide layer formed on the surface of nanocrystalline copper thin film contains a large density of high angle grain boundaries, whereas that formed on the surface of coarse-grained copper shows highly oriented oxide nuclei and appears to show a strong tendency for forming low angle grain boundaries. A correlation between the macroscopic corrosion properties and the structure characteristics is proposed for the nanocrystalline copper based on the concept of the "apparent" exchange current

The chemical and catalytic properties of nanocrystalline metal oxides prepared through modified sol-gel synthesis

NASA Astrophysics Data System (ADS)

Carnes, Corrie Leigh

The goal of this research was to synthesize, characterize and study the chemical properties of nanocrystalline metal oxides. Nanocrystalline (NC) ZnO, CuO, NiO, Al2O3, and the binary Al2O 3/MgO and ZnO/CuO were prepared through modified sol gel methods. These NC metal oxides were studied in comparison to the commercial (CM) metal oxides. The samples were characterized by XRD, TGA, FTIR, BET, and TEM. The NC samples were all accompanied by a significant increase in surface area and decrease in crystallite size. Several chemical reactions were studied to compare the NC samples to the CM samples. One of the reactions involved a high temperature reaction between carbon tetrachloride and the oxide to form carbon dioxide and the corresponding metal chloride. A similar high temperature reaction was conducted between the metal oxide and hydrogen sulfide to form water and the corresponding metal sulfide. A room temperature gas phase adsorption was studied where SO2 was adsorbed onto the oxide. A liquid phase adsorption conducted at room temperature was the destructive adsorption of paraoxon (a toxic insecticide). In all reactions the NC samples exhibited greater activity, destroying or adsorbing a larger amount of the toxins compared to the CM samples. To better study surface area effects catalytic reactions were also studied. The catalysis of methanol was studied over the nanocrystalline ZnO, CuO, NiO, and ZnO/CuO samples in comparison to their commercial counterparts. In most cases the NC samples proved to be more active catalysts, having higher percent conversions and turnover numbers. A second catalytic reaction was also studied, this reaction was investigated to look at the support effects. The catalysis of cyclopropane to propane was studied over Pt and Co catalysts. These catalysts were supported onto NC and CM alumina by impregnation. By observing differences in the catalytic behavior, support effects have become apparent.

Thermodynamic properties of gaseous ruthenium species.

PubMed

Miradji, Faoulat; Souvi, Sidi; Cantrel, Laurent; Louis, Florent; Vallet, Valérie

2015-05-21

The review of thermodynamic data of ruthenium oxides reveals large uncertainties in some of the standard enthalpies of formation, motivating the use of high-level relativistic correlated quantum chemical methods to reduce the level of discrepancies. The reaction energies leading to the formation of ruthenium oxides RuO, RuO2, RuO3, and RuO4 have been calculated for a series of reactions. The combination of different quantum chemical methods has been investigated [DFT, CASSCF, MRCI, CASPT2, CCSD(T)] in order to predict the geometrical parameters, the energetics including electronic correlation and spin-orbit coupling. The most suitable method for ruthenium compounds is the use of TPSSh-5%HF for geometry optimization, followed by CCSD(T) with complete basis set (CBS) extrapolations for the calculation of the total electronic energies. SO-CASSCF seems to be accurate enough to estimate spin-orbit coupling contributions to the ground-state electronic energies. This methodology yields very accurate standard enthalpies of formations of all species, which are either in excellent agreement with the most reliable experimental data or provide an improved estimate for the others. These new data will be implemented in the thermodynamical databases that are used by the ASTEC code (accident source term evaluation code) to build models of ruthenium chemistry behavior in severe nuclear accident conditions. The paper also discusses the nature of the chemical bonds both from molecular orbital and topological view points.

Method of making nanocrystalline alpha alumina

DOEpatents

Siegel, Richard W.; Hahn, Horst; Eastman, Jeffrey A.

1992-01-01

Method of making selected phases of nanocrystalline ceramic materials. Various methods of controlling the production of nanocrystalline alpha alumina and titanium oxygen phases are described. Control of the gas atmosphere and use of particular oxidation treatments give rise to the ability to control the particular phases provided in the aluminum/oxygen and titanium/oxygen system.

Kinetics and Photochemistry of Ruthenium Bisbipyridine Diacetonitrile Complexes: An Interdisciplinary Inorganic and Physical Chemistry Laboratory Exercise

ERIC Educational Resources Information Center

Rapp, Teresa L.; Phillips, Susan R.; Dmochowski, Ivan J.

2016-01-01

The study of ruthenium polypyridyl complexes can be widely applied across disciplines in the undergraduate curriculum. Ruthenium photochemistry has advanced many fields including dye-sensitized solar cells, photoredox catalysis, lightdriven water oxidation, and biological electron transfer. Equally promising are ruthenium polypyridyl complexes…

Fundamental Factors Impacting the Stability of Phosphonate-Derivatized Ruthenium Polypyridyl Sensitizers Adsorbed on Metal Oxide Surfaces.

PubMed

Raber, McKenzie; Brady, Matthew David; Troian-Gautier, Ludovic; Dickenson, John; Marquard, Seth L; Hyde, Jacob; Lopez, Santiago; Meyer, Gerald J; Meyer, Thomas J; Harrison, Daniel P

2018-06-08

A series of 18 ruthenium(II) polypyridyl complexes were synthesized and evaluated under electrochemically oxidative conditions, which generates the Ru(III) oxidation state and mimics the harsh conditions experienced during the kinetically-limited regime that can occur in dye-sensitized solar cells (DSSCs) and dye-sensitized photoelectrosynthesis cells (DSPECs), to further develop fundamental insights into the factors governing molecular sensitizer surface stability in aqueous 0.1 M HClO4 (aq). Both desorption and oxidatively induced ligand substitution were observed on planar fluorine doped tin oxide, FTO, electrodes, with a dependence on the E1/2 Ru(III/II) redox potential dictating the comparative ratios of the processes. Complexes such as RuP4OMe (E1/2 = 0.91 vs Ag/AgCl) displayed virtually only desorption, while complexes such as RuPbpz (E1/2 > 1.62 V vs Ag/AgCl) displayed only chemical decomposition. Comparing isomers of 4,4'- and 5,5-disubstituted-2,2'-bipyridine ancillary polypyridyl ligands, a dramatic increase in the rate of desorption of the Ru(III) complexes was observed for the 5,5'-ligands. Nanoscopic indium doped tin oxide thin films, nanoITO, were also sensitized and analyzed with cyclic voltammetry, UV-Vis absorption spectroscopy, and XPS, allowing for further distinction of desorption versus ligand substitution processes. Desorption loss to bulk solution associated with the planar surface of FTO is essentially non-existent on nanoITO, where both desorption and ligand substitution are shut down with RuP4OMe. These results revealed that minimizing time spent in the oxidized form, incorporating electron donating groups, maximizing hydrophobicity, and minimizing molecular bulk near the adsorbed ligand are critical to optimizing the performance of ruthenium(II) polypyridyl complexes in dye-sensitized solar cell devices.

Plasma-Assisted Synthesis of Monodispersed and Robust Ruthenium Ultrafine Nanocatalysts for Organosilane Oxidation and Oxygen Evolution Reactions.

PubMed

Gnanakumar, Edwin S; Ng, Wesley; Coşkuner Filiz, Bilge; Rothenberg, Gadi; Wang, Sheng; Xu, Hualong; Pastor-Pérez, Laura; Pastor-Blas, M Mercedes; Sepúlveda-Escribano, Antonio; Yan, Ning; Shiju, N Raveendran

2017-11-23

We report a facile and general approach for preparing ultrafine ruthenium nanocatalysts by using a plasma-assisted synthesis at <100 °C. The resulting Ru nanoparticles are monodispersed (typical size 2 nm) and remain that way upon loading onto carbon and TiO 2 supports. This gives robust catalysts with excellent activities in both organosilane oxidation and the oxygen evolution reaction.

Ruthenium-based, inert oxide electrodes for impregnating active materials in nickel plaques

NASA Astrophysics Data System (ADS)

Manoharan, R.; Uma, M.

Titanium electrodes coated with mixed ruthenium-iridium-titanium oxides are tested as inert counter electrodes for impregnating active materials in porous nickel plaques. The latter are to be used as the positive electrodes in nickel/cadmium cells. Weight losses and variations in bath voltage have been monitored while using these electrodes in the impregnation bath. A 2.85 Ah nickel/cadmium cell has been constructed using nickel electrodes developed by employing the coated electrodes of this study. The performances of these coated electrodes are compared with those of platinum electrodes that are currently employed by nickel/cadmium battery manufacturers. The results are found to be satisfactory.

Binuclear ruthenium(III) bis(thiosemicarbazone) complexes: Synthesis, spectral, electrochemical studies and catalytic oxidation of alcohol

NASA Astrophysics Data System (ADS)

Mohamed Subarkhan, M.; Ramesh, R.

2015-03-01

A new series of binuclear ruthenium(III) thiosemicarbazone complexes of general formula [(EPh3)2(X)2Ru-L-Ru(X)2(EPh3)2] (where E = P or As; X = Cl or Br; L = NS chelating bis(thiosemicarbazone ligands) has been synthesized and characterized by analytical and spectral (FT-IR, UV-Vis and EPR). IR spectra show that the thiosemicarbazones behave as monoanionic bidentate ligands coordinating through the azomethine nitrogen and thiolate sulphur. The electronic spectra of the complexes indicate that the presence of d-d and intense LMCT transitions in the visible region. The complexes are paramagnetic (low spin d5) in nature and all the complexes show rhombic distortion around the ruthenium ion with three different 'g' values (gx ≠ gy ≠ gz) at 77 K. All the complexes are redox active and exhibit an irreversible metal centered redox processes (RuIII-RuIII/RuIV-RuIV; RuIII-RuIII/RuII-RuII) within the potential range of 0.38-0.86 V and -0.39 to -0.66 V respectively, versus Ag/AgCl. Further, the catalytic efficiency of one of the complexes [Ru2Cl2(AsPh3)4(L1)] (4) has been investigated in the case of oxidation of primary and secondary alcohols into their corresponding aldehydes and ketones in the presence of N-methylmorpholine-N-oxide(NMO) as co-oxidant. The formation of high valent RuVdbnd O species is proposed as catalytic intermediate for the catalytic cycle.

Characterization of a trinuclear ruthenium species in catalytic water oxidation by Ru(bda)(pic)2 in neutral media.

PubMed

Zhang, Biaobiao; Li, Fei; Zhang, Rong; Ma, Chengbing; Chen, Lin; Sun, Licheng

2016-06-30

A Ru(III)-O-Ru(IV)-O-Ru(III) type trinuclear species was crystallographically characterized in water oxidation by Ru(bda)(pic)2 (H2bda = 2,2'-bipyridine-6,6'-dicarboxylic acid; pic = 4-picoline) under neutral conditions. The formation of a ruthenium trimer due to the reaction of Ru(IV)[double bond, length as m-dash]O with Ru(II)-OH2 was fully confirmed by chemical, electrochemical and photochemical methods. Since the oxidation of the trimer was proposed to lead to catalyst decomposition, the photocatalytic water oxidation activity was rationally improved by the suppression of the formation of the trimer.

Highly sensitive catalytic spectrophotometric determination of ruthenium

NASA Astrophysics Data System (ADS)

Naik, Radhey M.; Srivastava, Abhishek; Prasad, Surendra

2008-01-01

A new and highly sensitive catalytic kinetic method (CKM) for the determination of ruthenium(III) has been established based on its catalytic effect on the oxidation of L-phenylalanine ( L-Pheala) by KMnO 4 in highly alkaline medium. The reaction has been followed spectrophotometrically by measuring the decrease in the absorbance at 526 nm. The proposed CKM is based on the fixed time procedure under optimum reaction conditions. It relies on the linear relationship where the change in the absorbance (Δ At) versus added Ru(III) amounts in the range of 0.101-2.526 ng ml -1 is plotted. Under the optimum conditions, the sensitivity of the proposed method, i.e. the limit of detection corresponding to 5 min is 0.08 ng ml -1, and decreases with increased time of analysis. The method is featured with good accuracy and reproducibility for ruthenium(III) determination. The ruthenium(III) has also been determined in presence of several interfering and non-interfering cations, anions and polyaminocarboxylates. No foreign ions interfered in the determination ruthenium(III) up to 20-fold higher concentration of foreign ions. In addition to standard solutions analysis, this method was successfully applied for the quantitative determination of ruthenium(III) in drinking water samples. The method is highly sensitive, selective and very stable. A review of recently published catalytic spectrophotometric methods for the determination of ruthenium(III) has also been presented for comparison.

C-N bond cleavage of anilines by a (salen)ruthenium(VI) nitrido complex.

PubMed

Man, Wai-Lun; Xie, Jianhui; Pan, Yi; Lam, William W Y; Kwong, Hoi-Ki; Ip, Kwok-Wa; Yiu, Shek-Man; Lau, Kai-Chung; Lau, Tai-Chu

2013-04-17

We report experimental and computational studies of the facile oxidative C-N bond cleavage of anilines by a (salen)ruthenium(VI) nitrido complex. We provide evidence that the initial step involves nucleophilic attack of aniline at the nitrido ligand of the ruthenium complex, which is followed by proton and electron transfer to afford a (salen)ruthenium(II) diazonium intermediate. This intermediate then undergoes unimolecular decomposition to generate benzene and N2.

Enhancing the mechanical and biological performance of a metallic biomaterial for orthopedic applications through changes in the surface oxide layer by nanocrystalline surface modification.

PubMed

Bahl, Sumit; Shreyas, P; Trishul, M A; Suwas, Satyam; Chatterjee, Kaushik

2015-05-07

Nanostructured metals are a promising class of biomaterials for application in orthopedics to improve the mechanical performance and biological response for increasing the life of biomedical implants. Surface mechanical attrition treatment (SMAT) is an efficient way of engineering nanocrystalline surfaces on metal substrates. In this work, 316L stainless steel (SS), a widely used orthopedic biomaterial, was subjected to SMAT to generate a nanocrystalline surface. Surface nanocrystallization modified the nature of the oxide layer present on the surface. It increased the corrosion-fatigue strength in saline by 50%. This increase in strength is attributed to a thicker oxide layer, residual compressive stresses, high strength of the surface layer, and lower propensity for intergranular corrosion in the nanocrystalline layer. Nanocrystallization also enhanced osteoblast attachment and proliferation. Intriguingly, wettability and surface roughness, the key parameters widely acknowledged for controlling the cellular response remained unchanged after nanocrystallization. The observed cellular behavior is explained in terms of the changes in electronic properties of the semiconducting passive oxide film present on the surface of 316L SS. Nanocrystallization increased the charge carrier density of the n-type oxide film likely preventing denaturation of the adsorbed cell-adhesive proteins such as fibronectin. In addition, a net positive charge developed on the otherwise neutral oxide layer, which is known to facilitate cellular adhesion. The role of changes in the electronic properties of the oxide films on metal substrates is thus highlighted in this work. This study demonstrates the advantages of nanocrystalline surface modification by SMAT for processing metallic biomaterials used in orthopedic implants.

Dithia[3.3]paracyclophane-based monometal ruthenium acetylide complexes: synthesis, characterization and substituent effects.

PubMed

Zhu, Xingxun; Ou, Yaping; Zhang, Jing; Xia, Jian-Long; Yin, Jun; Yu, Guang-Ao; Liu, Sheng Hua

2013-05-21

A series of dithia[3.3]metaparacyclophane-based monometal ruthenium acetylide complexes have been synthesized. All of the complexes have been fully characterised by NMR spectrometry, X-ray crystallography and elemental analyses. At the same time, their basic optical properties, such as UV/Vis absorption spectra, and electrochemical properties have been determined. (1)H NMR and X-ray crystal structure studies reveal that there are intramolecular C-H···π interactions in these ruthenium complexes, in both solution and solid states. Electrochemical studies reveal that the substituted groups on the dithia[3.3]paracyclophane ring can clearly affect the oxidation activities of the ruthenium center by way of the intramolecular C-H···π interaction. In addition, electron-donating groups facilitate the oxidation of the ruthenium center compared with electron-deficient groups. UV/Vis absorption and IR spectra of some complexes in neutral and oxidized states also have been studied. IR spectra studies indicated that the substituents in the cyclophane have some effects on the ν(C≡C) bands of these complexes in the neutral state and little effect on ν(C≡C) of these complexes in the oxidized state.

Probing nanocrystalline grain dynamics in nanodevices

PubMed Central

Yeh, Sheng-Shiuan; Chang, Wen-Yao; Lin, Juhn-Jong

2017-01-01

Dynamical structural defects exist naturally in a wide variety of solids. They fluctuate temporally and hence can deteriorate the performance of many electronic devices. Thus far, the entities of these dynamic objects have been identified to be individual atoms. On the other hand, it is a long-standing question whether a nanocrystalline grain constituted of a large number of atoms can switch, as a whole, reversibly like a dynamical atomic defect (that is, a two-level system). This is an emergent issue considering the current development of nanodevices with ultralow electrical noise, qubits with long quantum coherence time, and nanoelectromechanical system sensors with ultrahigh resolution. We demonstrate experimental observations of dynamic nanocrystalline grains that repeatedly switch between two or more metastable coordinate states. We study temporal resistance fluctuations in thin ruthenium dioxide (RuO2) metal nanowires and extract microscopic parameters, including relaxation time scales, mobile grain sizes, and the bonding strengths of nanograin boundaries. These material parameters are not obtainable by other experimental approaches. When combined with previous in situ high-resolution transmission electron microscopy, our electrical method can be used to infer rich information about the structural dynamics of a wide variety of nanodevices and new two-dimensional materials. PMID:28691094

Nanocrystalline heterojunction materials

DOEpatents

Elder, Scott H.; Su, Yali; Gao, Yufei; Heald, Steve M.

2003-07-15

Mesoporous nanocrystalline titanium dioxide heterojunction materials are disclosed. In one disclosed embodiment, materials comprising a core of titanium dioxide and a shell of a molybdenum oxide exhibit a decrease in their photoadsorption energy as the size of the titanium dioxide core decreases.

Metal oxide films on metal

DOEpatents

Wu, Xin D.; Tiwari, Prabhat

1995-01-01

A structure including a thin film of a conductive alkaline earth metal oxide selected from the group consisting of strontium ruthenium trioxide, calcium ruthenium trioxide, barium ruthenium trioxide, lanthanum-strontium cobalt oxide or mixed alkaline earth ruthenium trioxides thereof upon a thin film of a noble metal such as platinum is provided.

Deposition and properties of cobalt- and ruthenium-based ultra-thin films

NASA Astrophysics Data System (ADS)

Henderson, Lucas Benjamin

Future copper interconnect systems will require replacement of the materials that currently comprise both the liner layer(s) and the capping layer. Ruthenium has previously been considered as a material that could function as a single material liner, however its poor ability to prevent copper diffusion makes it incompatible with liner requirements. A recently described chemical vapor deposition route to amorphous ruthenium-phosphorus alloy films could correct this problem by eliminating the grain boundaries found in pure ruthenium films. Bias-temperature stressing of capacitor structures using 5 nm ruthenium-phosphorus film as a barrier to copper diffusion and analysis of the times-to-failure at accelerated temperature and field conditions implies that ruthenium-phosphorus performs acceptably as a diffusion barrier for temperatures above 165°C. The future problems associated with the copper capping layer are primarily due to the poor adhesion between copper and the current Si-based capping layers. Cobalt, which adheres well to copper, has been widely proposed to replace the Si-based materials, but its ability to prevent copper diffusion must be improved if it is to be successfully implemented in the interconnect. Using a dual-source chemistry of dicobaltoctacarbonyl and trimethylphosphine at temperatures from 250-350°C, amorphous cobalt-phosphorus can be deposited by chemical vapor deposition. The films contain elemental cobalt and phosphorus, plus some carbon impurity, which is incorporated in the film as both graphitic and carbidic (bonded to cobalt) carbon. When deposited on copper, the adhesion between the two materials remains strong despite the presence of phosphorus and carbon at the interface, but the selectivity for growth on copper compared to silicon dioxide is poor and must be improved prior to consideration for application in interconnect systems. A single molecule precursor containing both cobalt and phosphorus atoms, tetrakis

Ruthenium on chitosan: A recyclable heterogeneous catalyst for aqueous hydration of nitriles to amides

EPA Science Inventory

Ruthenium has been immobilized over chitosan by simply stirring an aqueous suspension of chitosan in water with ruthenium chloride and has been utilized for the oxidation of nitriles to amides; the hydration of nitriles occurs in high yield and excellent selectivity, which procee...

4d Electronic structure analysis of ruthenium in the perovskite oxides by Ru K- and L-edge XAS.

PubMed

Kim, J Y; Hwang, S H; Kim, S J; Demazeau, G; Choy, J H; Shimada, H

2001-03-01

The 4d electronic structure of ruthenium in the perovskite oxides, La2MRuIVO6 (M = Zn, Mg, and Li) and Ba2YRuVO6, has been investigated by the Ru K-and L-edge XANES and EXAFS analyses. Such X-ray absorption spectroscopic results clarify that the RuIV (d4) and RuV (d3) ions are stabilized in nearly regular Oh site. Comparing the Ru L-edge XANES spectra of perovskites containing isovalent ruthenium, it has been found that the t2g state is mainly influenced by A site cation, whereas the eg is mainly affected by neighboring B site cation. The experimental EXAFS spectra in the range of R < or = approximately 4.5 A are well reproduced by ab-initio calculation based on crystallographic data, which supports the long-range structure presented by Rietveld refinement.

Ruthenium water oxidation catalysts containing the non-planar tetradentate ligand, biisoquinoline dicarboxylic acid (biqaH2).

PubMed

Scherrer, Dominik; Schilling, Mauro; Luber, Sandra; Fox, Thomas; Spingler, Bernhard; Alberto, Roger; Richmond, Craig J

2016-12-06

Two ruthenium complexes containing the tetradentate ligand [1,1'-biisoquinoline]-3,3'-dicarboxylic acid, and 4-picoline or 6-bromoisoquinoline as axial ligands have been prepared. The complexes have been fully characterised and initial studies on their potential to function as molecular water oxidation catalysts have been performed. Both complexes catalyse the oxidation of water in acidic media with Ce IV as a stoichiometric chemical oxidant, although turnover numbers and turnover frequencies are modest when compared with the closely related Ru-bda and Ru-pda analogues. Barriers for the water nucleophilic attack and intermolecular coupling pathways were obtained from density functional theory calculations and the crucial influence of the ligand framework in determining the most favourable reaction pathway was elucidated from a combined analysis of the theoretical and experimental results.

Ruthenium-catalyzed alkylation of indoles with tertiary amines by oxidation of a sp3 C-H bond and Lewis acid catalysis.

PubMed

Wang, Ming-Zhong; Zhou, Cong-Ying; Wong, Man-Kin; Che, Chi-Ming

2010-05-17

Ruthenium porphyrins (particularly [Ru(2,6-Cl(2)tpp)CO]; tpp=tetraphenylporphinato) and RuCl(3) can act as oxidation and/or Lewis acid catalysts for direct C-3 alkylation of indoles, giving the desired products in high yields (up to 82% based on 60-95% substrate conversions). These ruthenium compounds catalyze oxidative coupling reactions of a wide variety of anilines and indoles bearing electron-withdrawing or electron-donating substituents with high regioselectivity when using tBuOOH as an oxidant, resulting in the alkylation of N-arylindoles to 3-{[(N-aryl-N-alkyl)amino]methyl}indoles (yield: up to 82%, conversion: up to 95%) and the alkylation of N-alkyl or N-H indoles to 3-[p-(dialkylamino)benzyl]indoles (yield: up to 73%, conversion: up to 92%). A tentative reaction mechanism involving two pathways is proposed: an iminium ion intermediate may be generated by oxidation of an sp(3) C-H bond of the alkylated aniline by an oxoruthenium species; this iminium ion could then either be trapped by an N-arylindole (pathway A) or converted to formaldehyde, allowing a subsequent three-component coupling reaction of the in situ generated formaldehyde with an N-alkylindole and an aniline in the presence of a Lewis acid catalyst (pathway B). The results of deuterium-labeling experiments are consistent with the alkylation of N-alkylindoles via pathway B. The relative reaction rates of [Ru(2,6-Cl(2)tpp)CO]-catalyzed oxidative coupling reactions of 4-X-substituted N,N-dimethylanilines with N-phenylindole (using tBuOOH as oxidant), determined through competition experiments, correlate linearly with the substituent constants sigma (R(2)=0.989), giving a rho value of -1.09. This rho value and the magnitudes of the intra- and intermolecular deuterium isotope effects (k(H)/k(D)) suggest that electron transfer most likely occurs during the initial stage of the oxidation of 4-X-substituted N,N-dimethylanilines. Ruthenium-catalyzed three-component reaction of N-alkyl/N-H indoles

Impedance spectroscopic analysis of composite electrode from activated carbon/conductive materials/ruthenium oxide for supercapacitor applications

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

Taer, E.; Awitdrus,; Farma, R.

Activated carbon powders (ACP) were produced from the KOH treated pre-carbonized rubber wood sawdust. Different conductive materials (graphite, carbon black and carbon nanotubes (CNTs)) were added with a binder (polivinylidene fluoride (PVDF)) into ACP to improve the supercapacitive performance of the activated carbon (AC) electrodes. Symmetric supercapacitor cells, fabricated using these AC electrodes and 1 molar H{sub 2}SO{sub 4} electrolyte, were analyzed using a standard electrochemical impedance spectroscopy technique. The addition of graphite, carbon black and CNTs was found effective in reducing the cell resistance from 165 to 68, 23 and 49 Ohm respectively, and increasing the specific capacitance ofmore » the AC electrodes from 3 to 7, 17, 32 F g{sup −1} respectively. Since the addition of CNTs can produce the highest specific capacitance, CNTs were chosen as a conductive material to produce AC composite electrodes that were added with 2.5 %, 5 % and 10 % (by weight) electro-active material namely ruthenium oxide; PVDF binder and CNTs contents were kept at 5 % by weight in each AC composite produced. The highest specific capacitance of the cells obtained in this study was 86 F g{sup −1}, i.e. for the cell with the resistance of 15 Ohm and composite electrode consists of 5 % ruthenium oxide.« less

Nanocrystalline Heterojunction Materials

DOEpatents

Elder, Scott H.; Su, Yali; Gao, Yufei; Heald, Steve M.

2004-02-03

Mesoporous nanocrystalline titanium dioxide heterojunction materials and methods of making the same are disclosed. In one disclosed embodiment, materials comprising a core of titanium dioxide and a shell of a molybdenum oxide exhibit a decrease in their photoadsorption energy as the size of the titanium dioxide core decreases.

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

PubMed

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

2013-11-19

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

MWCNT-ruthenium oxide composite paste electrode as non-enzymatic glucose sensor.

PubMed

Tehrani, Ramin M A; Ab Ghani, Sulaiman

2012-01-01

A non-enzymatic glucose sensor of multi-walled carbon nanotube-ruthenium oxide/composite paste electrode (MWCNT-RuO(2)/CPE) was developed. The electrode was characterized by using XRD, SEM, TEM and EIS. Meanwhile, cyclic voltammetry and amperometry were used to check on the performances of the MWCNT-RuO(2)/CPE towards glucose. The proposed electrode has displayed a synergistic effect of RuO(2) and MWCNT on the electrocatalytic oxidation of glucose in 3M NaOH. This was possible via the formation of transitions of two redox pairs, viz. Ru(VI)/Ru(IV) and Ru(VII)/Ru(VI). A linear range of 0.5-50mM glucose and a limit of detection of 33 μM glucose (S/N=3) were observed. There was no significant interference observable from the traditional interferences, viz. ascorbic acid and uric acid. Indeed, results so obtained have indicated that the developed MWCNT-RuO(2)/CPE would pave the way for a better future to glucose sensor development as its fabrication was without the use of any enzyme. Copyright © 2012 Elsevier B.V. All rights reserved.

Thermodynamic assessment of the rhodium-ruthenium-oxygen (Rh-Ru-O) system

NASA Astrophysics Data System (ADS)

Gossé, S.; Bordier, S.; Guéneau, C.; Brackx, E.; Domenger, R.; Rogez, J.

2018-03-01

Ruthenium (Ru) and rhodium (Rh) are abundant platinum-group metals formed during burn-up of nuclear fuels. Under normal operating conditions, Rh and Ru accumulate and predominantly form metallic precipitates with other fission products like Mo, Pd and Tc. In the framework of vitrification of high-level nuclear waste, these fission products are poorly soluble in molten glasses. They precipitate as metallic particles and oxide phases. Moreover, these Ru and Rh rich phases strongly depend on temperature and the oxygen fugacity of the glass melt. In case of severe accidental conditions with air ingress, oxidation of the Ru and Rh is possible. At low temperatures (T < 1422 K for rhodium sesquioxide and T < 1815 K for ruthenium dioxide), the formed oxides are relatively stable. On the other hand, at high temperatures (T > 1422 K for rhodium sesquioxide and T > 1815 K for ruthenium dioxide), they may decompose into (Rh)-FCC or (Ru)-HCP metallic phases and radiotoxic volatile gaseous species. A thermodynamic assessment of the Rh-Ru-O system will enable the prediction of: (1) the metallic and oxide phases that form during the vitrification of high-level nuclear wastes and (2) the release of volatile gaseous species during a severe accident. The Calphad method developed herein employs a thermodynamic approach in the investigation of the thermochemistry of rhodium and ruthenium at high temperatures. Current literature on the thermodynamic properties and phase diagram data enables preliminary thermodynamic assessments of the Rh-O and Ru-O systems. Additionally, select compositions in the ternary Rh-Ru-O system underwent experimental tests to complement data found in literature and to establish the phase equilibria in the ternary system.

Photocatalytic degradation of Orange G dye under solar light using nanocrystalline semiconductor metal oxide.

PubMed

Thennarasu, G; Kavithaa, S; Sivasamy, A

2011-08-01

The photocatalytic degradation of Orange G (OG) dye has been investigated using synthesised nanocrystalline ZnO as a photocatalyst and sunlight as the irradiation source. The formation of ZnO prepared from its precursor was confirmed through FT-IR and powder X-ray diffraction analyses. Surface morphology was characterised by scanning electron microscope and transmission electron microscope analysis. Band gap energy of synthesised nanocrystalline ZnO was calculated using diffuse reflectance spectroscopy (DRS). Different experimental parameters such as effects of pH, dye concentrations and mass of catalyst were standardised in order to achieve complete degradation of the dye molecules under solar light irradiation. The kinetics of oxidation of OG was also studied. The complete degradation of OG was evident after 90 min of irradiation at an initial pH of 6.86. The degradation of OG was confirmed by UV-Visible spectrophotometer, high-pressure liquid chromatography, ESI-Mass and chemical oxygen demand analyses. The adsorption of dye onto catalytic surface was analysed employing model equations such as Langmuir and Freundlich isotherms, and it was found that the Langmuir isotherm model best fitted the adsorption data. The solar photodegradation of OG followed pseudo-first-order kinetics. HPLC and ESI-Mass analyses of the degraded samples suggested that the dye molecules were readily degraded under solar irradiation with nanocrystalline ZnO.

Nickel-foam-supported ruthenium oxide/graphene sandwich composite constructed via one-step electrodeposition route for high-performance aqueous supercapacitors

NASA Astrophysics Data System (ADS)

Li, Meng; He, Hanwei

2018-05-01

A high-performance supercapacitor both considered high power and high energy density is needed for its applications such as portable electronics and electric vehicles. Herein, we construct a high-performance ruthenium oxide/graphene (RuO2-ERG) composite directly grown on Ni foam through cyclic voltammetric deposition process. The RuO2-ERG composite with sandwich structure is achieved effectively from a mixed solution of graphene oxide and ruthenium trichloride in the -1.4 V to 1.0 V potential range at a scan rate of 5 mV s-1. The electrochemical performance is optimized by tuning the concentration of the ruthenium trichloride. This integrative RuO2-ERG composite electrode can effectively maintains the accessible surface for redox reaction and stable channels for electrolyte penetration, leading to an improved electrochemical performance. Symmetrical aqueous supercapacitors based on RuO2-ERG electrodes exhibit a wider operational voltage window of 1.5 V. The optimized RuO2-ERG electrode displays a superior specific capacitance with 89% capacitance retention upon increasing the current density by 50 times. A high energy density of 43.8 W h kg-1 at a power density of 0.75 kW kg-1 is also obtained, and as high as 39.1 W h kg-1 can be retained at a power density of 37.5 kW kg-1. In addition, the capacitance retention is still maintained at 92.8% even after 10,000 cycles. The excellent electrochemical performance, long-term cycle stability, and the ease of preparation demonstrate that this typical RuO2-ERG electrode has great potentialities to develop high-performance supercapacitors.

Graphene/Ruthenium Active Species Aerogel as Electrode for Supercapacitor Applications

PubMed Central

Gigot, Arnaud; Fontana, Marco; Pirri, Candido Fabrizio; Rivolo, Paola

2017-01-01

Ruthenium active species containing Ruthenium Sulphide (RuS2) is synthesized together with a self-assembled reduced graphene oxide (RGO) aerogel by a one-pot hydrothermal synthesis. Ruthenium Chloride and L-Cysteine are used as reactants. The hydrothermal synthesis of the innovative hybrid material occurs at 180 °C for 12 h, by using water as solvent. The structure and morphology of the hybrid material are fully characterized by Raman, XRD, XPS, FESEM and TEM. The XRD and diffraction pattern obtained by TEM display an amorphous nanostructure of RuS2 on RGO crystallized flakes. The specific capacitance measured in planar configuration in 1 M NaCl electrolyte at 5 mV s−1 is 238 F g−1. This supercapacitor electrode also exhibits perfect cyclic stability without loss of the specific capacitance after 15,000 cycles. In summary, the RGO/Ruthenium active species hybrid material demonstrates remarkable properties for use as active material for supercapacitor applications. PMID:29301192

Graphene/Ruthenium Active Species Aerogel as Electrode for Supercapacitor Applications.

PubMed

Gigot, Arnaud; Fontana, Marco; Pirri, Candido Fabrizio; Rivolo, Paola

2017-12-30

Ruthenium active species containing Ruthenium Sulphide (RuS₂) is synthesized together with a self-assembled reduced graphene oxide (RGO) aerogel by a one-pot hydrothermal synthesis. Ruthenium Chloride and L-Cysteine are used as reactants. The hydrothermal synthesis of the innovative hybrid material occurs at 180 °C for 12 h, by using water as solvent. The structure and morphology of the hybrid material are fully characterized by Raman, XRD, XPS, FESEM and TEM. The XRD and diffraction pattern obtained by TEM display an amorphous nanostructure of RuS₂ on RGO crystallized flakes. The specific capacitance measured in planar configuration in 1 M NaCl electrolyte at 5 mV s -1 is 238 F g -1 . This supercapacitor electrode also exhibits perfect cyclic stability without loss of the specific capacitance after 15,000 cycles. In summary, the RGO/Ruthenium active species hybrid material demonstrates remarkable properties for use as active material for supercapacitor applications.

Photoisomerization of ruthenium(ii) aquo complexes: mechanistic insights and application development.

PubMed

Hirahara, Masanari; Yagi, Masayuki

2017-03-21

Ruthenium(ii) complexes with polypyridyl ligands have been extensively studied as promising functional molecules due to their unique photochemical and photophysical properties as well as redox properties. In this context, we report the photoisomerization of distal-[Ru(tpy)(pynp)OH 2 ] 2+ (d-1) (tpy = 2,2';6',2''-terpyridine, pynp = 2-(2-pyridyl)-1,8-naphthyridine) to proximal-[Ru(tpy)(pynp)OH 2 ] 2+ (p-1), which has not been previously characterized for polypyridyl ruthenium(ii) aquo complexes. Herein, we review recent progress made by our group on the mechanistic insights and application developments related to the photoisomerization of polypyridyl ruthenium(ii) aquo complexes. We report a new strategic synthesis of dinuclear ruthenium(ii) complexes that can act as an active water oxidation catalyst, as well as the development of unique visible-light-responsive giant vesicles, both of which were achieved based on photoisomerization.

Strategic design of a ruthenium catalyst for both CO2 reduction and H2O oxidation: the electronic influence of the co-ligands.

PubMed

Das, Biswanath; Ezzedinloo, Lida; Bhadbhade, Mohan; Bucknall, Martin P; Colbran, Stephen B

2017-09-05

A new ruthenium(ii) complex capable of catalysing both CO 2 reduction and water oxidation was designed and synthesised. The electro-catalytic efficiency and robustness of the complex together with the electronic effect of its co-ligands were investigated to develop next generation dual activity electrocatalysts.

Carboxylate-assisted ruthenium-catalyzed alkyne annulations by C-H/Het-H bond functionalizations.

PubMed

Ackermann, Lutz

2014-02-18

To improve the atom- and step-economy of organic syntheses, researchers would like to capitalize upon the chemistry of otherwise inert carbon-hydrogen (C-H) bonds. During the past decade, remarkable progress in organometallic chemistry has set the stage for the development of increasingly viable metal catalysts for C-H bond activation reactions. Among these methods, oxidative C-H bond functionalizations are particularly attractive because they avoid the use of prefunctionalized starting materials. For example, oxidative annulations that involve sequential C-H and heteroatom-H bond cleavages allow for the modular assembly of regioselectively decorated heterocycles. These structures serve as key scaffolds for natural products, functional materials, crop protecting agents, and drugs. While other researchers have devised rhodium or palladium complexes for oxidative alkyne annulations, my laboratory has focused on the application of significantly less expensive, yet highly selective ruthenium complexes. This Account summarizes the evolution of versatile ruthenium(II) complexes for annulations of alkynes via C-H/N-H, C-H/O-H, or C-H/N-O bond cleavages. To achieve selective C-H bond functionalizations, we needed to understand the detailed mechanism of the crucial C-H bond metalation with ruthenium(II) complexes and particularly the importance of carboxylate assistance in this process. As a consequence, our recent efforts have resulted in widely applicable methods for the versatile preparation of differently decorated arenes and heteroarenes, providing access to among others isoquinolones, 2-pyridones, isoquinolines, indoles, pyrroles, or α-pyrones. Most of these reactions used Cu(OAc)2·H2O, which not only acted as the oxidant but also served as the essential source of acetate for the carboxylate-assisted ruthenation manifold. Notably, the ruthenium(II)-catalyzed oxidative annulations also occurred under an ambient atmosphere of air with cocatalytic amounts of Cu(OAc)2�

Role of Mediator and Effects of Temperature on ortho-C-N Bond Fusion Reactions of Aniline Using Ruthenium Templates: Isolation and Characterization of New Ruthenium Complexes of the in-Situ-Generated Ligands.

PubMed

Roy, Suman K; Sengupta, Debabrata; Rath, Santi Prasad; Saha, Tanushri; Samanta, Subhas; Goswami, Sreebrata

2017-05-01

In this work, ortho-C-N bond fusion reactions of aniline are followed by the use of two different ruthenium mediators. Reaction of aniline with [Ru III (terpy)Cl 3 ] (terpy = 2,2':6',2″-terpyridine) resulted in a trans bis-aniline ruthenium(II) complex [1] + which upon oxidation with H 2 O 2 produced compound [2] + of a bidentate ligand, N-phenyl-1,2-benzoquinonediimine, due to an oxidative ortho-C-N bond fusion reaction. Complex [1] + and aniline (neat) at 185 °C produced a bis-chelated ruthenium complex (3). A previously reported complex [Ru II (N-phenyl-1,2-benzoquinonediimine)(aniline) 2 (Cl) 2 ] (5) undergoes similar oxidation by air at 185 °C to produce complex [3]. A separate chemical reaction between aniline and strongly oxidizing tetra-n-propylammonium perruthenate [(n-pr) 4 N] + [RuO 4 ] - in air produced a ruthenium complex [4] of a N 4 -tetraamidophenylmacrocycle ligand via multiple ortho-C-N bond fusion reaction. Notably, the yield of this product is low (5%) at 100 °C but increases to 25% in refluxing aniline. All these complexes are characterized fully by their physicochemical characterizations and X-ray structure determination. From their structural parameters and other spectroscopic studies, complex [2] + is assigned as [Ru II (terpy)(N-phenyl-1,2-benzoquinonediimine)(Cl)] + whereas complex [4] is described as a ruthenium(VI) complex comprised of a reduced deprotonated N-phenyl-1,2-diamidobenzene and N 4 -tetraamidophenylmacrocyclic ligand. Complex [2] + exhibits one reversible oxidation at 1.32 V and one reversible reduction at -0.75 V vs Ag/AgCl reference electrode. EPR of the electrogenerated complexes has revealed that the oxidized complex is a ruthenium(III) complex with an axial EPR spectrum at g av = 2.06. The reduced complex [2], on the other hand, shows a single-line EPR signal at g av = 1.998. In contrast, complex [4] shows two successive one-electron oxidation waves at 0.5 and 0.8 V and an irreversible reduction wave at -0.9 V. EPR

Bandgap engineering through nanocrystalline magnetic alloy grafting on reduced graphene oxide.

PubMed

De, D; Chakraborty, M; Majumdar, S; Giri, S

2014-09-28

High conductivity and the absence of ferromagnetism in pristine graphene fail to satisfy primary criteria for possible technological application in spintronics. Opening of the bandgap in graphene is primarily desirable for such applications. We report a simplified and novel approach of controlled grafting of a magnetic alloy on reduced graphene oxide. This eventually leads to ferromagnetism of the stable hybrid material at room temperature, with a large moment (∼1.2 μB) and a remarkable decrease in conductivity (∼10 times) compared to highly ordered pyrolytic graphite. Our model band-structure calculation indicates that the combined effect of controlled vacancies and impurities attributed to the nanocrystalline alloy grafting leads to a promising step toward band gap engineering.

Electrooxidative Ruthenium-Catalyzed C-H/O-H Annulation by Weak O-Coordination.

PubMed

Qiu, Youai; Tian, Cong; Massignan, Leonardo; Rogge, Torben; Ackermann, Lutz

2018-05-14

Electrocatalysis has been identified as a powerful strategy for organometallic catalysis, and yet electrocatalytic C-H activation is restricted to strongly N-coordinating directing groups. The first example of electrocatalytic C-H activation by weak O-coordination is presented, in which a versatile ruthenium(II) carboxylate catalyst enables electrooxidative C-H/O-H functionalization for alkyne annulations in the absence of metal oxidants; thereby exploiting sustainable electricity as the sole oxidant. Mechanistic insights provide strong support for a facile organometallic C-H ruthenation and an effective electrochemical reoxidation of the key ruthenium(0) intermediate. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Highly Cooperative Tetrametallic Ruthenium-μ-Oxo-μ-Hydroxo Catalyst for the Alcohol Oxidation Reaction

PubMed Central

Yi, Chae S.; Zeczycki, Tonya N.; Guzei, Ilia A.

2008-01-01

The tetrametallic ruthenium-oxo-hydroxo-hydride complex {[(PCy3)(CO)RuH]4(μ4-O)(μ3-OH)(μ2-OH)} (1) was synthesized in two steps from the monomeric complex (PCy3)(CO)RuHCl (2). The tetrameric complex 1 was found to be a highly effective catalyst for the transfer dehydrogenation of alcohols. Complex 1 showed a different catalytic activity pattern towards primary and secondary benzyl alcohols, as indicated by the Hammett correlation for the oxidation reaction of p-X-C6H4CH2OH (ρ = −0.45) and p-X-C6H4CH(OH)CH3 (ρ = +0.22) (X = OMe, CH3, H, Cl, CF3). Both a sigmoidal curve from the plot of initial rate vs [PhCH(OH)CH3] (K0.5 = 0.34 M; Hill coefficient, n = 4.2±0.1) and the phosphine inhibition kinetics revealed the highly cooperative nature of the complex for the oxidation of secondary alcohols. PMID:18726005

Evidence of nanocrystalline semiconducting graphene monoxide during thermal reduction of graphene oxide in vacuum.

PubMed

Mattson, Eric C; Pu, Haihui; Cui, Shumao; Schofield, Marvin A; Rhim, Sonny; Lu, Ganhua; Nasse, Michael J; Ruoff, Rodney S; Weinert, Michael; Gajdardziska-Josifovska, Marija; Chen, Junhong; Hirschmugl, Carol J

2011-12-27

As silicon-based electronics are reaching the nanosize limits of the semiconductor roadmap, carbon-based nanoelectronics has become a rapidly growing field, with great interest in tuning the properties of carbon-based materials. Chemical functionalization is a proposed route, but syntheses of graphene oxide (G-O) produce disordered, nonstoichiometric materials with poor electronic properties. We report synthesis of an ordered, stoichiometric, solid-state carbon oxide that has never been observed in nature and coexists with graphene. Formation of this material, graphene monoxide (GMO), is achieved by annealing multilayered G-O. Our results indicate that the resulting thermally reduced G-O (TRG-O) consists of a two-dimensional nanocrystalline phase segregation: unoxidized graphitic regions are separated from highly oxidized regions of GMO. GMO has a quasi-hexagonal unit cell, an unusually high 1:1 O:C ratio, and a calculated direct band gap of ∼0.9 eV.

Nonvolatile memory behavior of nanocrystalline cellulose/graphene oxide composite films

NASA Astrophysics Data System (ADS)

Valentini, L.; Cardinali, M.; Fortunati, E.; Kenny, J. M.

2014-10-01

With the continuous advance of modern electronics, the demand for nonvolatile memory cells rapidly grows. In order to develop post-silicon electronic devices, it is necessary to find innovative solutions to the eco-sustainability problem of materials for nonvolatile memory cells. In this work, we realized a resistive memory device based on graphene oxide (GO) and GO/cellulose nanocrystals (CNC) thin films. Aqueous solutions of GO and GO with CNC have been prepared and drop cast between two metal electrodes. Such thin-film based devices showed a transition between low and high conductivity states upon the forward and backward sweeping of an external electric field. This reversible current density transition behavior demonstrates a typical memory characteristic. The obtained results open an easy route for electronic information storage based on the integration of nanocrystalline cellulose onto graphene based devices.

Nonvolatile memory behavior of nanocrystalline cellulose/graphene oxide composite films

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

Valentini, L., E-mail: luca.valentini@unipg.it; Cardinali, M.; Fortunati, E.

2014-10-13

With the continuous advance of modern electronics, the demand for nonvolatile memory cells rapidly grows. In order to develop post-silicon electronic devices, it is necessary to find innovative solutions to the eco-sustainability problem of materials for nonvolatile memory cells. In this work, we realized a resistive memory device based on graphene oxide (GO) and GO/cellulose nanocrystals (CNC) thin films. Aqueous solutions of GO and GO with CNC have been prepared and drop cast between two metal electrodes. Such thin-film based devices showed a transition between low and high conductivity states upon the forward and backward sweeping of an external electricmore » field. This reversible current density transition behavior demonstrates a typical memory characteristic. The obtained results open an easy route for electronic information storage based on the integration of nanocrystalline cellulose onto graphene based devices.« less

Catalytic oxidation of dimethyl ether

DOEpatents

Zelenay, Piotr; Wu, Gang; Johnston, Christina M.; Li, Qing

2016-05-10

A composition for oxidizing dimethyl ether includes an alloy supported on carbon, the alloy being of platinum, ruthenium, and palladium. A process for oxidizing dimethyl ether involves exposing dimethyl ether to a carbon-supported alloy of platinum, ruthenium, and palladium under conditions sufficient to electrochemically oxidize the dimethyl ether.

Selective Oxidation of n-Hexane by Cu (II) Nanoclusters Supported on Nanocrystalline Zirconia Catalyst.

PubMed

Acharyya, Shankha Shubhra; Ghosh, Shilpi; Adak, Shubhadeep; Singh, Raghuvir; Saran, Sandeep; Bal, Rajaram

2015-08-01

Cu (II) nanoclusters supported on nanocrystalline zirconia catalyst (with size ~15 nm), was prepared by using cationic surfactant cetyltrimethylammonium in a hydrothermal synthesis method. The catalyst was characterized by XRD, XPS, TGA, SEM, TEM, FTIR and ICP-AES. The catalyst was found to be efficient in selective oxidation of n-hexane to 2-hexanol. An n-hexane conversion of 55%, with a 2-hexanol selectivity of 70% was achieved over this catalyst in liquid phase, without the use of any solvent. The catalyst can be reused several times without any significant activity loss.

Diene Hydroacylation from the Alcohol or Aldehyde Oxidation Level via Ruthenium Catalyzed C-C Bond Forming Transfer Hydrogenation: Synthesis of β,γ-Unsaturated Ketones

PubMed Central

Shibahara, Fumitoshi; Bower, John F.; Krische, Michael J.

2011-01-01

Under the conditions of ruthenium catalyzed transfer hydrogenation, isoprene couples to benzylic and aliphatic alcohols 1a–1g to deliver β,γ-unsaturated ketones 3a–3g in good to excellent isolated yields. Under identical conditions, aldehydes 2a–2g couple to isoprene to provide an identical set of β,γ-unsaturated ketones 3a–3g in good to excellent isolated yields. As demonstrated by the coupling of butadiene, myrcene and 1,2-dimethylbutadiene to representative alcohols 1b, 1c and 1e, diverse acyclic dienes participate in transfer hydrogenative coupling to form β,γ-unsaturated ketones. In all cases, complete branch-regioselectivity is observed and, with the exception of adduct 3j, isomerization to the conjugated enone is not detected. Thus, formal intermolecular diene hydroacylation is achieved from the alcohol or aldehyde oxidation level. In earlier studies employing a related ruthenium catalyst, acyclic dienes were coupled to carbonyl partners from the alcohol or aldehyde oxidation level to furnish branched homoallylic alcohols. Thus, under transfer hydrogenative coupling conditions, all oxidations levels of substrate (alcohol or aldehyde) and product (homoallyl alcohol or β,γ-unsaturated ketone) are accessible. PMID:18841895

Oxidation-reduction catalyst and its process of use

NASA Technical Reports Server (NTRS)

Schryer, Jacqueline L. (Inventor); Oglesby, Donald M. (Inventor); Jordan, Jeffrey D. (Inventor); Watkins, Anthony Neal (Inventor)

2008-01-01

This invention relates generally to a ruthenium stabilized oxidation-reduction catalyst useful for oxidizing carbon monoxide, and volatile organic compounds, and reducing nitrogen oxide species in oxidizing environments, substantially without the formation of toxic and volatile ruthenium oxide species upon said oxidizing environment being at high temperatures.

Catalyzing the oxidation of sulfamethoxazole by permanganate using molecular sieves supported ruthenium nanoparticles.

PubMed

Zhang, Jing; Sun, Bo; Huang, Yuying; Guan, Xiaohong

2015-12-01

This study developed a heterogeneous catalytic permanganate oxidation system with three molecular sieves, i.e., nanosized ZSM-5 (ZSM-5A), microsized ZSM-5 (ZSM-5B) and MCM-41, supported ruthenium nanoparticles as catalyst, denoted as Ru/ZSM-5A, Ru/ZSM-5B and Ru/MCM-41, respectively. The presence of 0.5gL(-1) Ru/ZSM-5A, Ru/ZSM-5B and Ru/MCM-41 increased the oxidation rate of sulfamethoxazole (SMX) by permanganate at pH 7.0 by 27-1144 times. The catalytic performance of Ru catalysts toward SMX oxidation by permanganate was strongly dependent on Ru loading on the catalysts. The X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) analyses confirmed that Ru catalyst acted as an electron shuttle in catalytic permanganate oxidation process. Ru(III) deposited on the surface of catalysts was oxidized by permanganate to its higher oxidation state Ru(VII), which could work as a co-oxidant with permanganate to decompose SMX and was then reduced to its initial tri-valence. During the successive runs, Ru/ZSM-5A could not maintain its catalytic activity due to the deposition of MnO2, which was the reductive product of permanganate, onto the surface of Ru/ZSM-5A. Thus, the regeneration of partially deactivated Ru catalysts by reductant NH2OH⋅HCl or ascorbic acid was proposed. Ru/ZSM-5A regenerated by NH2OH⋅HCl displayed comparable catalytic ability to its virgin counterpart, while ascorbic acid could not completely remove the deposited MnO2. A trace amount of leaching of Ru into the reaction solution was also observed, which would be ameliorated by improving the preparation conditions in the future study. Copyright © 2015 Elsevier Ltd. All rights reserved.

Methanol oxidation reaction on core-shell structured Ruthenium-Palladium nanoparticles: Relationship between structure and electrochemical behavior

NASA Astrophysics Data System (ADS)

Kübler, Markus; Jurzinsky, Tilman; Ziegenbalg, Dirk; Cremers, Carsten

2018-01-01

In this work the relationship between structural composition and electrochemical characteristics of Palladium(Pd)-Ruthenium(Ru) nanoparticles during alkaline methanol oxidation reaction is investigated. The comparative study of a standard alloyed and a precisely Ru-core-Pd-shell structured catalyst allows for a distinct investigation of the electronic effect and the bifunctional mechanism. Core-shell catalysts benefit from a strong electronic effect and an efficient Pd utilization. It is found that core-shell nanoparticles are highly active towards methanol oxidation reaction for potentials ≥0.6 V, whereas alloyed catalysts show higher current outputs in the lower potential range. However, differential electrochemical mass spectrometry (DEMS) experiments reveal that the methanol oxidation reaction on core-shell structured catalysts proceeds via the incomplete oxidation pathway yielding formaldehyde, formic acid or methyl formate. Contrary, the alloyed catalyst benefits from the Ru atoms at its surface. Those are found to be responsible for high methanol oxidation activity at lower potentials as well as for complete oxidation of CH3OH to CO2 via the bifunctional mechanism. Based on these findings a new Ru-core-Pd-shell-Ru-terrace catalyst was synthesized, which combines the advantages of the core-shell structure and the alloy. This novel catalyst shows high methanol electrooxidation activity as well as excellent selectivity for the complete oxidation pathway.

Sol-gel processed thin-layer ruthenium oxide/carbon black supercapacitors: A revelation of the energy storage issues

NASA Astrophysics Data System (ADS)

Panić, V. V.; Dekanski, A. B.; Stevanović, R. M.

Hydrous ruthenium oxide/carbon black nanocomposites were prepared by impregnation of the carbon blacks by differently aged inorganic RuO 2 sols, i.e. of different particle size. Commercial Black Pearls 2000 ® (BP) and Vulcan ® XC-72 R (XC) carbon blacks were used. Capacitive properties of BP/RuO 2 and XC/RuO 2 composites were investigated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) in H 2SO 4 solution. Capacitance values and capacitance distribution through the composite porous layer were found different if high- (BP) and low- (XC) surface-area carbons are used as supports. The aging time (particle size) of Ru oxide sol as well as the concentration of the oxide solid phase in the impregnating medium influenced the capacitive performance of prepared composites. While the capacitance of BP-supported oxide decreases with the aging time, the capacitive ability of XC-supported oxide is promoted with increasing oxide particle size. The increase in concentration of the oxide solid phase in the impregnating medium caused an improvement of charging/discharging characteristics due to pronounced pseudocapacitance contribution of the increasing amount of inserted oxide. The effects of these variables in the impregnation process on the energy storage capabilities of prepared nanocomposites are envisaged as a result of intrinsic way of population of the pores of carbon material by hydrous Ru oxide particle.

X-ray reflectivity of ruthenium nano-oxide layer in a CoFe-Ru-CoFe trilayer system

NASA Astrophysics Data System (ADS)

Asghari Zadeh, Saeid; Sutton, Mark; Altonian, Zaven; Mao, Ming; Lee, Chih-Ling

2006-03-01

A grazing incidence X-ray reflectivity technique is used to determine electron density profile(EDP) as a function of depth in CoFe-Ru-CoFe and CoFe-Ru nano oxide layer(NOL)-CoFe trilayers. Four trilayers with ruthenium thicknesses of 8,8.5 and 9 å.08cm and one with Ru8.5.05cmå.05cmNOL, prepared by a dc planetary sputtering system, were investigated. For all samples, EDP shows a central peak which is related to the Ru layer. Natural oxidation in all samples introduces a graded EDP of the top CoFe layer that decreases gradually to zero. The large surface resistivity of Ru8.5 å.05cm NOL compared to Ru 8.5å.08cm can be related to the remarkable difference between their EDP.

Acetate- and thiol-capped monodisperse ruthenium nanoparticles: XPS, XAS, and HRTEM studies.

PubMed

Chakroune, Nassira; Viau, Guillaume; Ammar, Souad; Poul, Laurence; Veautier, Delphine; Chehimi, Mohamed M; Mangeney, Claire; Villain, Françoise; Fiévet, Fernand

2005-07-19

Monodisperse ruthenium nanoparticles were prepared by reduction of RuCl3 in 1,2-propanediol. The mean particle size was controlled by appropriate choice of the reduction temperature and the acetate ion concentration. Colloidal solutions in toluene were obtained by coating the metal particles with dodecanethiol. High-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), and X-ray absorption spectroscopy (XANES and EXAFS for the Ru K-absorption edge) were performed on particles of two different diameters, 2 and 4 nm, and in different environments, polyol/acetate or thiol. For particles stored in polyol/acetate XPS studies revealed superficial oxidation limited to one monolayer and a surface coating containing mostly acetate ions. Analysis of the EXAFS spectra showed both oxygen and ruthenium atoms around the ruthenium atoms with a Ru-Ru coordination number N smaller than the bulk value, as expected for fine particles. In the case of 2 nm acetate-capped particles N is consistent with particles made up of a metallic core and an oxidized monolayer. For 2 nm thiol-coated particles, a Ru-S bond was evidenced by XPS and XAS. For the 4 nm particles XANES and XPS studies showed that most of the ruthenium atoms are in the zerovalent state. Nevertheless, in both cases, when capped with thiol, the Ru-Ru coordination number inferred from EXAFS is much smaller than for particles of the same size stored in polyol. This is attributed to a structural disorganization of the particles by thiol chemisorption. HRTEM studies confirm the marked dependence of the structural properties of the ruthenium particles on their chemical environment; they show the acetate-coated particles to be single crystals, whereas the thiol-coated particles appear to be polycrystalline.

Structural and catalytic properties of some azo-rhodanine Ruthenium(III) complexes

NASA Astrophysics Data System (ADS)

Shoair, A. F.; El-Bindary, A. A.; Abd El-Kader, M. K.

2017-09-01

Novel azo-rhodanine ruthenium(III) complexes of the type trans-[Ru(Ln)2(AsPh3)2]Cl (Ln = monobasic bidentate anions of 5-(4‧-methoxyphenylazo)-3-phenylamino-2-thioxothiazolidin-4-one (HL1), 5-(phenylazo)-3-phenylamino-2-thioxothiazolidin-4-one (HL2) and 5-(4‧-chlorophenylazo)-3-phenylamino-2-thioxothiazolidin-4-one (HL3); AsPh3 = triphenylarsine) have been synthesized and characterized by elemental analysis, spectroscopic (IR, 1H NMR and UV-VIS), magnetic, X-ray diffraction, mass spectra and thermal analysis techniques. These techniques confirm the formation of octahedral ruthenium(III) complexes. The Ru(III) complexes were tested as a catalysts for the oxidation of benzyl alcohol to benzaldehyde with N-methylmorpholine-N-oxide as a co-oxidant. The effect of time, temperature, and solvent were also studied and the mechanism of this catalytic oxidation reaction is suggested. Molecular docking was used to predict the binding between azo rhodanine derivatives (HLn) with the receptor of 3qum- immune system receptor of human prostate specific antigen (PSA) in a Fab sandwich with a high affinity and a PCa selective antibody.

Recommendation of ruthenium source for sludge batch flowsheet studies

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

Woodham, W.

Included herein is a preliminary analysis of previously-generated data from sludge batches 7a, 7b, 8, and 9 sludge simulant and real-waste testing, performed to recommend a form of ruthenium for future sludge batch simulant testing under the nitric-formic flowsheet. Focus is given to reactions present in the Sludge Receipt and Adjustment Tank cycle, given that this cycle historically produces the most changes in chemical composition during Chemical Process Cell processing. Data is presented and analyzed for several runs performed under the nitric-formic flowsheet, with consideration given to effects on the production of hydrogen gas, nitrous oxide gas, consumption of formate,more » conversion of nitrite to nitrate, and the removal and recovery of mercury during processing. Additionally, a brief discussion is given to the effect of ruthenium source selection under the nitric-glycolic flowsheet. An analysis of data generated from scaled demonstration testing, sludge batch 9 qualification testing, and antifoam degradation testing under the nitric-glycolic flowsheet is presented. Experimental parameters of interest under the nitric-glycolic flowsheet include N2O production, glycolate destruction, conversion of glycolate to formate and oxalate, and the conversion of nitrite to nitrate. To date, the number of real-waste experiments that have been performed under the nitric-glycolic flowsheet is insufficient to provide a complete understanding of the effects of ruthenium source selection in simulant experiments with regard to fidelity to real-waste testing. Therefore, a determination of comparability between the two ruthenium sources as employed under the nitric-glycolic flowsheet is made based on available data in order to inform ruthenium source selection for future testing under the nitric-glycolic flowsheet.« less

SEPARATION OF RUTHENIUM FROM AQUEOUS SOLUTIONS

DOEpatents

Beederman, M.; Vogler, S.; Hyman, H.H.

1959-07-14

The separation of rathenium from a rathenium containing aqueous solution is described. The separation is accomplished by adding sodium nitrite, silver nitrate and ozone to the ruthenium containing aqueous solution to form ruthenium tetroxide and ihen volatilizing off the ruthenium tetroxide.

The influence of interfacial defects on fast charge trapping in nanocrystalline oxide-semiconductor thin film transistors

NASA Astrophysics Data System (ADS)

Kim, Taeho; Hur, Jihyun; Jeon, Sanghun

2016-05-01

Defects in oxide semiconductors not only influence the initial device performance but also affect device reliability. The front channel is the major carrier transport region during the transistor turn-on stage, therefore an understanding of defects located in the vicinity of the interface is very important. In this study, we investigated the dynamics of charge transport in a nanocrystalline hafnium-indium-zinc-oxide thin-film transistor (TFT) by short pulse I-V, transient current and 1/f noise measurement methods. We found that the fast charging behavior of the tested device stems from defects located in both the front channel and the interface, following a multi-trapping mechanism. We found that a silicon-nitride stacked hafnium-indium-zinc-oxide TFT is vulnerable to interfacial charge trapping compared with silicon-oxide counterpart, causing significant mobility degradation and threshold voltage instability. The 1/f noise measurement data indicate that the carrier transport in a silicon-nitride stacked TFT device is governed by trapping/de-trapping processes via defects in the interface, while the silicon-oxide device follows the mobility fluctuation model.

Nanocrystalline semiconductor doped rare earth oxide for the photocatalytic degradation studies on Acid Blue 113: A di-azo compound under UV slurry photoreactor.

PubMed

Suganya Josephine, G A; Mary Nisha, U; Meenakshi, G; Sivasamy, A

2015-11-01

Preventive measures for the control of environmental pollution and its remediation has received much interest in recent years due to the world-wide increase in the contamination of water bodies. Contributions of these harmful effluents are caused by the leather processing, pharmaceutical, cosmetic, textile, agricultural and other chemical industries. Nowadays, advanced oxidation processes considered to be better option for the complete destruction of organic contaminants in water and wastewater. Acid Blue 113 is a most widely used di-azo compound in leather, textile, dying and food industry as a color rending compound. In the present study, we have reported the photo catalytic degradation of Acid Blue 113 using a nanocrystalline semiconductor doped rare earth oxide as a photo catalyst under UV light irradiation. The photocatalyst was prepared by a simple precipitation technique and were characterized by XRD, FT-IR, UV-DRS and FE-SEM analysis. The experimental results proved that the prepared photo catalyst was nanocrystalline and highly active in the UV region. The UV-DRS results showed the band gap energy was 3.15eV for the prepared photo catalyst. The photodegradation efficiency was analyzed by various experimental parameters such as pH, catalyst dosage, variation of substrate concentration and effect of electrolyte addition. The photo degradation process followed a pseudo first order kinetics and was continuously monitored by UV-visible spectrophotometer. The experimental results proved the efficacy of the nanocrystalline zinc oxide doped dysprosium oxide which are highly active under UV light irradiations. It is also suggested that the prepared material would find wider applications in environmental remediation technologies to remove the carcinogenic and toxic moieties present in the industrial effluents. Copyright © 2015 Elsevier Inc. All rights reserved.

Synthesis and properties of nanocrystalline copper indium oxide thin films deposited by Rf magnetron sputtering.

PubMed

Singh, Mandeep; Singh, V N; Mehta, B R

2008-08-01

Nanocrystalline copper indium oxide (CuInO2) thin films with particle size ranging from 25 nm to 71 nm have been synthesized from a composite target using reactive Rf magnetron sputtering technique. X-ray photoelectron spectroscopy (XPS) combined with glancing angle X-ray diffraction (GAXRD) analysis confirmed the presence of delafossite CuInO2 phase in these films. The optical absorption studies show the presence of two direct band gaps at 3.3 and 4.3 eV, respectively. The resistance versus temperature measurements show thermally activated hopping with activation energy of 0.84 eV to be the conduction mechanism.

Hydrogen generation from water/methanol under visible light using aerogel prepared strontium titanate (SrTiO3) nanomaterials doped with ruthenium and rhodium metals

NASA Astrophysics Data System (ADS)

Kuo, Yenting; Klabunde, Kenneth J.

2012-07-01

Nanostructured strontium titanate visible-light-driven photocatalysts containing rhodium and ruthenium were synthesized by a modified aerogel synthesis using ruthenium chloride and rhodium nitrate as dopant precursors, and titanium isopropoxide and strontium metal as the metal sources. The well-defined crystalline SrTiO3 structure was confirmed by means of x-ray diffraction. After calcination at 500 °C, diffuse reflectance spectroscopy shows an increase in light absorption at 370 nm due to the presence of Rh3 + ; however an increase of the calcination temperature to 600 °C led to a decrease in intensity, probably due to a loss of surface area. An increase in the rhodium doping level also led to an increase in absorption at 370 nm however, the higher amounts of dopant lowered the photocatalytic activity. The modified aerogel synthesis allows greatly enhanced H2 production performance from an aqueous methanol solution under visible light irradiation compared with lower surface area conventional materials. We believe that this enhanced activity is due to the higher surface areas while high quality nanocrystalline materials are still obtained. Furthermore, the surface properties of these nanocrystalline aerogel materials are different, as exhibited by the higher activities in alkaline solutions, while conventional materials (obtained via high temperature solid-state synthesis methods) only exhibit reasonable hydrogen production in acidic solutions. Moreover, an aerogel synthesis approach gives the possibility of thin-film formation and ease of incorporation into practical solar devices.

Wet air oxidation of cresylic spent caustic - A model compound study over graphene oxide (GO) and ruthenium/GO catalysts.

PubMed

Barge, Aditti S; Vaidya, Prakash D

2018-04-15

Wet air oxidation (WAO) is a candidate technique for the effective treatment of spent caustic wastewater. In this work, cresols were chosen as model compounds to represent cresylic spent caustic wash. Graphene oxide (GO) is a promising catalyst as well as support for the wet oxidation process, due to its unique structure and properties. For the first time, GO and ruthenium supported on graphene oxide (Ru/GO) were employed for WAO of cresylic isomers. The aforesaid materials were synthesized by modified Hummer's method and characterized using scanning electron microscopy (SEM), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), Fourier transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD) and Brunauer-Emmett-Teller (BET) analysis. The performance of the investigated materials for WAO of cresols was studied in a slurry reactor. The best reaction conditions for GO were 175 °C and 0.69 MPa O 2 pressure. Total organic carbon (TOC) degradation achieved at these conditions was 54.9, 48.9 and 61.2% for o-cresol, m-cresol and p-cresol, respectively. The amount of TOC degradation obtained by using Ru/GO at the same reaction conditions was 66.4, 53.4 and 73.9% for o-cresol, m-cresol and p-cresol, respectively. It was found that the order of reactivity for cresols was p-cresol > o-cresol > m-cresol. Finally, kinetics of TOC destruction during CWAO of p-cresol over GO was described using a two-step power law model. Copyright © 2018 Elsevier Ltd. All rights reserved.

Electronic structure investigation of atomic layer deposition ruthenium(oxide) thin films using photoemission spectroscopy

NASA Astrophysics Data System (ADS)

Schaefer, Michael; Schlaf, Rudy

2015-08-01

Analyzing and manipulating the electronic band line-up of interfaces in novel micro- and nanoelectronic devices is important to achieve further advancement in this field. Such band alignment modifications can be achieved by introducing thin conformal interfacial dipole layers. Atomic layer deposition (ALD), enabling angstrom-precise control over thin film thickness, is an ideal technique for this challenge. Ruthenium (Ru0) and its oxide (RuO2) have gained interest in the past decade as interfacial dipole layers because of their favorable properties like metal-equivalent work functions, conductivity, etc. In this study, initial results of the electronic structure investigation of ALD Ru0 and RuO2 films via photoemission spectroscopy are presented. These experiments give insight into the band alignment, growth behavior, surface structure termination, and dipole formation. The experiments were performed in an integrated vacuum system attached to a home-built, stop-flow type ALD reactor without exposing the samples to the ambient in between deposition and analysis. Bis(ethylcyclopentadienyl)ruthenium(II) was used as precursor and oxygen as reactant. The analysis chamber was outfitted with X-ray photoemission spectroscopy (LIXPS, XPS). The determined growth modes are consistent with a strong growth inhibition situation with a maximum average growth rate of 0.21 Å/cycle for RuO2 and 0.04 Å/cycle for Ru.0 An interface dipole of up to -0.93 eV was observed, supporting the assumption of a strongly physisorbed interface. A separate experiment where the surface of a RuO film was sputtered suggests that the surface is terminated by an intermediate, stable, non-stoichiometric RuO2/OH compound whose surface is saturated with hydroxyl groups.

Oxidation-Based Continuous Laser Writing in Vertical Nano-Crystalline Graphite Thin Films

PubMed Central

Loisel, Loïc; Florea, Ileana; Cojocaru, Costel-Sorin; Tay, Beng Kang; Lebental, Bérengère

2016-01-01

Nano and femtosecond laser writing are becoming very popular techniques for patterning carbon-based materials, as they are single-step processes enabling the drawing of complex shapes without photoresist. However, pulsed laser writing requires costly laser sources and is known to cause damages to the surrounding material. By comparison, continuous-wave lasers are cheap, stable and provide energy at a more moderate rate. Here, we show that a continuous-wave laser may be used to pattern vertical nano-crystalline graphite thin films with very few macroscale defects. Moreover, a spatially resolved study of the impact of the annealing to the crystalline structure and to the oxygen ingress in the film is provided: amorphization, matter removal and high oxygen content at the center of the beam; sp2 clustering and low oxygen content at its periphery. These data strongly suggest that amorphization and matter removal are controlled by carbon oxidation. The simultaneous occurrence of oxidation and amorphization results in a unique evolution of the Raman spectra as a function of annealing time, with a decrease of the I(D)/I(G) values but an upshift of the G peak frequency. PMID:27194181

Oxidation-Based Continuous Laser Writing in Vertical Nano-Crystalline Graphite Thin Films

NASA Astrophysics Data System (ADS)

Loisel, Loïc; Florea, Ileana; Cojocaru, Costel-Sorin; Tay, Beng Kang; Lebental, Bérengère

2016-05-01

Nano and femtosecond laser writing are becoming very popular techniques for patterning carbon-based materials, as they are single-step processes enabling the drawing of complex shapes without photoresist. However, pulsed laser writing requires costly laser sources and is known to cause damages to the surrounding material. By comparison, continuous-wave lasers are cheap, stable and provide energy at a more moderate rate. Here, we show that a continuous-wave laser may be used to pattern vertical nano-crystalline graphite thin films with very few macroscale defects. Moreover, a spatially resolved study of the impact of the annealing to the crystalline structure and to the oxygen ingress in the film is provided: amorphization, matter removal and high oxygen content at the center of the beam; sp2 clustering and low oxygen content at its periphery. These data strongly suggest that amorphization and matter removal are controlled by carbon oxidation. The simultaneous occurrence of oxidation and amorphization results in a unique evolution of the Raman spectra as a function of annealing time, with a decrease of the I(D)/I(G) values but an upshift of the G peak frequency.

Studies on the synthesis, spectra, catalytic and antibacterial activities of binuclear ruthenium(II) complexes.

PubMed

Krishnamoorthy, P; Sathyadevi, P; Deepa, K; Dharmaraj, N

2010-09-15

A new series of stable binuclear ruthenium(II) carbonyl complexes of the general formula [{RuX(CO)(EPh(3))(2)}(2)L] (where X=H or Cl; E=P or As and L=dibasic tetradentate diacetyl resorcinol (H(2)-DAR)) have been synthesised by reacting ruthenium(II) starting complexes [RuHX(CO)(EPh(3))(3)] (where X=H or Cl; E=P or As) and 4,6-diacetylresorcinol (H(2)-DAR) ligand in benzene medium. The structure of the new binuclear ruthenium(II) carbonyl complexes was established using elemental analysis, spectra (FT-IR, UV-vis and (1)H NMR), electrochemical and thermal studies. In these reactions, the 4,6-diacetylresorcinol (H(2)-DAR) ligand behaves as a binegative tetradentate chelating ligand coordinating through O,O atoms of both the carbonyl and phenolic C-O groups by replacing a molecule of PPh(3)/AsPh(3) and a hydride ion from the starting complexes. Further, all these complexes were also employed as new catalysts for the oxidation of primary and secondary alcohols in the presence of N-methylmorpholine-N-oxide (NMO) as a more viable co-oxidant. The free ligand and their metal complexes have also been screened for their antibacterial activity against the growth of gram +ve and gram -ve bacterial cultures. Copyright 2010 Elsevier B.V. All rights reserved.

PRECIPITATION OF ZIRCONIUM, NIOBIUM, AND RUTHENIUM FROM AQUEOUS SOLUTIONS

DOEpatents

Wilson, A.S.

1958-08-12

An improvement on the"head end process" for decontaminating dissolver solutions of their Zr, Ni. and Ru values. The process consists in adding a water soluble symmetrical dialkyl ketone. e.g. acetone, before the formation of the manganese dioxide precipitate. The effect is that upon digestion, the ruthenium oxide does not volatilize, but is carried on the manganese dioxide precipitate.

Study on volatilization mechanism of ruthenium tetroxide from nitrosyl ruthenium nitrate by using mass spectrometer

NASA Astrophysics Data System (ADS)

Kato, Tetsuya; Usami, Tsuyoshi; Tsukada, Takeshi; Shibata, Yuki; Kodama, Takashi

2016-10-01

In a cooling malfunction accident of a high-level liquid waste (HLLW) tank, behavior of ruthenium (Ru) attracts much attention, since Ru could be oxidized to a volatile chemical form in the boiling and drying of HLLW, and part of radioactive Ru can potentially be released to the environment. In this study, nitrosyl Ru nitrate (Ru(NO)(NO3)3) dissolved in nitric acid (HNO3), which is commonly contained in a simulated HLLW, was dried and heated up to 723 K, and the evolved gas was introduced into a mass spectrometer. The well-known volatile species, ruthenium tetroxide (RuO4) was detected in a temperature range between 390 K and 500 K with the peak top around 440 K. Various gases such as HNO3, nitrogen dioxide (NO2), nitrogen monoxide (NO) also evolved due to evaporation of the nitric acid and decomposition of the nitrate ions. The ion current of RuO4 seems to increase with the increasing decomposition of nitrate, while the evaporation of HNO3 decreases. More volatilization of RuO4 was observed from the HNO3 solution containing not only Ru(NO)(NO3)3 but also cerium nitrate (Ce(NO3)3·6H2O) which was added for extra supply of nitrate ion, compared with that from the HNO3 solution containing only Ru(NO)(NO3)3. These experimental results suggest that Ru could be oxidized to form RuO4 by the nitrate ion as well as HNO3.

Tailoring the index of refraction of nanocrystalline hafnium oxide thin films

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

Vargas, Mirella; Murphy, N. R.; Ramana, C. V., E-mail: rvchintalapalle@utep.edu

2014-03-10

Hafnium oxide (HfO{sub 2}) films were grown by sputter-deposition by varying the growth temperature (T{sub s} = 25–700 °C). HfO{sub 2} films grown at T{sub s} < 200 °C were amorphous, while those grown at T{sub s} ≥ 200 °C were monoclinic, nanocrystalline with (1{sup ¯}11) texturing. X-ray reflectivity (XRR) analyses indicate that the film-density (ρ) increases with increasing T{sub s}. The index of refraction (n) profiles derived from spectroscopic ellipsometry analyses follow the Cauchy dispersion relation. Lorentz-Lorenz analysis (n{sub (λ)} = 550 nm) and optical-model adopted agree well with the XRR data/analyses. A direct T{sub s}-ρ-n relationship suggests that tailoring the optical quality is possible by tuning T{sub s} and themore » microstructure of HfO{sub 2} films.« less

Effects of surface crystallization and oxidation in nanocrystalline FeNbCuSiB(P) ribbons

NASA Astrophysics Data System (ADS)

Butvinová, B.; Butvin, P.; Brzózka, K.; Kuzminski, M.; Maťko, I.; Švec, P., Sr.; Chromčíková, M.

2017-02-01

Si-poor Fe74Nb3Cu1Si8B14-xPx, (x=0, 3) nanocrystalline ribbon-form alloys often form surfaces, which exert in-plane force on underlying ribbon interior when nanocrystallized in even modest presence of oxygen. Mostly unwanted hard-ribbon-axis magnetic anisotropy is standard result. Essential sources of the surface-caused stress have been sought and influence of P instead of B substitution on this effect was studied too. Preferred surface crystallization (PSC) was found to be the major reason. However P substitution suppresses PSC and promotes Fe-oxide formation, which eases the stress, softens the surfaces and provides different annealing evolution of surface properties.

Selective catalytic reduction system and process for treating NOx emissions using a palladium and rhodium or ruthenium catalyst

DOEpatents

Sobolevskiy, Anatoly [Orlando, FL; Rossin, Joseph A [Columbus, OH; Knapke, Michael J [Columbus, OH

2011-07-12

A process for the catalytic reduction of nitrogen oxides (NOx) in a gas stream (29) in the presence of H.sub.2 is provided. The process comprises contacting the gas stream with a catalyst system (38) comprising zirconia-silica washcoat particles (41), a pre-sulfated zirconia binder (44), and a catalyst combination (40) comprising palladium and at least one of rhodium, ruthenium, or a mixture of ruthenium and rhodium.

Tuning electronic properties by oxidation-reduction reactions at graphene-ruthenium interface

DOE PAGES

Kandyba, Viktor; Al-Mahboob, Abdullah; Giampietri, Alessio; ...

2018-06-06

Mass production of graphene is associated with the growth on catalysts used also in other chemical reactions. In this study, we exploit the oxidation-reduction to tailor the properties of single layer graphene domains with incorporated bi-layer patches on ruthenium. Using photoelectron spectromicroscopy techniques, we find that oxygen, intercalating under single layer and making it p-doped by the formation of Ru-O x, does not intercalate under the bilayer patches with n-doped upper layer, but decorates them under single layer surrounding creating lateral p-n junctions with chemical potential difference of 1.2 eV. O-reduction by thermal treatment in vacuum results in C-vacancy defectsmore » enhancing electronic coupling of remained graphene to Ru, whereas in H 2, vacancy formation is suppressed. Also, for the domains below 15–25 μm size, after O-reduction in H 2, graphene/Ru coupling is restored, while wrinkle pattern produced by O-intercalation is irreversible and can trap reaction products between the wrinkles and Ru surface step edges. In fact, in certain regions of bigger domains, the products, containing H 2O and/or its fragments, remain at the interface, making graphene decoupled and undoped.« less

Development and Application of Operando TEM to a Ruthenium Catalyst for CO Oxidation

NASA Astrophysics Data System (ADS)

Miller, Benjamin Kyle

Operando transmission electron microscopy (TEM) is an extension of in-situ TEM in which the performance of the material being observed is measured simultaneously. This is of great value, since structure-performance relationships lie at the heart of materials science. For catalyst materials, like the SiO2-supported Ru nanoparticles studied, the important performance metric, catalyst activity, is measured inside the microscope by determining the gas composition during imaging. This is accomplished by acquisition of electron energy loss spectra (EELS) of the gas in the environmental TEM while catalysis is taking place. In this work, automated methods for rapidly quantifying low-loss and core-loss EELS of gases were developed. A new sample preparation method was also established to increase catalytic conversion inside a differentially-pumped environmental TEM, and the maximum CO conversion observed was about 80%. A system for mixing gases and delivering them to the environmental TEM was designed and built, and a method for locating and imaging nanoparticles in zone axis orientations while minimizing electron dose rate was determined. After atomic resolution images of Ru nanoparticles observed during CO oxidation were obtained, the shape and surface structures of these particles was investigated. A Wulff model structure for Ru particles was compared to experimental images both by manually rotating the model, and by automatically determining a matching orientation using cross-correlation of shape signatures. From this analysis, it was determined that most Ru particles are close to Wulff-shaped during CO oxidation. While thick oxide layers were not observed to form on Ru during CO oxidation, thin RuO2 layers on the surface of Ru nanoparticles were imaged with atomic resolution for the first time. The activity of these layers is discussed in the context of the literature on the subject, which has thus far been inconclusive. We conclude that disordered oxidized ruthenium

Production of nanocrystalline metal powders via combustion reaction synthesis

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

Frye, John G.; Weil, Kenneth Scott; Lavender, Curt A.

Nanocrystalline metal powders comprising tungsten, molybdenum, rhenium and/or niobium can be synthesized using a combustion reaction. Methods for synthesizing the nanocrystalline metal powders are characterized by forming a combustion synthesis solution by dissolving in water an oxidizer, a fuel, and a base-soluble, ammonium precursor of tungsten, molybdenum, rhenium, or niobium in amounts that yield a stoichiometric burn when combusted. The combustion synthesis solution is then heated to a temperature sufficient to substantially remove water and to initiate a self-sustaining combustion reaction. The resulting powder can be subsequently reduced to metal form by heating in a reducing gas environment.

Nanocrystalline ceramic materials

DOEpatents

Siegel, Richard W.; Nieman, G. William; Weertman, Julia R.

1994-01-01

A method for preparing a treated nanocrystalline metallic material. The method of preparation includes providing a starting nanocrystalline metallic material with a grain size less than about 35 nm, compacting the starting nanocrystalline metallic material in an inert atmosphere and annealing the compacted metallic material at a temperature less than about one-half the melting point of the metallic material.

Study of Degradation Kinetics of Parathion Methyl On Mixed Nanocrystalline Titania-Zirconium and Titania-Cerium Oxides

NASA Astrophysics Data System (ADS)

Kuráň, Pavel; Pšenička, Martin; Šťastný, Martin; Benkocká, Monika; Janoš, Pavel

2016-10-01

The unique surface properties of some nanocrystalline metal oxides and their application for removal of various toxic compounds were reported in early 1990s. Recently, a reliable method for the preparation of reactive cerium dioxide sorbent and its application for degradation of the organophosphate pesticides, such as parathion methyl, chlorpyrifos, dichlofenthion, fenchlorphos, and prothiofos, as well as of some chemical warfare agents-nerve gases soman and O-ethyl S-[2-(diisopropylamino) ethyl] methylphosphonothioate (VX) was published. This paper reports on the kinetics study of degradation of parathion methyl as a representative organophosphate on nanocrystalline metal oxides TiO2, ZrO2, CeO2 and their mixtures in different molar ratios of particular elements. The tested sorbents except of CeO2 were prepared by different methods (e.g. sol-gel, precipitation) in cooperation with Institute of Inorganic Chemistry (Rez, Czech Republic). The degradation kinetics of parathion methyl on tested sorbents was followed by HPLC equipped with diode array detector. The basic kinetics parameters (half-lives of parathion methyl degradation, rate constants of degradation product formation) were calculated for each sorbent from Weber-Morris equation of 1st order diffusion kinetic model. The results proved the ability of prepared sorbents to degrade parathion methyl under formation of 4-nitrophenol as the main degradation product. The most efficient sorbents were TiCe (2:8), TiCe (1:1), TiCe (0:1) (50-70 %) followed by TiZr (1:1), TiCe (8:2), TiZr (8:2), TiZr (2:8) (20-30%) and TiO2, ZrO2 (less than 5 %).

Ruthenium nano-oxide layer in CoFe-Ru-CoFe trilayer system: An x-ray reflectivity study

NASA Astrophysics Data System (ADS)

Asgharizadeh, S.; Sutton, M.; Altounian, Z.; Mao, M.; Lee, C. L.

2008-05-01

A grazing incidence x-ray reflectivity technique is used to determine the electron density profile as a function of depth in CoFe-Ru-CoFe and CoFe-Ru nano-oxide layer (NOL)-CoFe trilayers. Four trilayers with ruthenium thicknesses of 8, 8.5, and 9Å and one with Ru 8.5Å NOL, prepared by a dc planetary sputtering system, were investigated. For all samples, the electron density profile (EDP) shows a central peak that is related to the Ru layer. Natural oxidation in all of the samples introduces a graded EDP of the top CoFe layers, which decreases gradually to zero. The large surface resistivity of Ru 8.5Å NOL as compared to Ru 8.5Å is related to the remarkable difference between their EDPs. EDP changes have also been investigated in Ru NOL trilayers after annealing at 280°C. The Ru phase in the EDP was observed to confirm the thermal stability of the spacer layer after annealing.

Nanocrystalline ceramic materials

DOEpatents

Siegel, R.W.; Nieman, G.W.; Weertman, J.R.

1994-06-14

A method is disclosed for preparing a treated nanocrystalline metallic material. The method of preparation includes providing a starting nanocrystalline metallic material with a grain size less than about 35 nm, compacting the starting nanocrystalline metallic material in an inert atmosphere and annealing the compacted metallic material at a temperature less than about one-half the melting point of the metallic material. 19 figs.

Polymer blend of PLA/PHBV based bionanocomposites reinforced with nanocrystalline cellulose for potential application as packaging material.

PubMed

Dasan, Y K; Bhat, A H; Ahmad, Faiz

2017-02-10

The current research discusses the development of poly (lactic acid) (PLA) and poly-(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) reinforced nanocrystalline cellulose bionanocomposites. The nanocrystalline cellulose was derived from waste oil palm empty fruit bunch fiber by acid hydrolysis process. The resulting nanocrystalline cellulose suspension was then surface functionalized by TEMPO-mediated oxidation and solvent exchange process. Furthermore, the PLA/PHBV/nanocrystalline cellulose bionanocomposites were produced by solvent casting method. The effect of the addition of nanocrystalline cellulose on structural, morphology, mechanical and barrier properties of bionanocomposites was investigated. The results revealed that the developed bionanocomposites showed improved mechanical properties and decrease in oxygen permeability rate. Therefore, the developed bio-based composite incorporated with an optimal composition of nanocrystalline cellulose exhibits properties as compared to the polymer blend. Copyright © 2016 Elsevier Ltd. All rights reserved.

Kinetics and Photochemistry of Ruthenium Bisbipyridine Diacetonitrile Complexes: An Interdisciplinary Inorganic and Physical Chemistry Laboratory Exercise.

PubMed

Rapp, Teresa L; Phillips, Susan R; Dmochowski, Ivan J

2016-12-13

The study of ruthenium polypyridyl complexes can be widely applied across disciplines in the undergraduate curriculum. Ruthenium photochemistry has advanced many fields including dye-sensitized solar cells, photoredox catalysis, light-driven water oxidation, and biological electron transfer. Equally promising are ruthenium polypyridyl complexes that provide a sterically bulky, photolabile moiety for transiently "caging" biologically active molecules. Photouncaging involves the use of visible (1-photon) or near-IR (2-photon) light to break one or more bonds between ruthenium and coordinated ligand(s), which can occur on short time scales and in high quantum yields. In this work we demonstrate the use of a model "caged" acetonitrile complex, Ru(2,2'-bipyridine) 2 (acetonitrile) 2 , or RuMeCN in an advanced synthesis and physical chemistry laboratory. Students made RuMeCN in an advanced synthesis laboratory course and performed UV-vis spectroscopy and electrochemistry. The following semester students investigated RuMeCN photolysis kinetics in a physical chemistry laboratory. These two exercises may also be combined to create a 2-week module in an advanced undergraduate laboratory course.

Kinetics and Photochemistry of Ruthenium Bisbipyridine Diacetonitrile Complexes: An Interdisciplinary Inorganic and Physical Chemistry Laboratory Exercise

PubMed Central

2016-01-01

The study of ruthenium polypyridyl complexes can be widely applied across disciplines in the undergraduate curriculum. Ruthenium photochemistry has advanced many fields including dye-sensitized solar cells, photoredox catalysis, light-driven water oxidation, and biological electron transfer. Equally promising are ruthenium polypyridyl complexes that provide a sterically bulky, photolabile moiety for transiently “caging” biologically active molecules. Photouncaging involves the use of visible (1-photon) or near-IR (2-photon) light to break one or more bonds between ruthenium and coordinated ligand(s), which can occur on short time scales and in high quantum yields. In this work we demonstrate the use of a model “caged” acetonitrile complex, Ru(2,2′-bipyridine)2(acetonitrile)2, or RuMeCN in an advanced synthesis and physical chemistry laboratory. Students made RuMeCN in an advanced synthesis laboratory course and performed UV–vis spectroscopy and electrochemistry. The following semester students investigated RuMeCN photolysis kinetics in a physical chemistry laboratory. These two exercises may also be combined to create a 2-week module in an advanced undergraduate laboratory course. PMID:28649139

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.

SOLVENT EXTRACTION OF RUTHENIUM

DOEpatents

Hyman, H.H.; Leader, G.R.

1959-07-14

The separation of rathenium from aqueous solutions by solvent extraction is described. According to the invention, a nitrite selected from the group consisting of alkali nitrite and alkaline earth nitrite in an equimolecular quantity with regard to the quantity of rathenium present is added to an aqueous solution containing ruthenium tetrantrate to form a ruthenium complex. Adding an organic solvent such as ethyl ether to the resulting mixture selectively extracts the rathenium complex.

Charge transfer from an adsorbed ruthenium-based photosensitizer through an ultra-thin aluminium oxide layer and into a metallic substrate

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

Gibson, Andrew J.; Temperton, Robert H.; Handrup, Karsten

2014-06-21

The interaction of the dye molecule N3 (cis-bis(isothiocyanato)bis(2,2-bipyridyl-4,4′-dicarbo-xylato) -ruthenium(II)) with the ultra-thin oxide layer on a AlNi(110) substrate, has been studied using synchrotron radiation based photoelectron spectroscopy, resonant photoemission spectroscopy, and near edge X-ray absorption fine structure spectroscopy. Calibrated X-ray absorption and valence band spectra of the monolayer and multilayer coverages reveal that charge transfer is possible from the molecule to the AlNi(110) substrate via tunnelling through the ultra-thin oxide layer and into the conduction band edge of the substrate. This charge transfer mechanism is possible from the LUMO+2 and 3 in the excited state but not from the LUMO,more » therefore enabling core-hole clock analysis, which gives an upper limit of 6.0 ± 2.5 fs for the transfer time. This indicates that ultra-thin oxide layers are a viable material for use in dye-sensitized solar cells, which may lead to reduced recombination effects and improved efficiencies of future devices.« less

Mechanical properties of nanocrystalline cobalt

NASA Astrophysics Data System (ADS)

Karimpoor, Amir A.; Erb, Uwe

2006-05-01

Due to their excellent wear and corrosion properties, nanocrystalline cobalt and several cobalt alloys made by electrodeposition are currently being developed as environmentally benign replacement coatings for hard chromium electrodeposits. The focus of this study is on the mechanical properties of nanocrystalline cobalt, which are currently not well understood. A comparison is presented for hardness, tensile properties, Charpy impact properties and fracture surface analysis of both nanocrystalline (grain size: 12 nm) and conventional polycrystalline (grain size: 4.8 m) cobalt. It is shown that the hardness and tensile strength of nanocrystalline cobalt is 2-3 times higher than for polycrystalline cobalt. However, in contrast to other nanocrystalline materials tested previously, nanocrystalline cobalt retains considerable ductility with elongation to fracture values up to 7%.

Platinum-ruthenium-palladium fuel cell electrocatalyst

DOEpatents

Gorer, Alexander

2006-02-07

A catalyst suitable for use in a fuel cell, especially as an anode catalyst, that contains platinum at a concentration that is between about 20 and about 60 atomic percent, ruthenium at a concentration that is between about 20 and about 60 atomic percent, palladium at a concentration that is between about 5 and about 45 atomic percent, and having an atomic ratio of platinum to ruthenium that is between about 0.7 and about 1.2. Alternatively, the catalyst may contain platinum at a concentration that is between about 25 and about 50 atomic percent, ruthenium at a concentration that is between about 25 and about 55 atomic percent, palladium at a concentration that is between about 5 and about 45 atomic percent, and having a difference between the concentrations of ruthenium and platinum that is no greater than about 20 atomic percent.

Synergistic oxygen atom transfer by ruthenium complexes with non-redox metal ions.

PubMed

Lv, Zhanao; Zheng, Wenrui; Chen, Zhuqi; Tang, Zhiming; Mo, Wanling; Yin, Guochuan

2016-07-28

Non-redox metal ions can affect the reactivity of active redox metal ions in versatile biological and heterogeneous oxidation processes; however, the intrinsic roles of these non-redox ions still remain elusive. This work demonstrates the first example of the use of non-redox metal ions as Lewis acids to sharply improve the catalytic oxygen atom transfer efficiency of a ruthenium complex bearing the classic 2,2'-bipyridine ligand. In the absence of Lewis acid, the oxidation of ruthenium(ii) complex by PhI(OAc)2 generates the Ru(iv)[double bond, length as m-dash]O species, which is very sluggish for olefin epoxidation. When Ru(bpy)2Cl2 was tested as a catalyst alone, only 21.2% of cyclooctene was converted, and the yield of 1,2-epoxycyclooctane was only 6.7%. As evidenced by electronic absorption spectra and EPR studies, both the oxidation of Ru(ii) by PhI(OAc)2 and the reduction of Ru(iv)[double bond, length as m-dash]O by olefin are kinetically slow. However, adding non-redox metal ions such as Al(iii) can sharply improve the oxygen transfer efficiency of the catalyst to 100% conversion with 89.9% yield of epoxide under identical conditions. Through various spectroscopic characterizations, an adduct of Ru(iv)[double bond, length as m-dash]O with Al(iii), Ru(iv)[double bond, length as m-dash]O/Al(iii), was proposed to serve as the active species for epoxidation, which in turn generated a Ru(iii)-O-Ru(iii) dimer as the reduced form. In particular, both the oxygen transfer from Ru(iv)[double bond, length as m-dash]O/Al(iii) to olefin and the oxidation of Ru(iii)-O-Ru(iii) back to the active Ru(iv)[double bond, length as m-dash]O/Al(iii) species in the catalytic cycle can be remarkably accelerated by adding a non-redox metal, such as Al(iii). These results have important implications for the role played by non-redox metal ions in catalytic oxidation at redox metal centers as well as for the understanding of the redox mechanism of ruthenium catalysts in the oxygen atom

Pulse I-V characterization of a nano-crystalline oxide device with sub-gap density of states

NASA Astrophysics Data System (ADS)

Kim, Taeho; Hur, Ji-Hyun; Jeon, Sanghun

2016-05-01

Understanding the charge trapping nature of nano-crystalline oxide semiconductor thin film transistors (TFTs) is one of the most important requirements for their successful application. In our investigation, we employed a fast-pulsed I-V technique for understanding the charge trapping phenomenon and for characterizing the intrinsic device performance of an amorphous/nano-crystalline indium-hafnium-zinc-oxide semiconductor TFT with varying density of states in the bulk. Because of the negligible transient charging effect with a very short pulse, the source-to-drain current obtained with the fast-pulsed I-V measurement was higher than that measured by the direct-current characterization method. This is because the fast-pulsed I-V technique provides a charge-trap free environment, suggesting that it is a representative device characterization methodology of TFTs. In addition, a pulsed source-to-drain current versus time plot was used to quantify the dynamic trapping behavior. We found that the charge trapping phenomenon in amorphous/nano-crystalline indium-hafnium-zinc-oxide TFTs is attributable to the charging/discharging of sub-gap density of states in the bulk and is dictated by multiple trap-to-trap processes.

Pulse I-V characterization of a nano-crystalline oxide device with sub-gap density of states.

PubMed

Kim, Taeho; Hur, Ji-Hyun; Jeon, Sanghun

2016-05-27

Understanding the charge trapping nature of nano-crystalline oxide semiconductor thin film transistors (TFTs) is one of the most important requirements for their successful application. In our investigation, we employed a fast-pulsed I-V technique for understanding the charge trapping phenomenon and for characterizing the intrinsic device performance of an amorphous/nano-crystalline indium-hafnium-zinc-oxide semiconductor TFT with varying density of states in the bulk. Because of the negligible transient charging effect with a very short pulse, the source-to-drain current obtained with the fast-pulsed I-V measurement was higher than that measured by the direct-current characterization method. This is because the fast-pulsed I-V technique provides a charge-trap free environment, suggesting that it is a representative device characterization methodology of TFTs. In addition, a pulsed source-to-drain current versus time plot was used to quantify the dynamic trapping behavior. We found that the charge trapping phenomenon in amorphous/nano-crystalline indium-hafnium-zinc-oxide TFTs is attributable to the charging/discharging of sub-gap density of states in the bulk and is dictated by multiple trap-to-trap processes.

Atomic layer deposition of ruthenium on plasma-treated vertically aligned carbon nanotubes for high-performance ultracapacitors.

PubMed

Kim, Jun Woo; Kim, Byungwoo; Park, Suk Won; Kim, Woong; Shim, Joon Hyung

2014-10-31

It is challenging to realize a conformal metal coating by atomic layer deposition (ALD) because of the high surface energy of metals. In this study, ALD of ruthenium (Ru) on vertically aligned carbon nanotubes (CNTs) was carried out. To activate the surface of CNTs that lack surface functional groups essential for ALD, oxygen plasma was applied ex situ before ALD. X-ray photoelectron spectroscopy and Raman spectroscopy confirmed surface activation of CNTs by the plasma pretreatment. Transmission electron microscopy analysis with energy-dispersive x-ray spectroscopy composition mapping showed that ALD Ru grew conformally along CNTs walls. ALD Ru/CNTs were electrochemically oxidized to ruthenium oxide (RuOx) that can be a potentially useful candidate for use in the electrodes of ultracapacitors. Electrode performance of RuOx/CNTs was evaluated using cyclic voltammetry and galvanostatic charge-discharge measurements.

In situ loading of well-dispersed silver nanoparticles on nanocrystalline magnesium oxide for real-time monitoring of catalytic reactions by surface enhanced Raman spectroscopy.

PubMed

Zhang, Kaige; Li, Gongke; Hu, Yuling

2015-10-28

The surface-enhanced Raman spectroscopy (SERS) technique is of great importance for insight into the transient reaction intermediates and mechanistic pathways involved in heterogeneously catalyzed chemical reactions under actual reaction conditions, especially in water. Herein, we demonstrate a facile method for in situ synthesis of nanocrystalline magnesium oxide-Ag(0) (nano MgO-Ag(0)) hybrid nanomaterials with dispersed Ag nanoparticles (Ag NPs) on the surface of nanocrystalline magnesium oxide (nano MgO) via Sn(2+) linkage and reduction. As a benefit from the synergy effect of nano MgO and Ag NPs, the nano MgO-Ag(0) exhibited both excellent SERS and catalytic activities for the reduction of 4-nitrothiophenol in the presence of NaBH4. The nano MgO-Ag(0) was used for real-time monitoring of the catalytic reaction process of 4-nitrothiophenol to 4-aminothiophenol in an aqueous medium by observing the SERS signals of the reactant, intermediate and final products. The intrinsic reaction kinetics and reaction mechanism of this reaction were also investigated. This SERS-based synergy technique provides a novel approach for quantitative in situ monitoring of catalytic chemical reaction processes.

Nanocrystalline films for gas-reactive applications

DOEpatents

Eastman, Jeffrey A.; Thompson, Loren J.

2004-02-17

A gas sensor for detection of oxidizing and reducing gases, including O.sub.2, CO.sub.2, CO, and H.sub.2, monitors the partial pressure of a gas to be detected by measuring the temperature rise of an oxide-thin-film-coated metallic line in response to an applied electrical current. For a fixed input power, the temperature rise of the metallic line is inversely proportional to the thermal conductivity of the oxide coating. The oxide coating contains multi-valent cation species that change their valence, and hence the oxygen stoichiometry of the coating, in response to changes in the partial pressure of the detected gas. Since the thermal conductivity of the coating is dependent on its oxygen stoichiometry, the temperature rise of the metallic line depends on the partial pressure of the detected gas. Nanocrystalline (<100 nm grain size) oxide coatings yield faster sensor response times than conventional larger-grained coatings due to faster oxygen diffusion along grain boundaries rather than through grain interiors.

Ruthenium red-induced bundling of bacterial cell division protein, FtsZ.

PubMed

Santra, Manas Kumar; Beuria, Tushar K; Banerjee, Abhijit; Panda, Dulal

2004-06-18

The assembly of FtsZ plays a major role in bacterial cell division, and it is thought that the assembly dynamics of FtsZ is a finely regulated process. Here, we show that ruthenium red is able to modulate FtsZ assembly in vitro. In contrast to the inhibitory effects of ruthenium red on microtubule polymerization, we found that a substoichiometric concentration of ruthenium red strongly increased the light-scattering signal of FtsZ assembly. Further, sedimentable polymer mass was increased by 1.5- and 2-fold in the presence of 2 and 10 microm ruthenium red, respectively. In addition, ruthenium red strongly reduced the GTPase activity and prevented dilution-induced disassembly of FtsZ polymers. Electron microscopic analysis showed that 4-10 microm of ruthenium red produced thick bundles of FtsZ polymers. The significant increase in the light-scattering signal and pelletable polymer mass in the presence of ruthenium red seemed to be due to the bundling of FtsZ protofilaments into larger polymers rather than the actual increase in the level of polymeric FtsZ. Furthermore, ruthenium red was found to copolymerize with FtsZ, and the copolymerization of substoichiometric amounts of ruthenium red with FtsZ polymers promoted cooperative assembly of FtsZ that produced large bundles. Calcium inhibited the binding of ruthenium red to FtsZ. However, a concentration of calcium 1000-fold higher than that of ruthenium red was required to produce similar effects on FtsZ assembly. Ruthenium red strongly modulated FtsZ polymerization, suggesting the presence of an important regulatory site on FtsZ and suggesting that a natural ligand, which mimics the action of ruthenium red, may regulate the assembly of FtsZ in bacteria.

Disorder induced semiconductor to metal transition and modifications of grain boundaries in nanocrystalline zinc oxide thin film

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

Singh, Fouran; Kumar, Vinod; Chaudhary, Babloo

2012-10-01

This paper report on the disorder induced semiconductor to metal transition (SMT) and modifications of grain boundaries in nanocrystalline zinc oxide thin film. Disorder is induced using energetic ion irradiation. It eliminates the possibility of impurities induced transition. However, it is revealed that some critical concentration of defects is needed for inducing such kind of SMT at certain critical temperature. Above room temperature, the current-voltage characteristics in reverse bias attributes some interesting phenomenon, such as electric field induced charge transfer, charge trapping, and diffusion of defects. The transition is explained by the defects induced disorder and strain in ZnO crystallitesmore » created by high density of electronic excitations.« less

Dual function catalysts. Dehydrogenation and asymmetric intramolecular Diels-Alder cycloaddition of N-hydroxy formate esters and hydroxamic acids: evidence for a ruthenium-acylnitroso intermediate.

PubMed

Chow, Chun P; Shea, Kenneth J

2005-03-23

The chiral ruthenium salen complex, 13b, functions as an efficient catalyst for the sequential oxidation and asymmetric Diels-Alder cycloaddition of hydroxamic acids and N-hydroxy formate esters. This result provides evidence for the formation of a ruthenium-nitroso formate (acyl nitroso) intermediate. The Diels-Alder precursors are prepared from simple building blocks, and the cycloadducts, bridged oxazinolactams, can serve as useful intermediates in organic synthesis.

Electroreduction of carbon monoxide to liquid fuel on oxide-derived nanocrystalline copper.

PubMed

Li, Christina W; Ciston, Jim; Kanan, Matthew W

2014-04-24

The electrochemical conversion of CO2 and H2O into liquid fuel is ideal for high-density renewable energy storage and could provide an incentive for CO2 capture. However, efficient electrocatalysts for reducing CO2 and its derivatives into a desirable fuel are not available at present. Although many catalysts can reduce CO2 to carbon monoxide (CO), liquid fuel synthesis requires that CO is reduced further, using H2O as a H(+) source. Copper (Cu) is the only known material with an appreciable CO electroreduction activity, but in bulk form its efficiency and selectivity for liquid fuel are far too low for practical use. In particular, H2O reduction to H2 outcompetes CO reduction on Cu electrodes unless extreme overpotentials are applied, at which point gaseous hydrocarbons are the major CO reduction products. Here we show that nanocrystalline Cu prepared from Cu2O ('oxide-derived Cu') produces multi-carbon oxygenates (ethanol, acetate and n-propanol) with up to 57% Faraday efficiency at modest potentials (-0.25 volts to -0.5 volts versus the reversible hydrogen electrode) in CO-saturated alkaline H2O. By comparison, when prepared by traditional vapour condensation, Cu nanoparticles with an average crystallite size similar to that of oxide-derived copper produce nearly exclusive H2 (96% Faraday efficiency) under identical conditions. Our results demonstrate the ability to change the intrinsic catalytic properties of Cu for this notoriously difficult reaction by growing interconnected nanocrystallites from the constrained environment of an oxide lattice. The selectivity for oxygenates, with ethanol as the major product, demonstrates the feasibility of a two-step conversion of CO2 to liquid fuel that could be powered by renewable electricity.

Effect of cadmium-selenide quantum dots on the conductivity and photoconductivity of nanocrystalline indium oxide

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

Il’in, A. S., E-mail: as.ilin@physics.msu.ru; Fantina, N. P.; Martyshov, M. N.

The effect of cadmium-selenide quantum dots addition on the electrical and photoelectric properties of nanocrystalline indium oxide with nanocrystal dimensions in the range from 7 to 40 nm is studied. By impedance spectroscopy, it is shown that the addition of quantum dots substantially influences the resistance of interfaces between In{sub 2}O{sub 3} crystals. A change in the character of the photoconductivity spectrum of In{sub 2}O{sub 3} upon the addition of CdSe quantum dots is detected, and it is established that this change depends on the In{sub 2}O{sub 3}-nanocrystal dimensions. An energy band diagram is proposed to explain the observed changemore » in the photoconductivity spectrum of In{sub 2}O{sub 3} upon the addition of CdSe quantum dots.« less

Process of forming catalytic surfaces for wet oxidation reactions

NASA Technical Reports Server (NTRS)

Jagow, R. B. (Inventor)

1977-01-01

A wet oxidation process was developed for oxidizing waste materials, comprising dissolved ruthenium salt in a reactant feed stream containing the waste materials. The feed stream is introduced into a reactor, and the reactor contents are then raised to an elevated temperature to effect deposition of a catalytic surface of ruthenium black on the interior walls of the reactor. The feed stream is then maintained in the reactor for a period of time sufficient to effect at least partial oxidation of the waste materials.

Metalorganic Chemical Vapor Deposition of Ruthenium-Doped Diamond like Carbon Films

NASA Technical Reports Server (NTRS)

Sunkara, M. K.; Ueno, M.; Lian, G.; Dickey, E. C.

2001-01-01

We investigated metalorganic precursor deposition using a Microwave Electron Cyclotron Resonance (ECR) plasma for depositing metal-doped diamondlike carbon films. Specifically, the deposition of ruthenium doped diamondlike carbon films was investigated using the decomposition of a novel ruthenium precursor, Bis(ethylcyclopentadienyl)-ruthenium (Ru(C5H4C2H5)2). The ruthenium precursor was introduced close to the substrate stage. The substrate was independently biased using an applied RF power. Films were characterized using Fourier Transform Infrared Spectroscopy (FTIR), Transmission Electron Microscopy (TEM) and Four Point Probe. The conductivity of the films deposited using ruthenium precursor showed strong dependency on the deposition parameters such as pressure. Ruthenium doped sample showed the presence of diamond crystallites with an average size of approx. 3 nm while un-doped diamondlike carbon sample showed the presence of diamond crystallites with an average size of 11 nm. TEM results showed that ruthenium was atomically dispersed within the amorphous carbon network in the films.

Reaction of a (Salen)ruthenium(VI) nitrido complex with thiols. C-H bond activation by (Salen)ruthenium(IV) sulfilamido species.

PubMed

Man, Wai-Lun; Lam, William W Y; Kwong, Hoi-Ki; Peng, Shie-Ming; Wong, Wing-Tak; Lau, Tai-Chu

2010-01-04

The reaction of [Ru(VI)(N)(L)(MeOH)](PF(6)) [1; L = N,N'-bis(salicylidene)-o-cyclohexyldiamine dianion] with a stoichiometric amount of RSH in CH(3)CN gives the corresponding (salen)ruthenium(IV) sulfilamido species [Ru(IV){N(H)SR}(L)(NCCH(3))](PF(6)) (2a, R = (t)Bu; 2b, R = Ph). Metathesis of 2a with NaN(3) in methanol affords [Ru(IV){N(H)S(t)Bu}(L)(N(3))] (2c). 2a undergoes further reaction with 1 equiv of RSH to afford a (salen)ruthenium(III) sulfilamine species, [Ru(III){N(H)(2)S(t)Bu}(L)(NCCH(3))](PF(6)) (3). On the other hand, 2b reacts with 2 equiv of PhSH to give a (salen)ruthenium(III) ammine species [Ru(III)(NH(3))(L)(NCCH(3))](PF(6)) (4); this species can also be prepared by treatment of 1 with 3 equiv of PhSH. The X-ray structures of 2c and 4 have been determined. Kinetic studies of the reaction of 1 with excess RSH indicate the following schemes: 1 --> 2a --> 3 (R = (t)Bu), 1 --> 2b --> 4 (R = Ph). The conversion of 1 to 2 probably involves nucleophilic attack of RSH at the nitrido ligand, followed by a proton shift. The conversions of 2a to 3 and 2b to 4 are proposed to involve rate-limiting H-atom abstraction from RSH by 2a or 2b. 2a and 2b are also able to abstract H atoms from hydrocarbons with weak C-H bonds. These reactions occur with large deuterium isotope effects; the kinetic isotope effect values for the oxidation of 9,10-dihydroanthracene, 1,4-cyclohexadiene, and fluorene by 2a are 51, 56, and 11, respectively.

METABOLISM OF RUTHENIUM IN THE RAT. Technical Documentary Report

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

Traynor, J.E.; Leeper, S.W.

1961-12-01

Seventeen Sprague-Dawley rats were injected intramuscularly and intraperitoneally with ruthenium-106. The amount of this isotope was determined daily for 5 weeks in the urine and feces. Animals were sacrificed at intervals and the various organs were analyzed for ruthenium. It was noted from this experiment that the pathways of absorption, metabolism, and excretion are dependent on the route of administration of ruthenium. (auth)

Effect of Temperature on Nucleation of Nanocrystalline Indium Tin Oxide Synthesized by Electron-Beam Evaporation

NASA Astrophysics Data System (ADS)

Shen, Yan; Zhao, Yujun; Shen, Jianxing; Xu, Xiangang

2017-07-01

Indium tin oxide (ITO) has been widely applied as a transparent conductive layer and optical window in light-emitting diodes, solar cells, and touch screens. In this paper, crystalline nano-sized ITO dendrites are obtained using an electron-beam evaporation technique. The surface morphology of the obtained ITO was studied for substrate temperatures of 25°C, 130°C, 180°C, and 300°C. Nano-sized crystalline dendrites were synthesized only at a substrate temperature of 300°C. The dendrites had a cubic structure, confirmed by the results of x-ray diffraction and transmission electron microscopy. The growth mechanism of the nano-crystalline dendrites could be explained by a vapor-liquid-solid (VLS) growth model. The catalysts of the VLS process were indium and tin droplets, confirmed by varying the substrate temperature, which further influenced the nucleation of the ITO dendrites.

Hydrous Ruthenium Oxide Nanoparticles Anchored to Graphene and Carbon Nanotube Hybrid Foam for Supercapacitors

PubMed Central

Wang, Wei; Guo, Shirui; Lee, Ilkeun; Ahmed, Kazi; Zhong, Jiebin; Favors, Zachary; Zaera, Francisco; Ozkan, Mihrimah; Ozkan, Cengiz S.

2014-01-01

In real life applications, supercapacitors (SCs) often can only be used as part of a hybrid system together with other high energy storage devices due to their relatively lower energy density in comparison to other types of energy storage devices such as batteries and fuel cells. Increasing the energy density of SCs will have a huge impact on the development of future energy storage devices by broadening the area of application for SCs. Here, we report a simple and scalable way of preparing a three-dimensional (3D) sub-5 nm hydrous ruthenium oxide (RuO2) anchored graphene and CNT hybrid foam (RGM) architecture for high-performance supercapacitor electrodes. This RGM architecture demonstrates a novel graphene foam conformally covered with hybrid networks of RuO2 nanoparticles and anchored CNTs. SCs based on RGM show superior gravimetric and per-area capacitive performance (specific capacitance: 502.78 F g−1, areal capacitance: 1.11 F cm−2) which leads to an exceptionally high energy density of 39.28 Wh kg−1 and power density of 128.01 kW kg−1. The electrochemical stability, excellent capacitive performance, and the ease of preparation suggest this RGM system is promising for future energy storage applications. PMID:24663242

Hydrous ruthenium oxide nanoparticles anchored to graphene and carbon nanotube hybrid foam for supercapacitors

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

Wang, Wei; Guo, S.; Lee, I.

2014-03-25

In real life applications, supercapacitors (SCs) often can only be used as part of a hybrid system together with other high energy storage devices due to their relatively lower energy density in comparison to other types of energy storage devices such as batteries and fuel cells. Increasing the energy density of SCs will have a huge impact on the development of future energy storage devices by broadening the area of application for SCs. Here, we report a simple and scalable way of preparing a three-dimensional (3D) sub-5 nm hydrous ruthenium oxide (RuO₂) anchored graphene and CNT hybrid foam (RGM) architecturemore » for high-performance supercapacitor electrodes. This RGM architecture demonstrates a novel graphene foam conformally covered with hybrid networks of RuO₂ nanoparticles and anchored CNTs. SCs based on RGM show superior gravimetric and per-area capacitive performance (specific capacitance: 502.78 F g⁻¹, areal capacitance: 1.11 F cm⁻²) which leads to an exceptionally high energy density of 39.28 Wh kg⁻¹ and power density of 128.01 kW kg⁻¹. The electrochemical stability, excellent capacitive performance, and the ease of preparation suggest this RGM system is promising for future energy storage applications.« less

Thermally Stable Nanocrystalline Steel

NASA Astrophysics Data System (ADS)

Hulme-Smith, Christopher Neil; Ooi, Shgh Woei; Bhadeshia, Harshad K. D. H.

2017-10-01

Two novel nanocrystalline steels were designed to withstand elevated temperatures without catastrophic microstructural changes. In the most successful alloy, a large quantity of nickel was added to stabilize austenite and allow a reduction in the carbon content. A 50 kg cast of the novel alloy was produced and used to verify the formation of nanocrystalline bainite. Synchrotron X-ray diffractometry using in situ heating showed that austenite was able to survive more than 1 hour at 773 K (500 °C) and subsequent cooling to ambient temperature. This is the first reported nanocrystalline steel with high-temperature capability.

Multiple electron injection dynamics in linearly-linked two dye co-sensitized nanocrystalline metal oxide electrodes for dye-sensitized solar cells.

PubMed

Shen, Qing; Ogomi, Yuhei; Park, Byung-wook; Inoue, Takafumi; Pandey, Shyam S; Miyamoto, Akari; Fujita, Shinsuke; Katayama, Kenji; Toyoda, Taro; Hayase, Shuzi

2012-04-07

Understanding the electron transfer dynamics at the interface between dye sensitizer and semiconductor nanoparticle is very important for both a fundamental study and development of dye-sensitized solar cells (DSCs), which are a potential candidate for next generation solar cells. In this study, we have characterized the ultrafast photoexcited electron dynamics in a newly produced linearly-linked two dye co-sensitized solar cell using both a transient absorption (TA) and an improved transient grating (TG) technique, in which tin(IV) 2,11,20,29-tetra-tert-butyl-2,3-naphthalocyanine (NcSn) and cis-diisothiocyanato-bis(2,2'-bipyridyl-4,4'-dicarboxylato)ruthenium(II) bis(tetrabutylammonium) (N719) are molecularly and linearly linked and are bonded to the surface of a nanocrystalline tin dioxide (SnO(2)) electrode by a metal-O-metal linkage (i.e. SnO(2)-NcSn-N719). By comparing the TA and TG kinetics of NcSn, N719, and hybrid NcSn-N719 molecules adsorbed onto both of the SnO(2) and zirconium dioxide (ZrO(2)) nanocrystalline films, the forward and backward electron transfer dynamics in SnO(2)-NcSn-N719 were clarified. We found that there are two pathways for electron injection from the linearly-linked two dye molecules (NcSn-N719) to SnO(2). The first is a stepwise electron injection, in which photoexcited electrons first transfer from N719 to NcSn with a transfer time of 0.95 ps and then transfer from NcSn to the conduction band (CB) of SnO(2) with two timescales of 1.6 ps and 4.2 ps. The second is direct photoexcited electron transfer from N719 to the CB of SnO(2) with a timescale of 20-30 ps. On the other hand, back electron transfer from SnO(2) to NcSn is on a timescale of about 2 ns, which is about three orders of magnitude slower compared to the forward electron transfer from NcSn to SnO(2). The back electron transfer from NcSn to N719 is on a timescale of about 40 ps, which is about one order slower compared to the forward electron transfer from N719 to Nc

Silicon heterojunction solar cells with novel fluorinated n-type nanocrystalline silicon oxide emitters on p-type crystalline silicon

NASA Astrophysics Data System (ADS)

Dhar, Sukanta; Mandal, Sourav; Das, Gourab; Mukhopadhyay, Sumita; Pratim Ray, Partha; Banerjee, Chandan; Barua, Asok Kumar

2015-08-01

A novel fluorinated phosphorus doped silicon oxide based nanocrystalline material have been used to prepare heterojunction solar cells on flat p-type crystalline silicon (c-Si) Czochralski (CZ) wafers. The n-type nc-SiO:F:H material were deposited by radio frequency plasma enhanced chemical vapor deposition. Deposited films were characterized in detail by using atomic force microscopy (AFM), high resolution transmission electron microscopy (HRTEM), Raman, fourier transform infrared spectroscopy (FTIR) and optoelectronics properties have been studied using temperature dependent conductivity measurement, Ellipsometry, UV-vis spectrum analysis etc. It is observed that the cell fabricated with fluorinated silicon oxide emitter showing higher initial efficiency (η = 15.64%, Jsc = 32.10 mA/cm2, Voc = 0.630 V, FF = 0.77) for 1 cm2 cell area compare to conventional n-a-Si:H emitter (14.73%) on flat c-Si wafer. These results indicate that n type nc-SiO:F:H material is a promising candidate for heterojunction solar cell on p-type crystalline wafers. The high Jsc value is associated with excellent quantum efficiencies at short wavelengths (<500 nm).

Layer-by-layer grown scalable redox-active ruthenium-based molecular multilayer thin films for electrochemical applications and beyond.

PubMed

Kaliginedi, Veerabhadrarao; Ozawa, Hiroaki; Kuzume, Akiyoshi; Maharajan, Sivarajakumar; Pobelov, Ilya V; Kwon, Nam Hee; Mohos, Miklos; Broekmann, Peter; Fromm, Katharina M; Haga, Masa-aki; Wandlowski, Thomas

2015-11-14

Here we report the first study on the electrochemical energy storage application of a surface-immobilized ruthenium complex multilayer thin film with anion storage capability. We employed a novel dinuclear ruthenium complex with tetrapodal anchoring groups to build well-ordered redox-active multilayer coatings on an indium tin oxide (ITO) surface using a layer-by-layer self-assembly process. Cyclic voltammetry (CV), UV-Visible (UV-Vis) and Raman spectroscopy showed a linear increase of peak current, absorbance and Raman intensities, respectively with the number of layers. These results indicate the formation of well-ordered multilayers of the ruthenium complex on ITO, which is further supported by the X-ray photoelectron spectroscopy analysis. The thickness of the layers can be controlled with nanometer precision. In particular, the thickest layer studied (65 molecular layers and approx. 120 nm thick) demonstrated fast electrochemical oxidation/reduction, indicating a very low attenuation of the charge transfer within the multilayer. In situ-UV-Vis and resonance Raman spectroscopy results demonstrated the reversible electrochromic/redox behavior of the ruthenium complex multilayered films on ITO with respect to the electrode potential, which is an ideal prerequisite for e.g. smart electrochemical energy storage applications. Galvanostatic charge-discharge experiments demonstrated a pseudocapacitor behavior of the multilayer film with a good specific capacitance of 92.2 F g(-1) at a current density of 10 μA cm(-2) and an excellent cycling stability. As demonstrated in our prototypical experiments, the fine control of physicochemical properties at nanometer scale, relatively good stability of layers under ambient conditions makes the multilayer coatings of this type an excellent material for e.g. electrochemical energy storage, as interlayers in inverted bulk heterojunction solar cell applications and as functional components in molecular electronics applications.

Reduced Graphene Oxide-Immobilized Tris(bipyridine)ruthenium(II) Complex for Efficient Visible-Light-Driven Reductive Dehalogenation Reaction.

PubMed

Li, Xiaoyan; Hao, Zhongkai; Zhang, Fang; Li, Hexing

2016-05-18

A sodium benzenesulfonate (PhSO3Na)-functionalized reduced graphene oxide was synthesized via a two-step aryl diazonium coupling and subsequent NaCl ion-exchange procedure, which was used as a support to immobilize tris(bipyridine)ruthenium(II) complex (Ru(bpy)3Cl2) by coordination reaction. This elaborated Ru(bpy)3-rGO catalyst exhibited excellent catalytic efficiency in visible-light-driven reductive dehalogenation reactions under mild conditions, even for ary chloride. Meanwhile, it showed the comparable reactivity with the corresponding homogeneous Ru(bpy)3Cl2 catalyst. This high catalytic performance could be attributed to the unique two-dimensional sheet-like structure of Ru(bpy)3-rGO, which efficiently diminished diffusion resistance of the reactants. Meanwhile, the nonconjugated PhSO3Na-linkage between Ru(II) complex and the support and the very low electrical conductivity of the catalyst inhibited energy/electron transfer from Ru(II) complex to rGO support, resulting in the decreased support-induced quenching effect. Furthermore, it could be easily recycled at least five times without significant loss of catalytic reactivity.

Insights into the Binding Sites of Organometallic Ruthenium Anticancer Compounds on Peptides Using Ultra-High Resolution Mass Spectrometry

NASA Astrophysics Data System (ADS)

Wills, Rebecca H.; Habtemariam, Abraha; Lopez-Clavijo, Andrea F.; Barrow, Mark P.; Sadler, Peter J.; O'Connor, Peter B.

2014-04-01

The binding sites of two ruthenium(II) organometallic complexes of the form [(η6-arene)Ru( N, N)Cl]+, where arene/ N, N = biphenyl (bip)/bipyridine (bipy) for complex AH076, and biphenyl (bip)/ o-phenylenediamine ( o-pda) for complex AH078, on the peptides angiotensin and bombesin have been investigated using Fourier transform ion cyclotron resonance (FTICR) mass spectrometry. Fragmentation was performed using collisionally activated dissociation (CAD), with, in some cases, additional data being provided by electron capture dissociation (ECD). The primary binding sites were identified as methionine and histidine, with further coordination to phenylalanine, potentially through a π-stacking interaction, which has been observed here for the first time. This initial peptide study was expanded to investigate protein binding through reaction with insulin, on which the binding sites proposed are histidine, glutamic acid, and tyrosine. Further reaction of the ruthenium complexes with the oxidized B chain of insulin, in which two cysteine residues are oxidized to cysteine sulfonic acid (Cys-SO3H), and glutathione, which had been oxidized with hydrogen peroxide to convert the cysteine to cysteine sulfonic acid, provided further support for histidine and glutamic acid binding, respectively.

Molecular level energy and electron transfer processes at nanocrystalline titanium dioxide interfaces

NASA Astrophysics Data System (ADS)

Farzad, Fereshteh

This thesis describes photo-induced molecular electron and energy transfer processes occurring at nanocrystalline semiconductor interfaces. The Introductory Chapter provides background and describes how these materials may be useful for solar energy conversion. In Chapter 2, results describing excitation of Ru(deeb)(bpy)2 2+, bis(2,2'-bipyridine)(2,2'-bipyridine-4,4 '-diethylester)ruthenium(II) hexafluorophosphate, bound to nanocrystalline TiO2 thin films, immersed in an acetonitrile bath are presented. The data indicates that light excitation forms predominately long-lived metal-to-ligand charge-transfer, MLCT, excited states under these conditions. Modeling of the data as a function of irradiance has been accomplished assuming parallel unimolecular and bimolecular excited state deactivation processes. The quantum yield for excited state formation depends on the excitation irradiance, consistent with triplet-triplet annihilation processes that occur with k > 1 x 108 s-1. Chapter 3 extends the work described in Chapter 2 to LiClO4 acetonitrile solutions. Li+ addition results in a red shift in the MLCT absorption and photoluminescence, PL, and a concentration dependent quenching of the PL intensity on TiO2. The Li+ induced spectroscopic changes were found to be reversible by varying the electrolyte composition. A second-order kinetic model quantified charge recombination transients. A model is proposed wherein Li+ ion adsorption stabilizes TiO2 acceptor states resulting in energetically more favorable interfacial electron transfer. The photophysical and photoelectrochemical properties of porous nanocrystalline anatase TiO2 electrodes modified with Ru(deeb)(bpy)2 2+, Os(deeb)(bpy)22+, and mixtures of both are described in Chapters 4 and 5. In regenerative solar cells with 0.5 M LiI/0.05 M I2 acetonitrile electrolyte, both compounds efficiently inject electrons into TiO2 producing monochromatic incident photon-to-current efficiencies (IPCE), IPCE (460 nm) = 0.70 + 0

Infrared photocurrent management in monolithic perovskite/silicon heterojunction tandem solar cells by using a nanocrystalline silicon oxide interlayer.

PubMed

Mazzarella, Luana; Werth, Matteo; Jäger, Klaus; Jošt, Marko; Korte, Lars; Albrecht, Steve; Schlatmann, Rutger; Stannowski, Bernd

2018-05-14

We performed optical simulations using hydrogenated nanocrystalline silicon oxide (nc-SiO x :H) as n-doped interlayer in monolithic perovskite/c-Si heterojunction tandem solar cells. Depending on the adjustable value of its refractive index (2.0 - 2.7) and thickness, nc-SiO x :H allows to optically manage the infrared light absorption in the c-Si bottom cell minimizing reflection losses. We give guidelines for nc-SiO x :H optimization in tandem devices in combination with a systematic investigation of the effect of the surface morphology (flat or textured) on the photocurrent density. For full-flat and rear textured devices, we found matched photocurrents higher than 19 and 20 mA/cm 2 , respectively, using a 90 nm nc-SiO x :H interlayer with a refractive index of 2.7.

Synthesis of PVP-stabilized ruthenium colloids with low boiling point alcohols.

PubMed

Zhang, Yuqing; Yu, Jiulong; Niu, Haijun; Liu, Hanfan

2007-09-15

A route to the preparation of poly(N-vinyl-2-pyrrolidone) (PVP)-stabilized ruthenium colloids by refluxing ruthenium(III) chloride in low boiling point alcohols was developed. Deep purple colloids with shuttle-like ruthenium particles were also synthesized. XPS measurement verified the nanoparticles were in the metallic state. The morphology of metal nanoparticles was characterized by UV-visible absorption spectrophotometry, TEM and XRD.

Ruthenium nanocatalysis on redox reactions.

PubMed

Veerakumar, Pitchaimani; Ramdass, Arumugam; Rajagopal, Seenivasan

2013-07-01

Nanoparticles have generated intense interest over the past 20 years due to their high potential applications in different areas such as catalysis, sensors, nanoscale electronics, fuel and solar cells and optoelectronics. As the large fractions of metal atoms are exposed to the surface, the use of metal nanoparticles as nanocatalysts allows mild reaction conditions and high catalytic efficiency in a large number of chemical transformations. They have emerged as sustainable heterogeneous catalysts and catalyst supports alternative to conventional materials. This review focuses on the synthesis, characterization and catalytic role of ruthenium nanoparticles (RuNPs) on the redox reactions of heteroatom containing organic compounds with the green reagent H2O2, a field that has attracted immense interest among the chemical, materials and industrial communities. We intend to present a broad overview of Ru nanocatalysts for redox reactions with an emphasis on their performance, stability and reusability. The growth in the chemistry of organic sulfoxides and N-oxides during last decade was due to their importance as synthetic intermediates for the production of a wide range of chemically and biologically active molecules. Thus design of efficient methods for the synthesis of sulfoxides and N-oxides becomes important. This review concentrates on the catalysis of RuNPs on the H2O2 oxidation of organic sulfides to sulfoxides and amines to N-oxides. The deoxygenation reactions of sulfoxides to sulfides and reduction of nitro compounds to amines are fundamental reactions in both chemistry and biology. Here, we also highlight the catalysis of metal nanoparticles on the deoxygenation of sulfoxides and sulfones and reduction of nitro compounds with particular emphasis on the mechanistic aspects.

Kinetic effects of sulfur oxidation on catalytic nitrile hydration: nitrile hydratase insights from bioinspired ruthenium(II) complexes.

PubMed

Kumar, Davinder; Nguyen, Tho N; Grapperhaus, Craig A

2014-12-01

Kinetic investigations inspired by the metalloenzyme nitrile hydratase were performed on a series of ruthenium(II) complexes to determine the effect of sulfur oxidation on catalytic nitrile hydration. The rate of benzonitrile hydration was quantified as a function of catalyst, nitrile, and water concentrations. Precatalysts L(n)RuPPh3 (n = 1-3; L(1) = 4,7-bis(2'-methyl-2'-mercapto-propyl)-1-thia-4,7-diazacyclononane; L(2) = 4-(2'-methyl-2'-sulfinatopropyl)-7-(2'-methyl-2'-mercapto-propyl)-1-thia-4,7-diazacyclononane; L(3) = 4-(2'-methyl-2'-sulfinatopropyl)-7-(2'-methyl-2'-sulfenato-propyl)-1-thia-4,7-diazacyclononane) were activated by substitution of triphenylphosphine with substrate in hot dimethylformamide solution. Rate measurements are consistent with a dynamic equilibrium between inactive aqua (L(n)Ru-OH2) and active nitrile (L(n)Ru-NCR) derivatives with K = 21 ± 1, 9 ± 0.9, and 23 ± 3 for L(1) to L(3), respectively. Subsequent hydration of the L(n)Ru-NCR intermediate yields the amide product with measured hydration rate constants (k's) of 0.37 ± 0.01, 0.82 ± 0.07, and 1.59 ± 0.12 M(-1) h(-1) for L(1) to L(3), respectively. Temperature dependent studies reveal that sulfur oxidation lowers the enthalpic barrier by 27 kJ/mol, but increases the entropic barrier by 65 J/(mol K). Density functional theory (DFT) calculations (B3LYP/LanL2DZ (Ru); 6-31G(d) (all other atoms)) support a nitrile bound catalytic cycle with lowering of the reaction barrier as a consequence of sulfur oxidation through enhanced nitrile binding and attack of the water nucleophile through a highly organized transition state.

Using ruthenium polypyridyl functionalized ZnO mesocrystals and gold nanoparticle dotted graphene composite for biological recognition and electrochemiluminescence biosensing

NASA Astrophysics Data System (ADS)

Liu, Suli; Zhang, Jinxing; Tu, Wenwen; Bao, Jianchun; Dai, Zhihui

2014-01-01

Using ruthenium polypyridyl functionalized ZnO mesocrystals as bionanolabels, a universal biological recognition and biosensing platform based on gold nanoparticle (AuNP) dotted reduced graphene oxide (rGO) composite was developed. AuNP-rGO accelerated electron transfer between the detection probe and the electrode, and increased the surface area of the working electrode to load greater amounts of the capture antibodies. The large surface area of ZnO mesocrystals was beneficial for loading a high content ruthenium polypyridyl complex, leading to an enhanced electrochemiluminescence signal. Using α-fetoprotein (AFP) as a model, a simple and sensitive sandwich-type electrochemiluminescence biosensor with tripropylamine (TPrA) as a coreactant for detection of AFP was constructed. The designed biosensor provided a good linear range from 0.04 to 500 ng mL-1 with a low detection limit of 0.031 ng mL-1 at a S/N of 3 for AFP determination. The proposed biological recognition and biosensing platform extended the application of ruthenium polypyridyl functionalized ZnO mesocrystals, which provided a new promising prospect.

PROCESS FOR DECONTAMINATING THORIUM AND URANIUM WITH RESPECT TO RUTHENIUM

DOEpatents

Meservey, A.A.; Rainey, R.H.

1959-10-20

The control of ruthenium extraction in solvent-extraction processing of neutron-irradiated thorium is presented. Ruthenium is rendered organic-insoluble by the provision of sulfite or bisulfite ions in the aqueous feed solution. As a result the ruthenium remains in the aqueous phase along with other fission product and protactinium values, thorium and uranium values being extracted into the organic phase. This process is particularly applicable to the use of a nitrate-ion-deficient aqueous feed solution and to the use of tributyl phosphate as the organic extractant.

Oriented conductive oxide electrodes on SiO2/Si and glass

DOEpatents

Jia, Quanxi; Arendt, Paul N.

2001-01-01

A thin film structure is provided including a silicon substrate with a layer of silicon dioxide on a surface thereof, and a layer of cubic oxide material deposited upon the layer of silicon dioxide by ion-beam-assisted-deposition, said layer of cubic oxide material characterized as biaxially oriented. Preferably, the cubic oxide material is yttria-stabilized zirconia. Additional thin layers of biaxially oriented ruthenium oxide or lanthanum strontium cobalt oxide are deposited upon the layer of yttria-stabilized zirconia. An intermediate layer of cerium oxide is employed between the yttria-stabilized zirconia layer and the lanthanum strontium cobalt oxide layer. Also, a layer of barium strontium titanium oxide can be upon the layer of biaxially oriented ruthenium oxide or lanthanum strontium cobalt oxide. Also, a method of forming such thin film structures, including a low temperature deposition of a layer of a biaxially oriented cubic oxide material upon the silicon dioxide surface of a silicon dioxide/silicon substrate is provided.

Oxidation of Bromide to Bromine by Ruthenium(II) Bipyridine-Type Complexes Using the Flash-Quench Technique.

PubMed

Tsai, Kelvin Yun-Da; Chang, I-Jy

2017-07-17

Six ruthenium complexes, [Ru(bpy) 3 ] 2+ (1), [Ru(bpy) 2 (deeb)] 2+ (2), [Ru(deeb) 2 (dmbpy)] 2+ (3), [Ru(deeb) 2 (bpy)] 2+ (4), [Ru(deeb) 3 ] 2+ (5), and [Ru(deeb) 2 (bpz)] 2+ (6) (bpy: 2,2'-bipyridine; deeb: 4,4'-diethylester-2,2'-bipyridine; dmbpy: 4,4'-dimethyl-2,2'-bipyridine, bpz: 2,2'-bipyrazine), have been employed to sensitize photochemical oxidation of bromide to bromine. The oxidation potential for complexes 1-6 are 1.26, 1.36, 1.42, 1.46, 1.56, and 1.66 V vs SCE, respectively. The bimolecular rate constants for the quenching of complexes 1-6 by ArN 2 + (bromobenzenediazonium) are determined as 1.1 × 10 9 , 1.6 × 10 8 , 1.4 × 10 8 , 1.2 × 10 8 , 6.4 × 10 7 , and 8.9 × 10 6 M -1 s -1 , respectively. Transient kinetics indicated that Br - reacted with photogenerated Ru(III) species at different rates. Bimolecular rate constants for the oxidation of Br - by the Ru(III) species derived from complexes 1-5 are observed as 1.2 × 10 8 , 1.3 × 10 9 , 4.0 × 10 9 , 4.8 × 10 9 , and 1.1 × 10 10 , M -1 s -1 , respectively. The last reaction kinetics observed in the three-component system consisting of a Ru sensitizer, quencher, and bromide is shown to be independent of the Ru sensitizer. The final product was identified as bromine by its reaction with hexene. The last reaction kinetics is assigned to the disproportionation reaction of Br 2 -• ions, for which the rate constant is determined as 5 × 10 9 M -1 s -1 . Though complex 6 has the highest oxidation potential in the Ru(II)/Ru(III) couple, its excited state fails to react with ArN 2 + sufficiently for subsequent reactions. The Ru(III) species derived from complex 1 reacts with Br - at the slowest rate. Complexes 2-5 are excellent photosensitizers to drive photooxidation of bromide to bromine.

Stabilized tin-oxide-based oxidation/reduction catalysts

NASA Technical Reports Server (NTRS)

Watkins, Anthony Neal (Inventor); Oglesby, Donald M. (Inventor); Gulati, Suresh T. (Inventor); Summers, Jerry C. (Inventor); Schryer, David R. (Inventor); Davis, Patricia P. (Inventor); Leighty, Bradley D. (Inventor); Jordan, Jeffrey D. (Inventor); Schryer, Jacqueline L. (Inventor)

2008-01-01

The invention described herein involves a novel approach to the production of oxidation/reduction catalytic systems. The present invention serves to stabilize the tin oxide reducible metal-oxide coating by co-incorporating at least another metal-oxide species, such as zirconium. In one embodiment, a third metal-oxide species is incorporated, selected from the group consisting of cerium, lanthanum, hafnium, and ruthenium. The incorporation of the additional metal oxide components serves to stabilize the active tin-oxide layer in the catalytic process during high-temperature operation in a reducing environment (e.g., automobile exhaust). Moreover, the additional metal oxides are active components due to their oxygen-retention capabilities. Together, these features provide a mechanism to extend the range of operation of the tin-oxide-based catalyst system for automotive applications, while maintaining the existing advantages.

Solid state consolidation nanocrystalline copper-tungsten using cold spray

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

Hall, Aaron Christopher; Sarobol, Pylin; Argibay, Nicolas

It is well known that nanostructured metals can exhibit significantly improved properties compared to metals with conventional grain size. Unfortunately, nanocrystalline metals typically are not thermodynamically stable and exhibit rapid grain growth at moderate temperatures. This severely limits their processing and use, making them impractical for most engineering applications. Recent work has shown that a number of thermodynamically stable nanocrystalline metal alloys exist. These alloys have been prepared as powders using severe plastic deformation (e.g. ball milling) processes. Consolidation of these powders without compromise of their nanocrystalline microstructure is a critical step to enabling their use as engineering materials. Wemore » demonstrate solid-state consolidation of ball milled copper-tantalum nanocrystalline metal powder using cold spray. Unfortunately, the nanocrystalline copper-tantalum powder that was consolidated did not contain the thermodynamically stable copper-tantalum nanostructure. Nevertheless, this does this demonstrates a pathway to preparation of bulk thermodynamically stable nanocrystalline copper-tantalum. Furthermore, it demonstrates a pathway to additive manufacturing (3D printing) of nanocrystalline copper-tantalum. Additive manufacturing of thermodynamically stable nanocrystalline metals is attractive because it enables maximum flexibility and efficiency in the use of these unique materials.« less

Inhibition of ammonia poisoning by addition of platinum to Ru/α-Al2 O3 for preferential CO oxidation in fuel cells.

PubMed

Sato, Katsutoshi; Yagi, Sho; Zaitsu, Shuhei; Kitayama, Godai; Kayada, Yuto; Teramura, Kentaro; Takita, Yusaku; Nagaoka, Katsutoshi

2014-12-01

In polymer electrolyte fuel cell (PEFC) systems, small amounts of ammonia (NH3 ) present in the reformate gas deactivate the supported ruthenium catalysts used for preferential oxidation (PROX) of carbon monoxide (CO). In this study, we investigated how the addition of a small amount of platinum to a Ru/α-Al2 O3 catalyst (Pt/Ru=1:9 w/w) affected the catalyst's PROX activity in both the absence and the presence of NH3 (130 ppm) under conditions mimicking the reformate conditions during steam reforming of natural gas. The activity of undoped Ru/α-Al2 O3 decreased sharply upon addition of NH3 , whereas Pt/Ru/α-Al2 O3 exhibited excellent PROX activity even in the presence of NH3 . Ruthenium K-edge X-ray absorption near-edge structure (XANES) spectra indicated that in the presence of NH3 , some of the ruthenium in the undoped catalyst was oxidized in the presence of NH3 , whereas ruthenium oxidation was not observed with Pt/Ru/α-Al2 O3 . These results suggest that ruthenium oxidation is retarded by the platinum, so that the catalyst shows high activity even in the presence of NH3 . © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Micromechanics Modeling of Fracture in Nanocrystalline Metals

NASA Technical Reports Server (NTRS)

Glaessgen, E. H.; Piascik, R. S.; Raju, I. S.; Harris, C. E.

2002-01-01

Nanocrystalline metals have very high theoretical strength, but suffer from a lack of ductility and toughness. Therefore, it is critical to understand the mechanisms of deformation and fracture of these materials before their full potential can be achieved. Because classical fracture mechanics is based on the comparison of computed fracture parameters, such as stress intlmsity factors, to their empirically determined critical values, it does not adequately describe the fundamental physics of fracture required to predict the behavior of nanocrystalline metals. Thus, micromechanics-based techniques must be considered to quanti@ the physical processes of deformation and fracture within nanocrystalline metals. This paper discusses hndamental physicsbased modeling strategies that may be useful for the prediction Iof deformation, crack formation and crack growth within nanocrystalline metals.

Wear-triggered self-healing behavior on the surface of nanocrystalline nickel aluminum bronze/Ti3SiC2 composites

NASA Astrophysics Data System (ADS)

Zhai, Wenzheng; Lu, Wenlong; Zhang, Po; Wang, Jian; Liu, Xiaojun; Zhou, Liping

2018-04-01

Self-healing can protect materials from diverse damages, but is intrinsically difficult in metals. This paper demonstrates a potential method through a simultaneous decomposition and oxidation of Ti3SiC2 to achieve healing of stress cracking on the surface of nickel aluminum bronze (NAB)/Ti3SiC2 nanocrystalline composites during fretting wear. At the finest nanocrystalline materials, a crack recovery would be attained at 76.5%. The repetitive fretting wear leads to a modest amount of 'flowability' of Ti3SiC2 toward the crack, facilitating crack recovery. Along with the wear-triggered self-healing, the NAB/Ti3SiC2 shows an improved tribological performance with the stable decreased friction torque due to the formation of lubrication TiO2 oxide.

Direct synthesis and characterization of optically transparent conformal zinc oxide nanocrystalline thin films by rapid thermal plasma CVD

NASA Astrophysics Data System (ADS)

Pedersen, Joachim D.; Esposito, Heather J.; Teh, Kwok Siong

2011-10-01

We report a rapid, self-catalyzed, solid precursor-based thermal plasma chemical vapor deposition process for depositing a conformal, nonporous, and optically transparent nanocrystalline ZnO thin film at 130 Torr (0.17 atm). Pure solid zinc is inductively heated and melted, followed by ionization by thermal induction argon/oxygen plasma to produce conformal, nonporous nanocrystalline ZnO films at a growth rate of up to 50 nm/min on amorphous and crystalline substrates including Si (100), fused quartz, glass, muscovite, c- and a-plane sapphire (Al2O3), gold, titanium, and polyimide. X-ray diffraction indicates the grains of as-deposited ZnO to be highly textured, with the fastest growth occurring along the c-axis. The individual grains are observed to be faceted by (103) planes which are the slowest growth planes. ZnO nanocrystalline films of nominal thicknesses of 200 nm are deposited at substrate temperatures of 330°C and 160°C on metal/ceramic substrates and polymer substrates, respectively. In addition, 20-nm- and 200-nm-thick films are also deposited on quartz substrates for optical characterization. At optical spectra above 375 nm, the measured optical transmittance of a 200-nm-thick ZnO film is greater than 80%, while that of a 20-nm-thick film is close to 100%. For a 200-nm-thick ZnO film with an average grain size of 100 nm, a four-point probe measurement shows electrical conductivity of up to 910 S/m. Annealing of 200-nm-thick ZnO films in 300 sccm pure argon at temperatures ranging from 750°C to 950°C (at homologous temperatures between 0.46 and 0.54) alters the textures and morphologies of the thin film. Based on scanning electron microscope images, higher annealing temperatures appear to restructure the ZnO nanocrystalline films to form nanorods of ZnO due to a combination of grain boundary diffusion and bulk diffusion. PACS: films and coatings, 81.15.-z; nanocrystalline materials, 81.07.Bc; II-VI semiconductors, 81.05.Dz.

Bioimaging of isosteric osmium and ruthenium anticancer agents by LA-ICP-MS.

PubMed

Klose, Matthias H M; Theiner, Sarah; Kornauth, Christoph; Meier-Menches, Samuel M; Heffeter, Petra; Berger, Walter; Koellensperger, Gunda; Keppler, Bernhard K

2018-03-01

Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) was used to study the spatial distribution of two metallodrugs with anticancer activities in vivo, namely the organoruthenium plecstatin-1 (1) and its isosteric osmium analogue (2), in liver, kidneys, muscles and tumours of treated mice bearing a CT-26 tumour after single-dose i.p. administration. To the best of our knowledge, this is the first time that the spatial distribution of an osmium drug candidate has been investigated using LA-ICP-MS in tissues. Independent measurements of the average ruthenium and osmium concentration via microwave digestion and ICP-MS in organs and tumours were in good agreement with the LA-ICP-MS results. Matrix-matched standards (MMS) ranging from 1 to 30 μg g -1 were prepared to quantify the spatial distributions of the metals and the average metal content of the MMS samples was additionally quantified by ICP-MS after microwave digestion. The recoveries for osmium and ruthenium in the MMS were 105% and 101% on average, respectively, validating the sample preparation procedure of the MMS. Preparation of MMS was carried out under an argon atmosphere to prevent oxidation of osmium-species to the volatile OsO 4 . The highest metal concentrations were found in the liver, followed by kidney, lung and tumour tissues, while muscles displayed only very low quantities of the respective metal. Both metallodrugs accumulated in the cortex of the kidneys more strongly compared to the medulla. Interestingly, osmium from 2 was largely located at the periphery and tissue edges, whereas ruthenium from 1 was observed to penetrate deeper into the organs and tumours.

Toxicology and pharmacology of some ruthenium compounds: Vascular smooth muscle relaxation by nitrosyl derivatives of ruthenium and iridium.

PubMed

Kruszyna, H; Kruszyna, R; Hurst, J; Smith, R P

1980-07-01

A series of compounds were synthesized from ruthenium trichloride, and their ip LD50s were determined in mice: pentamminenitrosylruthenium(II) chloride, 8.9; chloronitrobis(2,2'-dipyridyl)ruthenium(II), 55;dichlorobis(2,2'-dipyridyl)ruthenium(II), 63; ruthenium trichloride, 108; and potassium pentachloronitrosylruthenate(II), 127 mg/kg. The two bis-bipyridyl complexes produced death in convulsions within minutes, whereas the remaining compounds resulted in long, debilitating courses with death occurring in 4-7d. When given in massive overdoses, however, the compounds with inorganic ligands also produced rapid convulsive death in mice, and when given iv to anesthetized cats, they produced respiratory arrest. The major toxic effects of all the complexes appeared to be due to the metal and not to its associated ligands. Only complexes having nitrosyl ligand specifically relaxed vascular smooth muscle. Potassium pentabromoiridate(III) also relaxed rabbit aortic strips that had been contracted by adrenergic agonists, but potassium pentachloroiridate(III) did not. None of the complexes was as active as nitroprusside in relaxing aortic strips or in decreasing arterial blood pressure in cats. No compound tested was as potent as cisplatin in antitumor activity. The pentamminenitrosylruthenium(II) complex also relaxed guinea pig ileum and frog rectus abdominus when these isolated muscles had been contracted by acetylcho line. It appears that these organoruthenium compounds may produce death in central respiratory arrest, as do the inorganic complexes when given iv or ip in massive overdoses. In minimally lethal doses, the complexes with inorganic ligands may affect a variety of contractile tissues, perhaps by a general mechanism involving Ca. These complexes are apt to be generally cytotoxic as well.

Synthesis, characterization, and photocatalytic properties of nanocrystalline NZO thin films

NASA Astrophysics Data System (ADS)

Aryanto, D.; Hastuti, E.; Husniya, N.; Sudiro, T.; Nuryadin, B. W.

2018-03-01

Nanocrystalline Ni-doped ZnO (NZO) thin films were synthesized on glass substrate using sol-gel spin coating methods. The effect of annealing on the structural and optical properties of nanocrystalline thin film was studied using X-ray diffractometer (XRD), field emission scanning electron microscopy (FESEM), UV-VIS spectrophotometry, and photoluminescence (PL). The results showed that the annealing temperature strongly influenced the physical properties of nanocrystalline NZO thin films. The photocatalytic properties of nanocrystalline NZO thin films were evaluated using an aqueous solution of Rhodamine-B. The photocatalytic activity of nanocrystalline NZO thin films increased with the increase of annealing temperature. The results indicated that the structure, morphology, and band gap energy of nanocrystalline NZO thin films played an important role in photocatalytic activity.

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.

Simultaneous determination of epinephrene and paracetamol at copper-cobalt oxide spinel decorated nanocrystalline zeolite modified electrodes.

PubMed

Samanta, Subhajyoti; Srivastava, Rajendra

2016-08-01

In this study, CuCo2O4 and CuCo2O4 decorated nanocrystalline ZSM-5 materials were prepared. For comparative study, a series of MCo2O4 spinels were also prepared. Materials were characterized by the complementary combination of X-ray diffraction, N2-adsorption, UV-visible, and electron microscopic techniques. A simple and rapid method for the simultaneous determination of paracetamol and epinephrine at MCo2O4 spinels modified electrodes is presented in this manuscript. Among the materials investigated in this study, CuCo2O4 decorated nanocrystalline ZSM-5 exhibited the highest electrocatalytic activity with excellent stability, sensitivity, and selectivity. Analytical performance of the sensor was demonstrated in the determination of epinephrine and paracetamol in the commercial pharmaceutical samples. Copyright © 2016 Elsevier Inc. All rights reserved.

The inhibition of mitochondrial calcium transport by lanthanides and Ruthenium Red

PubMed Central

Reed, Ken C.; Bygrave, Fyfe L.

1974-01-01

An EGTA (ethanedioxybis(ethylamine)tetra-acetic acid)-quench technique was developed for measuring initial rates of 45Ca2+ transport by rat liver mitochondria. This method was used in conjunction with studies of Ca2+-stimulated respiration to examine the mechanisms of inhibition of Ca2+ transport by the lanthanides and Ruthenium Red. Ruthenium Red inhibits Ca2+ transport non-competitively with Ki 3×10−8m; there are 0.08nmol of carrier-specific binding sites/mg of protein. The inhibition by La3+ is competitive (Ki=2×10−8m); the concentration of lanthanide-sensitive sites is less than 0.001nmol/mg of protein. A further difference between their modes of action is that lanthanide inhibition diminishes with time whereas that by Ruthenium Red does not. Binding studies showed that both classes of inhibitor bind to a relatively large number of external sites (probably identical with the `low-affinity' Ca2+-binding sites). La3+ competes with Ruthenium Red for most of these sites, but a small fraction of the bound Ruthenium Red (less than 2nmol/mg of protein) is not displaced by La3+. The results are discussed briefly in relation to possible models for a Ca2+ carrier. PMID:4375957

Oxidized nanocrystalline Fe-Cu pseudoalloy subjected to high pressure and electrodischarge pulses: Mössbauer and x-ray investigations

NASA Astrophysics Data System (ADS)

Gavriliuk, A. G.; Voitkovsky, V. S.; Sidorov, V. A.; Filonenko, V. P.; Tsiok, O. B.; Khvostantsev, L. G.

1998-05-01

Nanocrystalline Fe15Cu85 pseudoalloy has been subjected to pulsed heating up to 1500 K at high pressure (8 GPa). Two regimes were studied: the direct heating using electrodischarge through the sample and indirect heating with the use of cylindrical heater around the sample. The temperature and time conditions in both types of experiments were adjusted to be equivalent. The discharge parameters (stored energy, discharge time, and magnitude of current pulse) were sufficient to move defects by conduction electrons, but insufficient to melt the sample. The properties of treated samples were studied using Mössbauer absorption spectra and x-ray diffraction for three types of samples: (a) primary powder treated by high pressure up to 8 GPa, (b) powder subjected to indirect pulsed heating at 8 GPa, (c) powder treated by electrical pulses at 8 GPa. The x-ray diffraction pattern of primary powder exhibits peaks of copper, iron, and copper oxide (CuO). The Mössbauer spectrum of primary powder exhibits six peaks of alpha iron and some peaks near zero velocity due to the small iron clusters in the copper matrix and ultrafine clusters of paramagnetic phase x-Fe2O3. The transformation of CuO to Cu2O takes place in the course of indirect heating, the Mössbauer spectrum being almost unchanged. The direct electrodischarge heating causes the appearance of new magnetic phase with the magnetic field on iron nucleus 505 kOe, which corresponds to α-Fe2O3. The formation of α-Fe2O3 was confirmed by x-ray diffraction. At the same time the transformation of CuO to Cu2O is incomplete. These experiments demonstrate that high density current pulses, causing the electron wind, can be a useful tool to influence the structure of nanocrystalline powder.

Nanocrystalline SnO2 formation by oxygen ion implantation in tin thin films

NASA Astrophysics Data System (ADS)

Kondkar, Vidya; Rukade, Deepti; Kanjilal, Dinakar; Bhattacharyya, Varsha

2018-03-01

Metallic tin thin films of thickness 100 nm are deposited on fused silica substrates by thermal evaporation technique. These films are implanted with 45 keV oxygen ions at fluences ranging from 5 × 1015 to 5 × 1016 ions cm-2. The energy of the oxygen ions is calculated using SRIM in order to form embedded phases at the film-substrate interface. Post-implantation, films are annealed using a tube furnace for nanocrystalline tin oxide formation. These films are characterized using x-ray diffraction, Raman spectroscopy, UV-vis spectroscopy and photoluminescence spectroscopy. XRD and Raman spectroscopy studies reveal the formation of single rutile phase of SnO2. The size of the nanocrystallites formed decreases with an increase in the ion fluence. The nanocrystalline SnO2 formation is also confirmed by UV-vis and photoluminescence spectroscopy.

Nonproductive events in ring-closing metathesis using ruthenium catalysts.

PubMed

Stewart, Ian C; Keitz, Benjamin K; Kuhn, Kevin M; Thomas, Renee M; Grubbs, Robert H

2010-06-30

The relative TONs of productive and nonproductive metathesis reactions of diethyl diallylmalonate are compared for eight different ruthenium-based catalysts. Nonproductive cross metathesis is proposed to involve a chain-carrying ruthenium methylidene. A second more-challenging substrate (dimethyl allylmethylallylmalonate) that forms a trisubstituted olefin product is used to further delineate the effect of catalyst structure on the relative efficiencies of these processes. A steric model is proposed to explain the observed trends.

The Bulk Nanocrystalline zn Produced by Mechanical Attrition

NASA Astrophysics Data System (ADS)

Zhu, X. K.; Zhao, K. Y.; Li, C. J.; Tao, J. M.; Chan, T. L.; Koch, C. C.

The purpose of experiment was to produce bulk nanocrystalline Zn by mechanical attrition. The bulk nanocrystalline Zn produced by mechanical attrition was studied. The microstructural evolution during cryomilling and subsequent room temperature milling was characterized using scanning electron microscopy (SEM) and X-ray diffraction (XRD). In this paper, Nanocrystalline Zn was produced by insitu consolidation of Zn elemental powder using mechanical attrition at liquid nitrogen and room temperature. For the samples studied, the longest elongation of 65% and highest stress of 200 MPa is obtained in nanocrystalline Zn during tensile testing at the condition of strain rate (10-3 sec-1) and 20°C which is equal to 0.43 Tm (Tm is the melting temperature of pure Zn).

Investigating the Thermal and Phase Stability of Nanocrystalline Ni-W Produced by Electrodeposition, Sputtering, and Mechanical Alloying

NASA Astrophysics Data System (ADS)

Marvel, Christopher Jonathan

diffusivity calculations conceptually suggested that increasing W alloying concentrations can decrease the grain growth rate. The strongest evidence of grain growth stagnation was via nanoscale oxide particle drag in highly contaminated electrodeposited alloys. Interestingly, W-segregation was also detected to the oxide phase boundaries and revealed a potential indirect mechanism of thermal stability. The phase stability of pure and contaminated Ni-W alloys was investigated with density functional theory. Primarily, the calculations suggested that the intermetallic phases NiW and NiW2 are thermodynamically unstable, meaning the binary phase diagram is incorrect, but the ternary carbides Ni 6W6C and Ni2W4C are stable. Several Ni-W binary and Ni-W-C ternary phase diagrams were constructed using a simplified CALPHAD approach to improve the understanding of Ni-W phase stability. Lastly, it was determined that the fabrication process greatly influences the impurity types and concentrations of the alloys, and therefore greatly dictate which thermal stability mechanisms are active. Mechanically alloyed samples were found to be the most resistant to grain growth. The findings of this research will hopefully guide future efforts to design more thermally stable nanocrystalline alloys. The link between phase stability and grain growth behavior of Ni-W was thoroughly discussed, as well as the dependence of bulk fabrication processing on the contamination found in the alloys. Ultimately, this research has greatly expanded the general understanding of nanocrystalline Ni-W microstructures, and it is likely that similar phenomena occur in other nanocrystalline systems.

Flow injection chemiluminescent determination of tetracycline using a tris(2,2'-bipyridine)ruthenium(II)-cerium(IV) sulphate system.

PubMed

Guo, Liangqia; Xie, Zenghong; Lin, Xucong; Liu, Xiaohua; Zhang, Weilin; Chen, Guonan

2004-01-01

A flow-injection chemiluminescence method for the determination of tetracycline was developed. The method is based on an enhancement by tetracycline of the chemiluminescence light emission of tris(2,2'-bipyridine)ruthenium(II). In sulphuric acid medium, the chemiluminescence is generated by the continuous oxidation of tris(2,2'-bipyridine)ruthenium(II) by cerium (IV) sulphate. The light-emission intensity is greatly enhanced in the presence of tetracycline. Under the optimum conditions, the calibration curve is linear over the range 3.75 x 10(-8) g/mL-1.5 x 10(-5) g/mL for tetracycline with the linear equation: deltaINT = 205.898 x C - 20.442 (R2 = 0.9974). The detection limit is 3.27 x 10(-8) g/mL. The proposed method was also successfully used to determine tetracycline in pharmaceutical formulation (mean recovery of tetracycline, 100.7%). Copyright 2004 John Wiley & Sons, Ltd.

Using ruthenium sawhorse based decarboxylation to produce industrial materials from oleic acid

USDA-ARS?s Scientific Manuscript database

Ruthenium catalyzed isomerization and decarboxylation of 9-cis-octadecenoic acid are reported as part of the effort to produce valuable industrial materials from biobased sources. Initial studies have demonstrated the efficacy of ruthenium sawhorse materials and further mechanistic studies uncovered...

Oxidant effect of La(NO3)3·6H2O solution on the crystalline characteristics of nanocrystalline ZrO2 films grown by atomic layer deposition

NASA Astrophysics Data System (ADS)

Oh, Nam Khen; Kim, Jin-Tae; Kang, Goru; An, Jong-Ki; Nam, Minwoo; Kim, So Yeon; Park, In-Sung; Yun, Ju-Young

2017-02-01

Nanocrystalline ZrO2 films were synthesized by atomic layer deposition method using CpZr[N(CH3)2]3 (Cp = C5H5) as the metal precursor and La(NO3)3·6H2O solution as the oxygen source. La element in the deposited ZrO2 films could not be detected as its content was below the resolution limit of the X-ray photoelectron spectroscopy. The alternative introduction of La(NO3)3·6H2O solution to conventionally used H2O as the oxidant effectively altered the crystalline structure, grain size, and surface roughness of the grown ZrO2 films. Specifically, the crystalline structure of the ZrO2 film changed from a mixture of tetragonal and monoclinic phases to monoclinic phase. The average grain size also increased, and the resulting film surface became rougher. The average grain sizes of the ZrO2 films prepared from La(NO3)3·6H2O solution at concentrations of 10, 20, 30, and 40% were 280, 256, 208, and 200 nm, respectively, whereas that prepared using H2O oxidant was 142 nm. However, the concentration of La(NO3)3·6H2O solution minimally influenced the crystalline characteristics of the nanocrystalline ZrO2 films i.e., the crystalline structure, grain size, and surface roughness except for crystallite size.

Platinum-ruthenium-nickel fuel cell electrocatalyst

DOEpatents

Gorer, Alexander

2005-07-26

A catalyst suitable for use in a fuel cell, especially as an anode catalyst, that contains platinum, ruthenium, and nickel, wherein the nickel is at a concentration that is less than about 10 atomic percent.

Highly efficient binuclear ruthenium catalyst for water oxidation.

PubMed

Sander, Anett C; Maji, Somnath; Francàs, Laia; Böhnisch, Torben; Dechert, Sebastian; Llobet, Antoni; Meyer, Franc

2015-05-22

Water splitting is one of the key steps in the conversion of sunlight into a usable renewable energy carrier such as dihydrogen or more complex chemical fuels. Developing rugged and highly efficient catalysts for the oxidative part of water splitting, the water oxidation reaction generating dioxygen, is a major challenge in the field. Herein, we introduce a new, and rationally designed, pyrazolate-based diruthenium complex with the highest activity in water oxidation catalysis for binuclear systems reported to date. Single-crystal X-ray diffraction showed favorable preorganization of the metal ions, well suited for binding two water molecules at a distance adequate for OO bond formation; redox titrations as well as spectroelectrochemistry allowed characterization of the system in several oxidation states. Low oxidation potentials reflect the trianionic character of the elaborate compartmental pyrazolate ligand furnished with peripheral carboxylate groups. Water oxidation has been mediated both by a chemical oxidant (Ce(IV) )-by means of manometry and a Clark electrode for monitoring the dioxygen production-and electrochemically with impressive activities. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Production of hydrogen using nanocrystalline protein-templated catalysts on m13 phage.

PubMed

Neltner, Brian; Peddie, Brian; Xu, Alex; Doenlen, William; Durand, Keith; Yun, Dong Soo; Speakman, Scott; Peterson, Andrew; Belcher, Angela

2010-06-22

For decades, ethanol has been in use as a fuel for the storage of solar energy in an energy-dense, liquid form. Over the past decade, the ability to reform ethanol into hydrogen gas suitable for a fuel cell has drawn interest as a way to increase the efficiency of both vehicles and stand-alone power generators. Here we report the use of extremely small nanocrystalline materials to enhance the performance of 1% Rh/10% Ni@CeO(2) catalysts in the oxidative steam reforming of ethanol with a ratio of 1.7:1:10:11 (air/EtOH/water/argon) into hydrogen gas, achieving 100% conversion of ethanol at only 300 degrees C with 60% H(2) in the product stream and less than 0.5% CO. Additionally, nanocrystalline 10% Ni@CeO(2) was shown to achieve 100% conversion of ethanol at 400 degrees C with 73% H(2), 2% CO, and 2% CH(4) in the product stream. Finally, we demonstrate the use of biological templating on M13 to improve the resistance of this catalyst to deactivation over 52 h tests at high flow rates (120 000 h(-1) GHSV) at 450 degrees C. This study suggests that the use of highly nanocrystalline, biotemplated catalysts to improve activity and stability is a promising route to significant gains over traditional catalyst manufacture methods.

Nickel/ruthenium catalyst and method for aqueous phase reactions

DOEpatents

Elliott, Douglas C.; Sealock, John L.

1998-01-01

A method of hydrogenation using a catalyst in the form of a plurality of porous particles wherein each particle is a support having nickel metal catalytic phase or reduced nickel deposited thereon in a first dispersed phase and an additional ruthenium metal deposited onto the support in a second dispersed phase. The additional ruthenium metal is effective in retarding or reducing agglomeration or sintering of the nickel metal catalytic phase thereby increasing the life time of the catalyst during hydrogenation reactions.

Metal-metal interactions in linear tri-, penta-, hepta-, and nona-nuclear ruthenium string complexes.

PubMed

Niskanen, Mika; Hirva, Pipsa; Haukka, Matti

2012-05-01

Density functional theory (DFT) methodology was used to examine the structural properties of linear metal string complexes: [Ru(3)(dpa)(4)X(2)] (X = Cl(-), CN(-), NCS(-), dpa = dipyridylamine(-)), [Ru(5)(tpda)(4)Cl(2)], and hypothetical, not yet synthesized complexes [Ru(7)(tpta)(4)Cl(2)] and [Ru(9)(ppta)(4)Cl(2)] (tpda = tri-α-pyridyldiamine(2-), tpta = tetra-α-pyridyltriamine(3-), ppta = penta-α-pyridyltetraamine(4-)). Our specific focus was on the two longest structures and on comparison of the string complexes and unsupported ruthenium backboned chain complexes, which have weaker ruthenium-ruthenium interactions. The electronic structures were studied with the aid of visualized frontier molecular orbitals, and Bader's quantum theory of atoms in molecules (QTAIM) was used to study the interactions between ruthenium atoms. The electron density was found to be highest and distributed most evenly between the ruthenium atoms in the hypothetical [Ru(7)(tpta)(4)Cl(2)] and [Ru(9)(ppta)(4)Cl(2)] string complexes.

Organometallic ruthenium anticancer complexes inhibit human glutathione-S-transferase π.

PubMed

Lin, Yu; Huang, Yongdong; Zheng, Wei; Wang, Fuyi; Habtemariam, Abraha; Luo, Qun; Li, Xianchan; Wu, Kui; Sadler, Peter J; Xiong, Shaoxiang

2013-11-01

The organometallic ruthenium(II) anticancer complexes [(η(6)-arene)Ru(en)Cl](+) (arene = p-cymene (1), biphenyl (2) or 9,10-dihydrophenanthrene (3); en = ethylenediamine), exhibit in vitro and in vivo anticancer activities. In the present work, we show that they inhibit human glutathione-S-transferase π (GSTπ) with IC50 values of 59.4 ± 1.3, 63.2 ± 0.4 and 37.2 ± 1.1 μM, respectively. Mass spectrometry revealed that complex 1 binds to the S-donors of Cys15, Cys48 within the G-site and Cys102 at the interface of the GSTπ dimer, while complex 2 binds to Cys48 and Met92 at the dimer interface and complex 3 to Cys15, Cys48 and Met92. Moreover, the binding of complex 1 to Cys15 and Cys102, complex 2 to Cys48 and complex 3 to Cys15 induces the irreversible oxidation of the coordinated thiolates to sulfenates. Molecular modeling studies indicate that the coordination of the {(arene)Ru(en)}(2+) fragment to Cys48 blocks the hydrophilic G-site sterically, perhaps preventing substrate from proper positioning and accounting for the reduction in enzymatic activity of ruthenated GSTπ. The binding of the ruthenium arene complexes to Cys102 or Met92 disrupts the dimer interface which is an essential structural feature for the proper functioning of GSTπ, perhaps also contributing to the inhibition of GSTπ. © 2013.

Ruthenium-Catalyzed Cycloaddition of 1-Haloalkynes with Nitrile Oxides and Organic Azides; Synthesis of 4-Halo Isoxazoles and 5-Halo Triazoles

PubMed Central

Oakdale, James S.; Sit, Rakesh K.

2015-01-01

(Cyclopentadienyl)(cyclooctadiene) ruthenium(II) chloride [CpRuCl(cod)] catalyzes the reaction between nitrile oxides and electronically deficient 1-choro-, 1-bromo- and 1-iodoalkynes leading to 4-haloisoxazoles. Organic azides are also suitable 1,3-dipoles, resulting in 5-halo-1,2,3-triazoles. These air tolerant reactions can be performed at room temperature with 1.25 equiv of the respective 1,3-dipole relative to the alkyne component. Reactive 1-haloalkynes include propiolic amides, esters, ketones and phosphonates. Post-functionalization of the halogenated azole products can be accomplished using palladium-catalyzed cross-coupling reactions as well as via manipulation of reactive amide groups. The lack of catalysis observed with Cp*RuCl(cod) is attributed to steric demands of the Cp* (η5-C5Me5) ligand in comparison to the parent Cp (η5-C5H5). This hypothesis is supported by the poor reactivity of (η5-C5Me4CF3)RuCl(cod), which serves as a an isosteric mimic of Cp* and as an isoelectronic analog of Cp. PMID:25059647

A ruthenium(II) complex as turn-on Cu(II) luminescent sensor based on oxidative cyclization mechanism and its application in vivo

NASA Astrophysics Data System (ADS)

Zhang, Yunfei; Liu, Zonglun; Yang, Kui; Zhang, Yi; Xu, Yongqian; Li, Hongjuan; Wang, Chaoxia; Lu, Aiping; Sun, Shiguo

2015-02-01

Copper ions play a vital role in a variety of fundamental physiological processes not only in human beings and plants, but also for extensive insects and microorganisms. In this paper, a novel water-soluble ruthenium(II) complex as a turn-on copper(II) ions luminescent sensor based on o-(phenylazo)aniline was designed and synthesized. The azo group would undergo a specific oxidative cyclization reaction with copper(II) ions and turn into high luminescent benzotriazole, triggering significant luminescent increasements which were linear to the concentrations of copper(II) ions. The sensor distinguished by its high sensitivity (over 80-fold luminescent switch-on response), good selectivity (the changes of the emission intensity in the presence of other metal ions or amino acids were negligible) and low detection limit (4.42 nM) in water. Moreover, the copper(II) luminescent sensor exhibited good photostability under light irradiation. Furthermore, the applicability of the proposed sensor in biological samples assay was also studied and imaged copper(II) ions in living pea aphids successfully.

Nickel/ruthenium catalyst and method for aqueous phase reactions

DOEpatents

Elliott, D.C.; Sealock, J.L.

1998-09-29

A method of hydrogenation is described using a catalyst in the form of a plurality of porous particles wherein each particle is a support having nickel metal catalytic phase or reduced nickel deposited thereon in a first dispersed phase and an additional ruthenium metal deposited onto the support in a second dispersed phase. The additional ruthenium metal is effective in retarding or reducing agglomeration or sintering of the nickel metal catalytic phase thereby increasing the life time of the catalyst during hydrogenation reactions. 2 figs.

Reactivity of nitrido complexes of ruthenium(VI), osmium(VI), and manganese(V) bearing Schiff base and simple anionic ligands.

PubMed

Man, Wai-Lun; Lam, William W Y; Lau, Tai-Chu

2014-02-18

Nitrido complexes (M≡N) may be key intermediates in chemical and biological nitrogen fixation and serve as useful reagents for nitrogenation of organic compounds. Osmium(VI) nitrido complexes bearing 2,2':6',2″-terpyridine (terpy), 2,2'-bipyridine (bpy), or hydrotris(1-pyrazolyl)borate anion (Tp) ligands are highly electrophilic: they can react with a variety of nucleophiles to generate novel osmium(IV)/(V) complexes. This Account describes our recent results studying the reactivity of nitridocomplexes of ruthenium(VI), osmium(VI), and manganese(V) that bear Schiff bases and other simple anionic ligands. We demonstrate that these nitrido complexes exhibit rich chemical reactivity. They react with various nucleophiles, activate C-H bonds, undergo N···N coupling, catalyze the oxidation of organic compounds, and show anticancer activities. Ruthenium(VI) nitrido complexes bearing Schiff base ligands, such as [Ru(VI)(N)(salchda)(CH3OH)](+) (salchda = N,N'-bis(salicylidene)o-cyclohexyldiamine dianion), are highly electrophilic. This complex reacts readily at ambient conditions with a variety of nucleophiles at rates that are much faster than similar reactions using Os(VI)≡N. This complex also carries out unique reactions, including the direct aziridination of alkenes, C-H bond activation of alkanes and C-N bond cleavage of anilines. The addition of ligands such as pyridine can enhance the reactivity of [Ru(VI)(N)(salchda)(CH3OH)](+). Therefore researchers can tune the reactivity of Ru≡N by adding a ligand L trans to nitride: L-Ru≡N. Moreover, the addition of various nucleophiles (Nu) to Ru(VI)≡N initially generate the ruthenium(IV) imido species Ru(IV)-N(Nu), a new class of hydrogen-atom transfer (HAT) reagents. Nucleophiles also readily add to coordinated Schiff base ligands in Os(VI)≡N and Ru(VI)≡N complexes. These additions are often stereospecific, suggesting that the nitrido ligand has a directing effect on the incoming nucleophile. M≡N is also

Aging of Nanocrystalline Mackinawite (FeS): Mineralogical and Physicochemical Properties

NASA Astrophysics Data System (ADS)

Jeong, H. Y.; Lee, H.

2011-12-01

Due to the extraordinary physical properties and high surface areas, nanocrystalline minerals have been widely investigated for their potential uses in treating contaminated groundwaters and surface waters. Most previous studies in this field have focused on either preparation of nanocrystalline minerals or measurement of their reactivity with environmental contaminants. Nanocrystalline minerals, due to the inherent thermodynamic instability, tend to change the physicochemical and mineralogical properties over time, usually resulting in the decreased reactivity. Thus, to better assess the long-term effectiveness of nanocrystalline minerals in field applications, such "aging" effects should be clearly delineated. In the present work, we have investigated the aging impact on nanocrystalline mackinawite (FeS), the ubiquitous Fe-bearing mineral in anoxic sulfidic sediments. Mackinawite (FeS) is known to be an effective scavenger for metal pollutants and a strong reducing reagent for chromate and chlorinated organic compounds. Our preliminary results indicate that nanocrystalline FeS ages via Ostwald ripening, particle aggregation, or mineralogical transformation. By X-ray diffraction (XRD) analysis, aging of nanocrystalline FeS via Ostwald ripening is found to be dominant at acidic pH. Cryogenic transmission electron microscopy (TEM) shows that particle aggregation is most evident at neutral pH. Transformation of nanosized FeS into a more thermodynamically stable greigite (Fe3S4) is observed in the presence of folic acid at acidic pH. The pH-dependent aging process may be linked with changes in the apparent solubility and surface charge of FeS with pH. The Ostwald ripening or particle aggregation of nanocrystalline FeS leads to the decrease surface area, thus causing the decreased reactivity. Given the less reactivity of greigite, the transformation of nanocrystalline FeS to greigite is also expected to result in the decreased reactivity.

Tin-decorated ruthenium nanoparticles: a way to tune selectivity in hydrogenation reaction

NASA Astrophysics Data System (ADS)

Bonnefille, Eric; Novio, Fernando; Gutmann, Torsten; Poteau, Romuald; Lecante, Pierre; Jumas, Jean-Claude; Philippot, Karine; Chaudret, Bruno

2014-07-01

Two series of ruthenium nanoparticles stabilized either by a polymer (polyvinylpyrrolidone; Ru/PVP) or a ligand (bisdiphenylphosphinobutane; Ru/dppb) were reacted with tributyltin hydride [(n-C4H9)3SnH] leading to tin-decorated ruthenium nanoparticles, Ru/PVP/Sn and Ru/dppb/Sn. The Sn/Ru molar ratio was varied in order to study the influence of the surface tin content on the properties of these new nanoparticles, by comparison with Ru/PVP and Ru/dppb. Besides HRTEM and WAXS analyses, spectroscopic techniques (IR, NMR and Mössbauer) combined with theoretical calculations and a simple catalytic test (styrene hydrogenation) allowed us to evidence the formation of μ3-bridging ``SnR'' groups on the ruthenium surface as well as to rationalize their influence on surface chemistry and catalytic activity.Two series of ruthenium nanoparticles stabilized either by a polymer (polyvinylpyrrolidone; Ru/PVP) or a ligand (bisdiphenylphosphinobutane; Ru/dppb) were reacted with tributyltin hydride [(n-C4H9)3SnH] leading to tin-decorated ruthenium nanoparticles, Ru/PVP/Sn and Ru/dppb/Sn. The Sn/Ru molar ratio was varied in order to study the influence of the surface tin content on the properties of these new nanoparticles, by comparison with Ru/PVP and Ru/dppb. Besides HRTEM and WAXS analyses, spectroscopic techniques (IR, NMR and Mössbauer) combined with theoretical calculations and a simple catalytic test (styrene hydrogenation) allowed us to evidence the formation of μ3-bridging ``SnR'' groups on the ruthenium surface as well as to rationalize their influence on surface chemistry and catalytic activity. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr00791c

Methodology for the effective stabilization of tin-oxide-based oxidation/reduction catalysts

NASA Technical Reports Server (NTRS)

Jordan, Jeffrey D. (Inventor); Schryer, David R. (Inventor); Leighty, Bradley D. (Inventor); Watkins, Anthony N. (Inventor); Summers, Jerry C. (Inventor); Davis, Patricia P. (Inventor); Oglesby, Donald M. (Inventor); Schryer, Jacqueline L. (Inventor); Gulati, Suresh T. (Inventor)

2011-01-01

The invention described herein involves a novel approach to the production of oxidation/reduction catalytic systems. The present invention serves to stabilize the tin oxide reducible metal-oxide coating by co-incorporating at least another metal-oxide species, such as zirconium. In one embodiment, a third metal-oxide species is incorporated, selected from the group consisting of cerium, lanthanum, hafnium, and ruthenium. The incorporation of the additional metal oxide components serves to stabilize the active tin-oxide layer in the catalytic process during high-temperature operation in a reducing environment (e.g., automobile exhaust). Moreover, the additional metal oxides are active components due to their oxygen-retention capabilities. Together, these features provide a mechanism to extend the range of operation of the tin-oxide-based catalyst system for automotive applications, while maintaining the existing advantages.

Synergetic effect of palladium-ruthenium nanostructures for ethanol electrooxidation in alkaline media

NASA Astrophysics Data System (ADS)

Monyoncho, Evans A.; Ntais, Spyridon; Soares, Felipo; Woo, Tom K.; Baranova, Elena A.

2015-08-01

Palladium-ruthenium nanoparticles supported on carbon PdxRu1-x/C (x = 1, 0.99, 0.95, 0.90, 0.80, 0.50) were prepared using a polyol method for ethanol electrooxidation in alkaline media. The resulting bimetallic catalysts were found to be primarily a mix of Pd metal, Ru oxides and Pd oxides. Their electrocatalytic activity towards ethanol oxidation reaction (EOR) in 1M KOH was studied using cyclic voltammetry and chronoamperometry techniques. Addition of 1-10 at.% Ru to Pd not only lowers the onset oxidation potential for EOR but also produces higher current densities at lower potentials compared to Pd by itself. Thus, Pd90Ru10/C and Pd99Ru1/C provide the current densities of up to six times those of Pd/C at -0.96 V and -0.67 V vs MSE, respectively. The current density at different potentials was found to be dependent on the surface composition of PdxRu1-x/C nanostructures. Pd90Ru10/C catalyst with more surface oxides was found to be active at lower potential compared to Pd99Ru1/C with less surface oxides, which is active at higher potentials. The steady-state current densities of the two best catalysts, Pd90Ru10/C and Pd99Ru1/C, showed minimal surface deactivation from EOR intermediates/products during chronoamperometry.

Complex of transferrin with ruthenium for medical applications

DOEpatents

Richards, Powell; Srivastava, Suresh C.; Meinken, George E.

1984-05-15

A novel Ruthenium-transferrin complex, prepared by reacting iron-free human transferrin dissolved in a sodium acetate solution at pH 7 with ruthenium by heating at about 40.degree. C. for about 2 hours, and purifying said complex by means of gel chromotography with pH 7 sodium acetate as eluent. The mono- or di-metal complex produced can be used in nuclear medicine in the diagnosis and/or treatment of tumors and abscesses. Comparative results with Ga-67-citrate, which is the most widely used tumor-localizing agent in nuclear medicine, indicate increased sensitivity of detection and greater tumor uptake with the Ru-transferrin complex.

Steric and Electronic Effects of Bidentate Phosphine Ligands on Ruthenium(II)-Catalyzed Hydrogenation of Carbon Dioxide.

PubMed

Zhang, Pan; Ni, Shao-Fei; Dang, Li

2016-09-20

The reactivity difference between the hydrogenation of CO2 catalyzed by various ruthenium bidentate phosphine complexes was explored by DFT. In addition to the ligand dmpe (Me2 PCH2 CH2 PMe2 ), which was studied experimentally previously, a more bulky diphosphine ligand, dmpp (Me2 PCH2 CH2 CH2 PMe2 ), together with a more electron-withdrawing diphosphine ligand, PN(Me) P (Me2 PCH2 N(Me) CH2 PMe2 ), have been studied theoretically to analyze the steric and electronic effects on these catalyzed reactions. Results show that all of the most favorable pathways for the hydrogenation of CO2 catalyzed by bidentate phosphine ruthenium dihydride complexes undergo three major steps: cis-trans isomerization of ruthenium dihydride complex, CO2 insertion into the Ru-H bond, and H2 insertion into the ruthenium formate ion. Of these steps, CO2 insertion into the Ru-H bond has the lowest barrier compared with the other two steps in each preferred pathway. For the hydrogenation of CO2 catalyzed by ruthenium complexes of dmpe and dmpp, cis-trans isomerization of ruthenium dihydride complex has a similar barrier to that of H2 insertion into the ruthenium formate ion. However, in the reaction catalyzed by the PN(Me) PRu complex, cis-trans isomerization of the ruthenium dihydride complex has a lower barrier than H2 insertion into the ruthenium formate ion. These results suggest that the steric effect caused by the change of the outer sphere of the diphosphine ligand on the reaction is not clear, although the electronic effect is significant to cis-trans isomerization and H2 insertion. This finding refreshes understanding of the mechanism and provides necessary insights for ligand design in transition-metal-catalyzed CO2 transformation. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Metallomics for drug development: a further insight into intracellular activation chemistry of a ruthenium(III)-based anticancer drug gained using a multidimensional analytical approach.

PubMed

Matczuk, Magdalena; Prządka, Monika; Aleksenko, Svetlana S; Czarnocki, Zbigniew; Pawlak, Katarzyna; Timerbaev, Andrei R; Jarosz, Maciej

2014-01-01

The mechanism by which the most relevant ruthenium anticancer drugs are activated in tumors to commence their tumor-inhibiting action remains one of the challenging research tasks of present-day metallomics. This contribution aims to capture and identify eventually more reactive species of one of two bis-indazole tetrachloridoruthenate(III) compounds that are progressing in clinical trials. In view of the fact that the transport of ruthenium into cancer cells is governed by transferrin receptors, the susceptibility of the Ru drug adduct with holo-transferrin to exposure by glutathione and ascorbic acid (at their cancer cytosol concentrations) was studied by inductively coupled plasma mass spectrometry (ICP-MS), following isolation of the reaction products by ultrafiltration. Next, capillary electrophoresis coupled to ICP-MS was applied to monitor changes in the Ru speciation both under simulated cancer cytosol conditions and in real cytosol and to assign the charge state of novel metal species. The latter were identified by using tandem electrospray ionization MS in the respective ion mode. The formation of ruthenium(II) species was for the first time revealed, in which the central metal is coordinated by the reduced (GSH) or the oxidized (GSSG) form of glutathione, i.e. [Ru(II)HindCl4(GSH)](2-) and [Ru(II)HindCl4(GSSG)](2-), respectively (Hind = indazole). Ascorbic acid released the ruthenium functionality from the protein-bound form in a different way, the products of adduct cleavage containing aqua ligands. Distribution of low-molecular mass species of Ru in human cytosol was found to have very much in common with the ruthenium speciation assayed under simulated cytosol conditions.

Design and development of novel MRI compatible zirconium- ruthenium alloys with ultralow magnetic susceptibility.

PubMed

Li, H F; Zhou, F Y; Li, L; Zheng, Y F

2016-04-19

In the present study, novel MRI compatible zirconium-ruthenium alloys with ultralow magnetic susceptibility were developed for biomedical and therapeutic devices under MRI diagnostics environments. The results demonstrated that alloying with ruthenium into pure zirconium would significantly increase the strength and hardness properties. The corrosion resistance of zirconium-ruthenium alloys increased significantly. High cell viability could be found and healthy cell morphology observed when culturing MG 63 osteoblast-like cells and L-929 fibroblast cells with zirconium-ruthenium alloys, whereas the hemolysis rates of zirconium-ruthenium alloys are <1%, much lower than 5%, the safe value for biomaterials according to ISO 10993-4 standard. Compared with conventional biomedical 316L stainless steel, Co-Cr alloys and Ti-based alloys, the magnetic susceptibilities of the zirconium-ruthenium alloys (1.25 × 10(-6) cm(3)·g(-1)-1.29 × 10(-6) cm(3)·g(-1) for zirconium-ruthenium alloys) are ultralow, about one-third that of Ti-based alloys (Ti-6Al-4V, ~3.5 × 10(-6) cm(3)·g(-1), CP Ti and Ti-6Al-7Nb, ~3.0 × 10(-6) cm(3)·g(-1)), and one-sixth that of Co-Cr alloys (Co-Cr-Mo, ~7.7 × 10(-6) cm(3)·g(-1)). Among the Zr-Ru alloy series, Zr-1Ru demonstrates enhanced mechanical properties, excellent corrosion resistance and cell viability with lowest magnetic susceptibility, and thus is the optimal Zr-Ru alloy system as therapeutic devices under MRI diagnostics environments.

Design and development of novel MRI compatible zirconium- ruthenium alloys with ultralow magnetic susceptibility

PubMed Central

Li, H.F.; Zhou, F.Y.; Li, L.; Zheng, Y.F.

2016-01-01

In the present study, novel MRI compatible zirconium-ruthenium alloys with ultralow magnetic susceptibility were developed for biomedical and therapeutic devices under MRI diagnostics environments. The results demonstrated that alloying with ruthenium into pure zirconium would significantly increase the strength and hardness properties. The corrosion resistance of zirconium-ruthenium alloys increased significantly. High cell viability could be found and healthy cell morphology observed when culturing MG 63 osteoblast-like cells and L-929 fibroblast cells with zirconium-ruthenium alloys, whereas the hemolysis rates of zirconium-ruthenium alloys are <1%, much lower than 5%, the safe value for biomaterials according to ISO 10993-4 standard. Compared with conventional biomedical 316L stainless steel, Co–Cr alloys and Ti-based alloys, the magnetic susceptibilities of the zirconium-ruthenium alloys (1.25 × 10−6 cm3·g−1–1.29 × 10−6 cm3·g−1 for zirconium-ruthenium alloys) are ultralow, about one-third that of Ti-based alloys (Ti–6Al–4V, ~3.5 × 10−6 cm3·g−1, CP Ti and Ti–6Al–7Nb, ~3.0 × 10−6 cm3·g−1), and one-sixth that of Co–Cr alloys (Co–Cr–Mo, ~7.7 × 10−6 cm3·g−1). Among the Zr–Ru alloy series, Zr–1Ru demonstrates enhanced mechanical properties, excellent corrosion resistance and cell viability with lowest magnetic susceptibility, and thus is the optimal Zr–Ru alloy system as therapeutic devices under MRI diagnostics environments. PMID:27090955

Synthesis and mechanical/magnetic properties of nano-grained iron-oxides prepared with an inert gas condensation and pulse electric current sintering process

NASA Astrophysics Data System (ADS)

Choa, Yong-Ho; Nakayama, Tatachika; Sekino, Tohru; Niihara, Koichi

1999-04-01

Nanocrystalline iron-oxide powder was fabricated with an inert gas condensation (IGC) method combined with evaporation, and in-situ oxidation techniques. The particle size of iron-oxide powder was controlled by varying the helium gas pressure between 0.1 and 10 Torr, with the smallest one =10 nm at 0.1 Torr. The nanostructure was characterized by TEM. Nanocrystalline iron-oxide powder was sintered with the pulse electric current sintering (PECS) method to obtain densified γ-Fe2O3 materials, and suitably densified nano-grained γ-Fe2O3 materials (≈ 40 nm) of great hardness were obtained. The correlation between the nanostructure and magnetic properties of nanocrystalline powder and densified γ-Fe2O3 materials was also investigated.

A new approach to synthesize supported ruthenium phosphides for hydrodesulfurization

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

Wang, Qingfang; Key Laboratory of Advanced Energy Materials Chemistry; Wang, Zhiqiang

2016-02-15

Highlights: • We bring out a new method to synthesize noble metal phosphides at low temperature. • Both RuP and Ru{sub 2}P were synthesized using triphenylphosphine as phosphorus sources. • Ru{sub 2}P was the better active phase for HDS than RuP and metal Ru. • RuP/SiO{sub 2} prepared by new method had better HDS activity to that by TPR method. - Abstract: Supported noble metal ruthenium phosphides were synthesized by one-step H{sub 2}-thermal treatment method using triphenylphosphine (TPP) as phosphorus sources at low temperatures. Two phosphides RuP and Ru{sub 2}P can be prepared by this method via varying the molarmore » ratio of metal salt and TPP. The as-prepared phosphides were characterized by X-ray powder diffraction (XRD), low-temperature N{sub 2} adsorption, CO chemisorption and transmission electronic microscopy (TEM). The supported ruthenium phosphides prepared by new method and conventional method together with contradistinctive metallic ruthenium were evaluated in hydrodesulfurization (HDS) of dibenzothiophene (DBT). The catalytic results showed that metal-rich Ru{sub 2}P was the better active phase for HDS than RuP and metal Ru. Besides this, ruthenium phosphide catalyst prepared by new method exhibited superior HDS activity to that prepared by conventional method.« less

Synthesis of Nano-Crystalline Gamma-TiAl Materials

NASA Technical Reports Server (NTRS)

Hales, Stephen J.; Vasquez, Peter

2003-01-01

One of the principal problems with nano-crystalline materials is producing them in quantities and sizes large enough for valid mechanical property evaluation. The purpose of this study was to explore an innovative method for producing nano-crystalline gamma-TiAl bulk materials using high energy ball milling and brief secondary processes. Nano-crystalline powder feedstock was produced using a Fritsch P4(TM) vario-planetary ball mill recently installed at NASA-LaRC. The high energy ball milling process employed tungsten carbide tooling (vials and balls) and no process control agents to minimize contamination. In a collaborative effort, two approaches were investigated, namely mechanical alloying of elemental powders and attrition milling of pre-alloyed powders. The objective was to subsequently use RF plasma spray deposition and short cycle vacuum hot pressing in order to effect consolidation while retaining nano-crystalline structure in bulk material. Results and discussion of the work performed to date are presented.

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.

Nitrated metalloporphyrins as catalysts for alkane oxidation

DOEpatents

Ellis, P.E. Jr.; Lyons, J.E.

1994-01-18

Compositions of matter comprising nitro-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has nitro groups attached thereto in meso and/or [beta]-pyrrolic positions.

Nitrated metalloporphyrins as catalysts for alkane oxidation

DOEpatents

Ellis, Jr., Paul E.; Lyons, James E.

1994-01-01

Compositions of matter comprising nitro-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has nitro groups attached thereto in meso and/or .beta.-pyrrolic positions.

Ruthenium nanoparticles in ionic liquids: structural and stability effects of polar solutes.

PubMed

Salas, Gorka; Podgoršek, Ajda; Campbell, Paul S; Santini, Catherine C; Pádua, Agílio A H; Costa Gomes, Margarida F; Philippot, Karine; Chaudret, Bruno; Turmine, Mireille

2011-08-14

Ionic liquids are a stabilizing medium for the in situ synthesis of ruthenium nanoparticles. Herein we show that the addition of molecular polar solutes to the ionic liquid, even in low concentrations, eliminates the role of the ionic liquid 3D structure in controlling the size of ruthenium nanoparticles, and can induce their aggregation. We have performed the synthesis of ruthenium nanoparticles by decomposition of [Ru(COD)(COT)] in 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C(1)C(4)Im][NTf(2)], under H(2) in the presence of varying amounts of water or 1-octylamine. For water added during the synthesis of metallic nanoparticles, a decrease of the solubility in the ionic liquid was observed, showed by nanoparticles located at the interface between aqueous and ionic phases. When 1-octylamine is present during the synthesis, stable nanoparticles of a constant size are obtained. When 1-octylamine is added after the synthesis, aggregation of the ruthenium nanoparticles is observed. In order to explain these phenomena, we have explored the molecular interactions between the different species using (13)C-NMR and DOSY (Diffusional Order Spectroscopy) experiments, mixing calorimetry, surface tension measurements and molecular simulations. We conclude that the behaviour of the ruthenium nanoparticles in [C(1)C(4)Im][NTf(2)] in the presence of 1-octylamine depends on the interaction between the ligand and the nanoparticles in terms of the energetics but also of the structural arrangement of the amine at the nanoparticle's surface.

Complex of transferrin with ruthenium for medical applications

DOEpatents

Richards, P.; Srivastava, S.C.; Meinken, G.E.

1984-05-15

A novel ruthenium-transferrin complex is disclosed which is prepared by reacting iron-free human transferrin dissolved in a sodium acetate solution at pH 7 with ruthenium by heating at about 40 C for about 2 hours. The complex is purified by means of gel chromotography with pH 7 sodium acetate as eluent. The mono- or di-metal complex produced can be used in nuclear medicine in the diagnosis and/or treatment of tumors and abscesses. Comparative results with Ga-67-citrate, which is the most widely used tumor-localizing agent in nuclear medicine, indicate increased sensitivity of detection and greater tumor uptake with the Ru-transferrin complex. No Drawings

Ruthenium-Catalyzed Cascade C—H Functionalization of Phenylacetophenones**

PubMed Central

Mehta, Vaibhav P; García-López, José-Antonio; Greaney, Michael F

2014-01-01

Three orthogonal cascade C—H functionalization processes are described, based on ruthenium-catalyzed C—H alkenylation. 1-Indanones, indeno indenes, and indeno furanones were accessed through cascade pathways by using arylacetophenones as substrates under conditions of catalytic [{Ru(p-cymene)Cl2}2] and stoichiometric Cu(OAc)2. Each transformation uses C—H functionalization methods to form C—C bonds sequentially, with the indeno furanone synthesis featuring a C—O bond formation as the terminating step. This work demonstrates the power of ruthenium-catalyzed alkenylation as a platform reaction to develop more complex transformations, with multiple C—H functionalization steps taking place in a single operation to access novel carbocyclic structures. PMID:24453063

Ruthenium-Catalyzed Cascade Annulation of Indole with Propargyl Alcohols.

PubMed

Kaufmann, Julia; Jäckel, Elisabeth; Haak, Edgar

2018-05-14

Cascade transformations forming multiple bonds and one-pot procedures provide rapid access to natural-product-like scaffolds from simple precursors. These atom-economic processes are valuable tools in organic synthesis and drug discovery. Herein, we report on ruthenium-catalyzed cascade annulations of indole with readily available propargyl alcohols. These provide rapid access to diverse carbazoles, cyclohepta[b]indoles, and further fused polycycles with high selectivity. A bifunctional ruthenium complex featuring a redox-coupled cyclopentadienone ligand acts as a common catalyst for the different cascade processes. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bimetallic Nickel/Ruthenium Catalysts Synthesized by Atomic Layer Deposition for Low-Temperature Direct Methanol Solid Oxide Fuel Cells.

PubMed

Jeong, Heonjae; Kim, Jun Woo; Park, Joonsuk; An, Jihwan; Lee, Tonghun; Prinz, Fritz B; Shim, Joon Hyung

2016-11-09

Nickel and ruthenium bimetallic catalysts were heterogeneously synthesized via atomic layer deposition (ALD) for use as the anode of direct methanol solid oxide fuel cells (DMSOFCs) operating in a low-temperature range. The presence of highly dispersed ALD Ru islands over a porous Ni mesh was confirmed, and the Ni/ALD Ru anode microstructure was observed. Fuel cell tests were conducted using Ni-only and Ni/ALD Ru anodes with approximately 350 μm thick gadolinium-doped ceria electrolytes and platinum cathodes. The performance of fuel cells was assessed using pure methanol at operating temperatures of 300-400 °C. Micromorphological changes of the anode after cell operation were investigated, and the content of adsorbed carbon on the anode side of the operated samples was measured. The difference in the maximum power density between samples utilizing Ni/ALD Ru and Pt/ALD Ru, the latter being the best catalyst for direct methanol fuel cells, was observed to be less than 7% at 300 °C and 30% at 350 °C. The improved electrochemical activity of the Ni/ALD Ru anode compared to that of the Ni-only anode, along with the reduction of the number of catalytically active sites due to agglomeration of Ni and carbon formation on the Ni surface as compared to Pt, explains this decent performance.

Application of micro- and nanocrystalline cellulose

NASA Astrophysics Data System (ADS)

Sotnikova, Yu S.; Demina, T. S.; Istomin, A. V.; Goncharuk, G. P.; Grandfils, Ch; Akopova, T. A.; Zelenetskii, A. N.; Babayevsky, P. G.

2018-04-01

Micro- and nanocrystalline forms of cellulose were extracted from flax stalks and evaluated in terms of their applicability for various materials science tasks. It was revealed that both form of cellulose had anisometric morphology with length of 27.1 μm and 159 nm; diameter of 8.7 μm and 85 nm, respectively. They were used as reinforcing fillers for fabrication of composite films based on hydroxyethylcellulose. Film-forming and mechanical properties of the composite materials were significantly varied in dependence on filler content (0–10 wt.%) and size. As a second option of micro- and nanocrystalline cellulose application, a study of their effectiveness as stabilizing agents for oil/water Pickering emulsions was carried out. In contrast to micron-sized cellulose the nanocrystalline form appeared to be successful in the process of CH2Cl2/water interface stabilization and fabrication of polylactide microparticles via oil/water Pickering emulsion solvent evaporation technique.

New donor-acceptor conjugates based on a trifluorenylporphyrin linked to a redox-switchable ruthenium unit.

PubMed

Merhi, Areej; Zhang, Xu; Yao, Dandan; Drouet, Samuel; Mongin, Olivier; Paul, Frédéric; Williams, J A Gareth; Fox, Mark A; Paul-Roth, Christine O

2015-05-28

Reactions of the 16-electron ruthenium complex [Ru(dppe)2Cl][PF6] with metal-free and zinc ethynylphenyltrifluorenylporphyrins and respectively, gave the new dyads and with ethynylruthenium group as a potential electron donor and the porphyrin as a potential electron acceptor. The redox properties of the porphyrins were investigated by cyclic voltammetry and UV spectroelectrochemistry (SEC), which reveal that the monocation and monoanion of metal-free porphyrin are stable under these conditions whereas the formation of the corresponding radical cation or anion of the zinc porphyrin was accompanied by partial decomplexation of the zinc ion. Oxidations of the dyads and gave stable radical cations as probed using IR, NIR and UV SEC methods. These cations show similar NIR and IR bands to those reported for the known 17-electron [Ru(dppe)2(C[triple bond, length as m-dash]CPh)Cl](+) radical cation. Remarkably, the dyad has four stable redox states +2/+1/0/-1 where the second oxidation and first reduction processes take place at the porphyrin unit. Simulated absorption spectra on at optimised geometries obtained by TD-DFT computations with the CAM-B3LYP functional are shown to be in very good agreement with the observed UV absorption spectra of . The spectra of and their oxidised and reduced species were interpreted with the aid of the TD-DFT data. Fluorescence measurements reveal that the dyads and are only weakly emitting compared to and , indicative of quenching of the porphyrinic singlet excited state by the ruthenium centre.

Carrier mobility enhancement of nano-crystalline semiconductor films: Incorporation of redox -relay species into the grain boundary interface

NASA Astrophysics Data System (ADS)

Desilva, L. A.; Bandara, T. M. W. J.; Hettiarachchi, B. H.; Kumara, G. R. A.; Perera, A. G. U.; Rajapaksa, R. M. G.; Tennakone, K.

Dye-sensitized and perovskite solar cells and other nanostructured heterojunction electronic devices require securing intimate electronic contact between nanostructured surfaces. Generally, the strategy is solution phase coating of a hole -collector over a nano-crystalline high-band gap n-type oxide semiconductor film painted with a thin layer of the light harvesting material. The nano-crystallites of the hole - collector fills the pores of the painted oxide surface. Most ills of these devices are associated with imperfect contact and high resistance of the hole conducting layer constituted of nano-crystallites. Denaturing of the delicate light harvesting material forbid sintering at elevated temperatures to reduce the grain boundary resistance. It is found that the interfacial and grain boundary resistance can be significantly reduced via incorporation of redox species into the interfaces to form ultra-thin layers. Suitable redox moieties, preferably bonded to the surface, act as electron transfer relays greatly reducing the film resistance offerring a promising method of enhancing the effective hole mobility of nano-crystalline hole-collectors and developing hole conductor paints for application in nanostructured devices.

Investigations of Nanocrystalline Alloy Electrospark Coating Made of Nanocrystalline Alloy Based on 5БДCP Ferrum

NASA Astrophysics Data System (ADS)

Kolomeichenko, A. V.; Kuznetsov, I. S.; Izmaylov, A. Yu; Solovyev, R. Yu; Sharifullin, S. N.

2017-09-01

The article describes the properties of wear resistant electrospark coating made of nanocrystalline alloy of type 5БДCP (Finemet). It is proved that electrospark coating has nanocrystalline structure which is like amorphous matrix with nanocrystals α - Fe. Coating thickness is 33 μm, micro-hardness is 8461 - 11357 MPa, wear resistance is 0,55×104s/g. Coating ofnanocrystalline alloy of type 5БДCP can be used to increase wear resistance of machinery working surfaces.

Nanocrystalline diamond sensor targeted for selective CRP detection: an ATR-FTIR spectroscopy study.

PubMed

Andersson, Per Ola; Viberg, Pernilla; Forsberg, Pontus; Nikolajeff, Fredrik; Österlund, Lars; Karlsson, Mikael

2016-05-01

Protein immobilization on functionalized fluorine-terminated nanocrystalline (NCD) films was studied by attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy using an immobilization protocol developed to specifically bind C-reactive protein (CRP). Using an ATR-FTIR spectroscopy method employing a force-controlled anvil-type configuration, three critical steps of the ex situ CRP immobilization were analyzed. First, the NCD surface was passivated by deposition of a copolymer layer consisting of polyethylene oxide and polypropylene oxide. Second, a synthetic modified polypeptide binder with high affinity to CRP was covalently attached to the polymeric film. Third, CRP dissolved in aqueous buffer in concentrations of 10-20 μg/mL was added on the functionalized NCD surface. Both the amide I and II bands, due to the polypeptide binder and CRP, were clearly observed in ATR-FTIR spectra. CRP amide I bands were extracted from difference spectra and yielded bands that agreed well with the reported amide I band of free (non-bonded) CRP in solution. Thus, our results show that CRP retains its secondary structure when it is attached to the polypeptide binders. Compared to previous IR studies of CRP in solution, about 200 times lower concentration was applied in the present study. Graphical Abstract Direct non-destructive ATR-FTIR analysis of C-reactive protein (CRP) selectively bound to functionalized nanocrystalline diamond (NCD) sensor surface.

Characterization of Nanocrystalline Aluminum Alloy 5083 Powders Produced by Cryogenic Attrition

DTIC Science & Technology

2014-11-01

Characterization of Nanocrystalline Aluminum Alloy 5083 Powders Produced by Cryogenic Attrition by Tiffany Ngo ARL-TN-0643...November 2014 Characterization of Nanocrystalline Aluminum Alloy 5083 Powders Produced by Cryogenic Attrition Tiffany Ngo Weapons and...3. DATES COVERED (From - To) August 2014 4. TITLE AND SUBTITLE Characterization of Nanocrystalline Aluminum Alloy 5083 Powders Produced by

Oxidation and reduction under cover: Chemistry at the confined space between ultra-thin nanoporous silicates and Ru(0001)

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

J. Anibal Boscoboinik; Zhong, Jian -Qiang; Kestell, John

2016-03-23

The oxidation and reduction of Ru(0001) surfaces at the confined space between two-dimensional nanoporous silica frameworks and Ru(0001) have been investigated using synchrotron-based ambient pressure X-ray photoelectron spectroscopy (AP-XPS). The porous nature of the frameworks and the weak interaction between the silica and the ruthenium substrate allow oxygen and hydrogen molecules to go through the nanopores and react with the metal at the interface between the silica framework and the metal surface. In this work, three types of two-dimensional silica frameworks have been used to study their influence in the oxidation and reduction of the ruthenium surface at elevated pressuresmore » and temperatures. These frameworks are bilayer silica (0.5 nm thick), bilayer aluminosilicate (0.5 nm thick), and zeolite MFI nanosheets (3 nm thick). It is found that the silica frameworks stay essentially intact under these conditions, but they strongly affect the oxidation of ruthenium, with the 0.5 nm thick aluminosilicate bilayer completely inhibiting the oxidation. Furthermore, the latter is believed to be related to the lower chemisorbed oxygen content arising from electrostatic interactions between the negatively charged aluminosilicate framework and the Ru(0001) substrate.« less

Nanocrystalline cellulose from coir fiber: preparation, properties, and applications

USDA-ARS?s Scientific Manuscript database

Nanocrystalline cellulose derived from various botanical sources offers unique and potentially useful characteristics. In principle, any cellulosic material can be considered as a potential source of a nanocrystalline material, including crops, crop residues, and agroindustrial wastes. Because of t...

Potential of nanocrystalline cellulose-fibrin nanocomposites for artificial vascular graft applications

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

Brown, Elvie; Hu, Dehong; Abu-Lail, Nehal

2013-02-19

Nanocrystalline cellulose, a new bio-nanomaterial is utilized as a reinforcing material for biocompatible fibrin matrix to form into a nanocomposite for small-diameter replacement vascular graft application (SDRVG). The periodate oxidation of NCC, which provided it with a reactive carbonyl group, allowed molecular interaction between NCC and fibrin. Such interaction resulted into an effective mechanical reinforcement indicated by the improvement of max. force, elongation at break and modulus when oxidized NCC (ONCC) was incorporated into fibrin. The nanocomposite’s mechanical properties can be manipulated to conform to the native blood vessel by varying the ONCC to fibrin ratio and/or by controlling themore » degree of oxidation of NCC. Using atomic force microscopy had provided fundamental information on the effects of molecular interactions to the nanolevel mechanical properties of NCC/fibrin nanocomposites. This fundamental information established the positive feasibility and commenced continuing investigation for the practical SDRVG application of NCC/fibrin nanocomposite.« less

Nanocrystalline (U0.5Ce0.5)O2±x solid solutions through citrate gel-combustion

NASA Astrophysics Data System (ADS)

Maji, D.; Ananthasivan, K.; Venkata Krishnan, R.; Balakrishnan, S.; Amirthapandian, S.; Joseph, Kitheri; Dasgupta, Arup

2018-04-01

Nanocrystalline powders of (U0.5Ce0.5)O2±x solid solutions were synthesized in bulk (100-200 g) through the citrate gel combustion. The fuel (citric acid) to oxidant (nitrate) mole ratio (R) was varied from 0.1 to 1.0. Two independent lots of the products obtained through the gel-combustion were calcined at 973 K in air and in a mixture of argon containing 8% H2 respectively. All these powders were characterized for their bulk density, X-ray crystallite size, specific surface area, size distribution of the particles, porosity as well as residual carbon. The morphology and microstructures of these powders were studied by using scanning electron microscopy (SEM) and transmission electron microscopy (TEM) respectively. Nanocrystalline single phase fluorite solid solutions having a typical crystallite size of about (7-15 nm) were obtained. These powders were highly porous comprising cuboidal flaky agglomerates. The combustion mixture with an 'R' value of 0.25 was found to undergo volume combustion and was found to yield a product that was distinctly different. The systematic investigation on synthesis and characterization of nanocrystalline UCeO2 is reported for the first time.

Heteroleptic monometallic and trimetallic ruthenium(II) complexes incorporating a π-extended dipyrrin ligand: Light-activated reactions with the A549 lung cancer cell line.

PubMed

Swavey, Shawn; Morford, Krista; Tsao, Max; Comfort, Kristen; Kilroy, Mary Kate

2017-10-01

A heteroleptic monometallic ruthenium(II) and a heteroleptic trimetallic ruthenium(II) complex have been synthesized and characterized. Both complexes have an overall 3+ charge, with the charge density greater for the monometallic complex. The electronic spectra of the monometallic ruthenium(II) complex exhibits intense π-π* transitions associated with the bipyridyl groups along with overlapping metal to ligand charge transfer (MLCT) and ligand centered π-π* transitions ranging from 520nm to approximately 600nm. The trimetallic ruthenium(II) complex, on the other hand, displays more well defined transitions with the expected π-π* transition of the bipyridyl groups at 294nm and Ru(dπ) to bpy(π*) MLCT transitions at 355nm and 502nm. In addition to these absorption bands an intense transition, 578nm, resulting from overlapping dipyrrin (π-π*) and Ru(dπ) to dipyrrin(π*) transitions is observed. Electrochemical and spectroelectrochemical experiments were used to help in assigning these transitions. Irradiation of the complexes in the presence of plasmid DNA within the photodynamic therapy window (600nm to 850nm) reveal, using electrophoresis, that both complexes are capable of causing photo-damage to the DNA backbone. The trimetallic ruthenium(II) complex; however, also shows the ability to generate photoinduced DNA damage in the absence of oxygen, suggesting a photo-oxidative process. Studies of the complexes toward lung cancer cells (A549 cell line) in the absence of light indicate little cytotoxicity up to 50μM. Upon irradiation of the cells with a low power 420nm light source the trimetallic complex showed considerably greater photo-cytotoxicity compared to the monometallic analog. A dose-dependent response curve gives an IC50 of 92μM for complex B. Copyright © 2017 Elsevier Inc. All rights reserved.

Structural, spectral, DFT and biological studies on macrocyclic mononuclear ruthenium (II) complexes

NASA Astrophysics Data System (ADS)

Muthukkumar, M.; Kamal, C.; Venkatesh, G.; Kaya, C.; Kaya, S.; Enoch, Israel V. M. V.; Vennila, P.; Rajavel, R.

2017-11-01

Macrocyclic mononuclear ruthenium (II) complexes have been synthesized by condensation method [Ru (L1, L2, L3) Cl2] L1 = (C36 H31 N9), L2= (C42H36N8), L3= (C32H32 N8)]. These ruthenium complexes have been established by elemental analyses and spectroscopic techniques (Fourier transform infrared spectroscopy (FT-IR), 1H- nuclear magnetic resonance (NMR), 13C- NMR and Electrospray ionization mass spectrometry (ESI-MS)). The coordination mode of the ligand has been confirmed and the octahedral geometry around the ruthenium ion has been revealed. Binding affinity and binding mode of ruthenium (II) complexes with Bovine serum Albumin (BSA) have been characterized by Emission spectra analysis. UV-Visible and fluorescence spectroscopic techniques have also been utilized to examine the interaction between ligand and its complexes L1, L2, & L3 with BSA. Chemical parameters and molecular structure of Ru (II) complexes L1H, L2H, & L3H have been determined by DFT coupled with B3LYP/6-311G** functional in both the gaseous and aqueous phases.

Method for producing nanocrystalline multicomponent and multiphase materials

DOEpatents

Eastman, Jeffrey A.; Rittner, Mindy N.; Youngdahl, Carl J.; Weertman, Julia R.

1998-01-01

A process for producing multi-component and multiphase nanophase materials is provided wherein a plurality of elements are vaporized in a controlled atmosphere, so as to facilitate thorough mixing, and then condensing and consolidating the elements. The invention also provides for a multicomponent and multiphase nanocrystalline material of specified elemental and phase composition having component grain sizes of between approximately 1 nm and 100 nm. This material is a single element in combination with a binary compound. In more specific embodiments, the single element in this material can be a transition metal element, a non-transition metal element, a semiconductor, or a semi-metal, and the binary compound in this material can be an intermetallic, an oxide, a nitride, a hydride, a chloride, or other compound.

Highly efficient quenching of tris(2,2'-bipyridyl)ruthenium(II) electrochemiluminescence by ozone using formaldehyde, methylglyoxal, and glyoxalate as co-reactants and its application to ozone sensing.

PubMed

Gao, Ying; Liu, Xiaoyun; Qi, Wenjing; Gao, Wenyue; Li, Yunhui; Xu, Guobao

2015-06-21

Most electrochemiluminescence (ECL) systems require high concentrations of quencher to totally quench ECL. In this study, we found that ozone can quench tris(2,2'-bipyridyl)ruthenium(II) ECL using formaldehyde, methylglyoxal, or glyoxalate as co-reactants at a glassy carbon electrode with remarkable efficiencies even when the concentration of ozone is merely 0.25% of that of the co-reactant. The strongest quenching is observed with the tris(2,2'-bipyridyl)ruthenium(II)/formaldehyde ECL system. The tris(2,2'-bipyridyl)ruthenium(II)/formaldehyde ECL intensities decrease linearly with the ozone concentration over the range of 0.025-25 μM (r = 0.9947) with a limit of detection of 8 nM. The method is more sensitive and faster than most methods. It shows high selectivity in the presence of other ROS or oxidants and some metal ions, such as H2O2, ClO(-), Mg(2+), Ni(2+), etc. The method exhibits high recoveries for the detection of ozone in a ventilated photocopy room.

Mechanochemical stabilization and sintering of nanocrystalline the (ZrO2)0.97 (Y2O3)0.03 solid solution from pure oxides

NASA Astrophysics Data System (ADS)

Rendtorff, N. M.; Suárez, G.; Sakka, Y.; Aglietti, E. F.

2011-10-01

The mechanochemical activation processing has proved to be an effective technique to enhance a solid-state reaction at relatively low temperatures. In such a process, the mechanical effects of milling, such as reduction of particle size and mixture homogenization, are accompanied by chemical effects, such as partial decomposition of salts or hydroxides resulting in very active reactants. The objective of the present work is to obtain (ZrO2)0.97(Y2O3)0.03 nanocrystalline tetragonal solid solution powders directly using a high energy milling on a mixture of the pure oxides. A second objective is to evaluate the efficiency of the processing proposed and to characterize both textural and structural evolution of the mixtures during the milling processes and throughout posterior low temperature treatments. The Textural and structural evolution were studied by XRD analysis, specific area measurements (BET) and SEM. Firstly a decrease of the crystallinity of the reactants was observed, followed by the disappearance of Y2O3 diffraction peaks and the partial appearance of the tetragonal phase at room temperature. The solid solution proportion was increased with the high energy milling time, obtaining complete stabilization of the tetragonal solid solution with long milling treatments (60 min).The obtained powders were uniaxially pressed and sintered at different temperatures (600-1400°C) the influence of the milling time was correlated with the sinterization degree and final crystalline composition of the materials. Finally, fully stabilized nanocrystalline zirconia materials were obtained satisfactorily by the proposed method.

The Mystery of the Electronic Spectrum of Ruthenium Monophosphide

NASA Astrophysics Data System (ADS)

Adam, Allan G.; Christensen, Ryan M.; Dore, Jacob M.; Konder, Ricarda M.; Tokaryk, Dennis W.

2016-06-01

Using PH3 as a reactant gas and ruthenium as the target metal in the UNB laser ablation spectrometer, the ruthenium monophosphide molecule (RuP) has been detected. Dispersed fluorescence experiments have been performed to determine ground state vibrational frequencies and the presence of any low-lying electronic states. Rotationally resolved spectra of two vibrational bands at 577nm and 592nm have been taken; the bands have been identified as 1-0 and 0-0 bands based on isotopic shifts. Ruthenium has seven stable isotopes and rotational transitions have been observed for six of the RuP isotopologues. RuP is isoelectronic to RuN so it is expected that RuP will have a 2Σ+ ground state and low resolution spectra indicated a likely 2Σ+ - 2Σ+ electronic transition. Further investigation has led us to believe we are observing a 2Π - 2Σ+ transition but mysteriously some important rotational branches are missing. It is hoped that new data to be recorded on a second electronic system we have observed at 535nm will help shed light on this mystery.

Methods for preparation of nanocrystalline rare earth phosphates for lighting applications

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

Comanzo, Holly Ann; Manoharan, Mohan; Martins Loureiro, Sergio Paulo

Disclosed here are methods for the preparation of optionally activated nanocrystalline rare earth phosphates. The optionally activated nanocrystalline rare earth phosphates may be used as one or more of quantum-splitting phosphor, visible-light emitting phosphor, vacuum-UV absorbing phosphor, and UV-emitting phosphor. Also disclosed herein are discharge lamps comprising the optionally activated nanocrystalline rare earth phosphates provided by these methods.

Ruthenium on rutile catalyst, catalytic system, and method for aqueous phase hydrogenations

DOEpatents

Elliot, Douglas C.; Werpy, Todd A.; Wang, Yong; Frye, Jr., John G.

2001-01-01

An essentially nickel- and rhenium-free catalyst is described comprising ruthenium on a titania support where the titania is greater than 75% rutile. A catalytic system containing a nickel-free catalyst comprising ruthenium on a titania support where the titania is greater than 75% rutile, and a method using this catalyst in the hydrogenation of an organic compound in the aqueous phase is also described.

Magnetic Silica-Supported Ruthenium Nanoparticles: An Efficient Catalyst for Transfer Hydrogenation of Carbonyl Compounds

EPA Science Inventory

One-pot synthesis of ruthenium nanoparticles on magnetic silica is described which involve the in situ generation of magnetic silica (Fe3O4@ SiO2) and ruthenium nano particles immobilization; the hydration of nitriles and transfer hydrogenation of carbonyl compounds occurs in hi...

On the suitability of nanocrystalline ferrites as a magnetic carrier for drug delivery: functionalization, conjugation and drug release kinetics.

PubMed

Rana, S; Gallo, A; Srivastava, R S; Misra, R D K

2007-03-01

Superparamagnetic nickel ferrite nanoparticles functionalized with polyvinyl alcohol, polyethylene oxide and polymethacrylic acid (PMAA) polymers and subsequently conjugated with doxorubicin anti-cancer drug are studied for their use as a magnetic carrier for drug delivery. Fourier transform infrared spectroscopy enabled examination of the ability of the nanoparticles to be functionalized with polymers and conjugated with doxorubicin drug. The functionalized polymer-coated nanocrystalline nickel ferrites retain the magnetic characteristics of non-functionalized nanocrystalline nickel ferrites (superparamagnetism, absence of hysteresis, remanence and coercivity at room temperature), encouraging their application as a magnetic carrier for drug delivery. The PMAA-coated nanoferrites are demonstrated as being a potentially superior magnetically targeted drug carrier based on FTIR results and drug release kinetics in the absence and presence of an external magnetic field.

Molecular water oxidation catalyst

DOEpatents

Gratzel, Michael; Munavalli, Shekhar; Pern, Fu-Jann; Frank, Arthur J.

1993-01-01

A dimeric composition of the formula: ##STR1## wherein L', L", L'", and L"" are each a bidentate ligand having at least one functional substituent, the ligand selected from bipyridine, phenanthroline, 2-phenylpyridine, bipyrimidine, and bipyrazyl and the functional substituent selected from carboxylic acid, ester, amide, halogenide, anhydride, acyl ketone, alkyl ketone, acid chloride, sulfonic acid, phosphonic acid, and nitro and nitroso groups. An electrochemical oxidation process for the production of the above functionally substituted bidentate ligand diaqua oxo-bridged ruthenium dimers and their use as water oxidation catalysts is described.

Vacancy-like defects in nanocrystalline SnO2: influence of the annealing treatment under different atmospheres

NASA Astrophysics Data System (ADS)

Macchi, C.; Ponce, M. A.; Desimone, P. M.; Aldao, C. M.; Somoza, A.

2018-03-01

The study of electronic and chemical properties of semiconductor oxides is motivated by their several applications. In particular, tin oxide is widely used as a solid state gas sensor material. In this regard, the defect structure has been proposed to be crucial in determining the resulting film conductivity and then its sensitivity. Here, the characteristics of vacancy-like defects in nanocrystalline commercial high-purity tin oxide powders and the influence of the annealing treatment under different atmospheres are presented. Specifically, SnO2 nanopowders were annealed at 330 °C under three different types of atmospheres: inert (vacuum), oxidative (oxygen) and reductive (hydrogen). The obtained experimental results are discussed in terms of the vacancy-like defects detected, shedding light to the basic conduction mechanisms, which are responsible for gas detection.

Electrocatalyst for alcohol oxidation in fuel cells

DOEpatents

Adzic, Radoslav R.; Marinkovic, Nebojsa S.

2001-01-01

Binary and ternary electrocatalysts are provided for oxidizing alcohol in a fuel cell. The binary electrocatalyst includes 1) a substrate selected from the group consisting of NiWO.sub.4 or CoWO.sub.4 or a combination thereof, and 2) Group VIII noble metal catalyst supported on the substrate. The ternary electrocatalyst includes 1) a substrate as described above, and 2) a catalyst comprising Group VIII noble metal, and ruthenium oxide or molybdenum oxide or a combination thereof, said catalyst being supported on said substrate.

Fatigue stress concentration and notch sensitivity in nanocrystalline metals

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

Furnish, Timothy A.; Boyce, Brad L.; Sharon, John A.

Recent studies have shown the potential for nanocrystalline metals to possess excellent fatigue resistance compared to their coarse-grained counterparts. Although the mechanical properties of nanocrystalline metals are believed to be particularly susceptible to material defects, a systematic study of the effects of geometric discontinuities on their fatigue performance has not yet been performed. In the present work, nanocrystalline Ni–40 wt%Fe containing both intrinsic and extrinsic defects were tested in tension–tension fatigue. The defects were found to dramatically reduce the fatigue resistance, which was attributed to the relatively high notch sensitivity in the nanocrystalline material. Microstructural analysis within the crack-initiation zonesmore » underneath the defects revealed cyclically-induced abnormal grain growth (AGG) as a predominant deformation and crack initiation mechanism during high-cycle fatigue. Furthermore, the onset of AGG and the ensuing fracture is likely accelerated by the stress concentrations, resulting in the reduced fatigue resistance compared to the relatively defect-free counterparts.« less

Fatigue stress concentration and notch sensitivity in nanocrystalline metals

DOE PAGES

Furnish, Timothy A.; Boyce, Brad L.; Sharon, John A.; ...

2016-03-11

Recent studies have shown the potential for nanocrystalline metals to possess excellent fatigue resistance compared to their coarse-grained counterparts. Although the mechanical properties of nanocrystalline metals are believed to be particularly susceptible to material defects, a systematic study of the effects of geometric discontinuities on their fatigue performance has not yet been performed. In the present work, nanocrystalline Ni–40 wt%Fe containing both intrinsic and extrinsic defects were tested in tension–tension fatigue. The defects were found to dramatically reduce the fatigue resistance, which was attributed to the relatively high notch sensitivity in the nanocrystalline material. Microstructural analysis within the crack-initiation zonesmore » underneath the defects revealed cyclically-induced abnormal grain growth (AGG) as a predominant deformation and crack initiation mechanism during high-cycle fatigue. Furthermore, the onset of AGG and the ensuing fracture is likely accelerated by the stress concentrations, resulting in the reduced fatigue resistance compared to the relatively defect-free counterparts.« less

Characterisation of Suspension Precipitated Nanocrystalline Hydroxyapatite Powders

NASA Astrophysics Data System (ADS)

Mallik, P. K.; Swain, P. K.; Patnaik, S. C.

2016-02-01

Hydroxyapatite (HA) is a well-known biomaterial for coating on femoral implants, filling of dental cavity and scaffold for tissue replacement. Hydroxyapatite possess limited load bearing capacity due to their brittleness. In this paper, the synthesis of nanocrystalline hydroxyapatite powders was prepared by dissolving calcium oxide in phosphoric acid, followed by addition of ammonia liquor in a beaker. The prepared solution was stirred by using magnetic stirrer operated at temperature of 80°C for an hour. This leads to the formation of hydroxyapatite precipitate. The precipitate was dried in oven for overnight at 100°C. The dried agglomerated precipitate was calcined at 800°C in conventional furnace for an hour. The influence of calcium oxide concentration and pH on the resulting precipitates was studied using BET, XRD and SEM. As result, a well-defined sub-rounded morphology of powders size of ∼41 nm was obtained with a salt concentration of 0.02 M. Finally, it can be concluded that small changes in the reaction conditions led to large changes in final size, shape and degree of aggregation of the hydroxyapatite particles.

Nanoscale assembly of high-temperature oxidation-resistant nanocomposites.

PubMed

Peng, Xiao

2010-02-01

Structural considerations for designing a high-temperature oxidation-resistant metallic material are proposed, based on the dependence of the material structure on a promotion of the development of a protective scale of chromia or alumina. The material should have numerous sites on its surface for nucleating the protective oxides at the onset of oxidation and abundant grain boundaries in deeper areas for simultaneously supplying sufficient flux of the protective-oxide-forming elements toward the surface for a rapid linkage of the oxide nuclei through their lateral growth. Based on these considerations, we fabricated, using an electrochemical deposition method, novel nanocomposites which have a nanocrystalline metal matrix containing Cr and/or Al nanoparticles dispersed at the nano length scale. The validity of the design considerations is verified by comparing the high-temperature oxidation of a typical Ni-Cr nanocomposite system with two types of conventional Ni-Cr materials having similar or higher Cr content but different structure: one is a composite having a nanocrystalline Ni matrix containing Cr microparticles dispersed at the microscale and the other are micron-grained Ni-Cr alloys with the Cr distribution at the atomic length scale.

Nanoscale assembly of high-temperature oxidation-resistant nanocomposites

NASA Astrophysics Data System (ADS)

Peng, Xiao

2010-02-01

Structural considerations for designing a high-temperature oxidation-resistant metallic material are proposed, based on the dependence of the material structure on a promotion of the development of a protective scale of chromia or alumina. The material should have numerous sites on its surface for nucleating the protective oxides at the onset of oxidation and abundant grain boundaries in deeper areas for simultaneously supplying sufficient flux of the protective-oxide-forming elements toward the surface for a rapid linkage of the oxide nuclei through their lateral growth. Based on these considerations, we fabricated, using an electrochemical deposition method, novel nanocomposites which have a nanocrystalline metal matrix containing Cr and/or Al nanoparticles dispersed at the nano length scale. The validity of the design considerations is verified by comparing the high-temperature oxidation of a typical Ni-Cr nanocomposite system with two types of conventional Ni-Cr materials having similar or higher Cr content but different structure: one is a composite having a nanocrystalline Ni matrix containing Cr microparticles dispersed at the microscale and the other are micron-grained Ni-Cr alloys with the Cr distribution at the atomic length scale.

The catalytic removal of ammonia and nitrogen oxides from spacecabin atmospheres

NASA Technical Reports Server (NTRS)

Gully, A. J.; Graham, R. R.; Halligan, J. E.; Bentsen, P. C.

1973-01-01

Investigations were made on methods for the removal of ammonia and to a lesser extent nitrogen oxides in low concentrations from air. The catalytic oxidation of ammonia was studied over a temperature range of 250 F to 600 F and a concentration range 20 ppm to 500 ppm. Of the catalysts studied, 0.5 percent ruthenium supported on alumina was found to be superior. This material is active at temperatures as low as 250 F and was found to produce much less nitrous oxide than the other two active catalysts, platinum on alumina and Hopcalite. A quantitative design model was developed which will permit the performance of an oxidizer to be calculated. The ruthenium was found to be relatively insensitive to low concentrations of water and to oxygen concentration between 21 percent and 100 percent. Hydrogen sulfide was found to be a poison when injected in relatively large quantities. The adsorption of ammonia by copper sulfate treated silica gel was investigated at temperatures of 72 F and 100 F. A quantitative model was developed for predicting adsorption bed behavior.

Platinum supported on titanium–ruthenium oxide is a remarkably stable electrocatayst for hydrogen fuel cell vehicles

PubMed Central

Parrondo, Javier; Han, Taehee; Niangar, Ellazar; Wang, Chunmei; Dale, Nilesh; Adjemian, Kev; Ramani, Vijay

2014-01-01

We report a unique and highly stable electrocatalyst—platinum (Pt) supported on titanium–ruthenium oxide (TRO)—for hydrogen fuel cell vehicles. The Pt/TRO electrocatalyst was exposed to stringent accelerated test protocols designed to induce degradation and failure mechanisms identical to those seen during extended normal operation of a fuel cell automobile—namely, support corrosion during vehicle startup and shutdown, and platinum dissolution during vehicle acceleration and deceleration. These experiments were performed both ex situ (on supports and catalysts deposited onto a glassy carbon rotating disk electrode) and in situ (in a membrane electrode assembly). The Pt/TRO was compared against a state-of-the-art benchmark catalyst—Pt supported on high surface-area carbon (Pt/HSAC). In ex situ tests, Pt/TRO lost only 18% of its initial oxygen reduction reaction mass activity and 3% of its oxygen reduction reaction-specific activity, whereas the corresponding losses for Pt/HSAC were 52% and 22%. In in situ-accelerated degradation tests performed on membrane electrode assemblies, the loss in cell voltage at 1 A · cm−2 at 100% RH was a negligible 15 mV for Pt/TRO, whereas the loss was too high to permit operation at 1 A · cm−2 for Pt/HSAC. We clearly show that electrocatalyst support corrosion induced during fuel cell startup and shutdown is a far more potent failure mode than platinum dissolution during fuel cell operation. Hence, we posit that the need for a highly stable support (such as TRO) is paramount. Finally, we demonstrate that the corrosion of carbon present in the gas diffusion layer of the fuel cell is only of minor concern. PMID:24367118

Platinum supported on titanium-ruthenium oxide is a remarkably stable electrocatayst for hydrogen fuel cell vehicles.

PubMed

Parrondo, Javier; Han, Taehee; Niangar, Ellazar; Wang, Chunmei; Dale, Nilesh; Adjemian, Kev; Ramani, Vijay

2014-01-07

We report a unique and highly stable electrocatalyst-platinum (Pt) supported on titanium-ruthenium oxide (TRO)-for hydrogen fuel cell vehicles. The Pt/TRO electrocatalyst was exposed to stringent accelerated test protocols designed to induce degradation and failure mechanisms identical to those seen during extended normal operation of a fuel cell automobile-namely, support corrosion during vehicle startup and shutdown, and platinum dissolution during vehicle acceleration and deceleration. These experiments were performed both ex situ (on supports and catalysts deposited onto a glassy carbon rotating disk electrode) and in situ (in a membrane electrode assembly). The Pt/TRO was compared against a state-of-the-art benchmark catalyst-Pt supported on high surface-area carbon (Pt/HSAC). In ex situ tests, Pt/TRO lost only 18% of its initial oxygen reduction reaction mass activity and 3% of its oxygen reduction reaction-specific activity, whereas the corresponding losses for Pt/HSAC were 52% and 22%. In in situ-accelerated degradation tests performed on membrane electrode assemblies, the loss in cell voltage at 1 A · cm(-2) at 100% RH was a negligible 15 mV for Pt/TRO, whereas the loss was too high to permit operation at 1 A · cm(-2) for Pt/HSAC. We clearly show that electrocatalyst support corrosion induced during fuel cell startup and shutdown is a far more potent failure mode than platinum dissolution during fuel cell operation. Hence, we posit that the need for a highly stable support (such as TRO) is paramount. Finally, we demonstrate that the corrosion of carbon present in the gas diffusion layer of the fuel cell is only of minor concern.

Ga2O3 and GaN nanocrystalline film: reverse micelle assisted solvothermal synthesis and characterization.

PubMed

Sinha, Godhuli; Ganguli, Dibyendu; Chaudhuri, Subhadra

2008-03-01

Gallium oxide (beta-Ga2O3) nanoparticles were successfully deposited on quartz glass substrates using sodium bis(2-ethylhexyl) sulfosuccinate (AOT)/n-hexane/ethylene glycol monomethyl ether (EGME) reverse micelle-mediated solvothermal process with different omega values. The mean diameter of Ga2O3 particles was approximately 2-3 nm and found to be approximately independent of omega values of the reverse micelles. However, when the Ga2O3 nanocrystalline films were nitrided at 900 degrees C under flowing NH3 atmosphere for 1 h, the mean diameter of the resulted gallium nitride (wurtzite-GaN) nanoparticles varied from 3-9 nm. Both nanocrystalline films of Ga2O3 and GaN were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy, UV-vis spectroscopy and photoluminescence in order to study their chemical and physical properties explicitly.

Pentamethylcyclopentadienyl-ruthenium catalysts for regio- and enantioselective allylation of nucleophiles.

PubMed

Bruneau, Christian; Renaud, Jean-Luc; Demerseman, Bernard

2006-07-05

Ruthenium(II) complexes containing the pentamethylcyclopentadienyl ligand efficiently perform the activation of allylic carbonates and halides to generate cationic and dicationic ruthenium(IV) complexes. This activation has been transferred as a key step to the catalytic allylation of nucleophiles. The structural and electronic properties of the allylic moieties lead to the regioselective formation of chiral products resulting from nucleophilic addition to their most substituted terminus. The catalytic activity of various Ru(Cp*) precatalysts in several allylic substitutions by C and O nucleophiles will be presented. The enantioselective version that has been demonstrated by using optically pure bisoxazoline ligands will also be discussed.

Characterization of Self-Assembled Monolayers on a Ruthenium Surface

PubMed Central

2017-01-01

We have modified and stabilized the ruthenium surface by depositing a self-assembled monolayer (SAM) of 1-hexadecanethiol on a polycrystalline ruthenium thin film. The growth mechanism, dynamics, and stability of these monolayers were studied. SAMs, deposited under ambient conditions, on piranha-cleaned and piranha + H2SO4 cleaned substrates were compared to monolayers formed on H-radical-cleaned Ru surfaces. We found that alkanethiols on H-radical-cleaned Ru formed densely packed monolayers that remained stable when kept in a nitrogen atmosphere. X-ray photoelectron spectroscopy (XPS) shows a distinct sulfur peak (BE = 162.3 eV), corresponding to metal–sulfur bonding. When exposed to ambient conditions, the SAM decayed over a period of hours. PMID:28585831

Development and application of a ruthenium(II) complex-based photoluminescent and electrochemiluminescent dual-signaling probe for nitric oxide.

PubMed

Zhang, Wenzhu; Zhang, Jingmei; Zhang, Hailei; Cao, Liyan; Zhang, Run; Ye, Zhiqiang; Yuan, Jingli

2013-11-15

A ruthenium(II) complex, [Ru(bpy)2(DA-phen)](PF6)2 (bpy: 2,2'-bipyridine; DA-phen: 5,6-diamino-1,10-phenanthroline), has been developed as a photoluminescent (PL) and electrochemiluminescent (ECL) dual-signaling probe for the highly sensitive and selective detection of nitric oxide (NO) in aqueous and biological samples. Due to the presence of electron transfer process from diamino group to the excited-state of the Ru(II) complex, the PL and ECL intensities of the probe are very weak. After the probe was reacted with NO in physiological pH aqueous media under aerobic conditions to afford its triazole derivative, [Ru(bpy)2(TA-phen)](2+) (TA-phen: 5,6-triazole-1,10-phenanthroline), the electron transfer process was inhibited, so that the PL and ECL efficiency of the Ru(II) complex was remarkably increased. The PL and ECL responses of the probe to NO in physiological pH media are highly sensitive with the detection limits at low micromolar concentration level, and highly specific without the interferences of other reactive oxygen/nitrogen species (ROS/RNS) and metal ions. Moreover, the probe has good cell-membrane permeability, and can be rapidly transferred into living cells for trapping the intracellular NO molecules. These features enabled the probe to be successfully used for the monitoring of the endogenous NO production in living biological cell and tissue samples with PL and ECL dual-modes. Copyright © 2013 Elsevier B.V. All rights reserved.

A ruthenium anticancer compound interacts with histones and impacts differently on epigenetic and death pathways compared to cisplatin

PubMed Central

Capuozzo, Antonelle; Ali, Moussa; Santamaria, Rita; Armant, Olivier; Delalande, Francois; Dorsselaer, Alain Van; Cianferani, Sarah; Spencer, John; Pfeffer, Michel; Mellitzer, Georg; Gaiddon, Christian

2017-01-01

Ruthenium complexes are considered as potential replacements for platinum compounds in oncotherapy. Their clinical development is handicapped by a lack of consensus on their mode of action. In this study, we identify three histones (H3.1, H2A, H2B) as possible targets for an anticancer redox organoruthenium compound (RDC11). Using purified histones, we confirmed an interaction between the ruthenium complex and histones that impacted on histone complex formation. A comparative study of the ruthenium complex versus cisplatin showed differential epigenetic modifications on histone H3 that correlated with differential expression of histone deacetylase (HDAC) genes. We then characterized the impact of these epigenetic modifications on signaling pathways employing a transcriptomic approach. Clustering analyses showed gene expression signatures specific for cisplatin (42%) and for the ruthenium complex (30%). Signaling pathway analyses pointed to specificities distinguishing the ruthenium complex from cisplatin. For instance, cisplatin triggered preferentially p53 and folate biosynthesis while the ruthenium complex induced endoplasmic reticulum stress and trans-sulfuration pathways. To further understand the role of HDACs in these regulations, we used suberanilohydroxamic acid (SAHA) and showed that it synergized with cisplatin cytotoxicity while antagonizing the ruthenium complex activity. This study provides critical information for the characterization of signaling pathways differentiating both compounds, in particular, by the identification of a non-DNA direct target for an organoruthenium complex. PMID:27935863

Cyano- and polycyanometallo-porphyrins as catalysts for alkane oxidation

DOEpatents

Ellis, P.E. Jr.; Lyons, J.E.

1995-01-17

New compositions of matter comprising cyano-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has cyano groups attached thereto in meso and/or [beta]-pyrrolic positions.

Cyano- and polycyanometallo-porphyrins as catalysts for alkane oxidation

DOEpatents

Ellis, P.E. Jr.; Lyons, J.E.

1993-05-18

New compositions of matter comprising cyano-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has cyano groups attached thereto in meso- and/or [beta]-pyrrolic positions.

Cyano- and polycyanometallo-porphyrins as catalysts for alkane oxidation

DOEpatents

Ellis, Jr., Paul E.; Lyons, James E.

1993-01-01

New compositions of matter comprising cyano-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has cyano groups attached thereto in meso and/or .beta.-pyrrolic positions.

Cyano- and polycyanometallo-porphyrins as catalysts for alkane oxidation

DOEpatents

Ellis, Jr., Paul E.; Lyons, James E.

1995-01-01

New compositions of matter comprising cyano-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has cyano groups attached thereto in meso and/or .beta.-pyrrolic positions.

Some aspects of pulsed laser deposition of Si nanocrystalline films

NASA Astrophysics Data System (ADS)

Polyakov, B.; Petruhins, A.; Butikova, J.; Kuzmin, A.; Tale, I.

2009-11-01

Nanocrystalline silicon films were deposited by a picosecond laser ablation on different substrates in vacuum at room temperature. A nanocrystalline structure of the films was evidenced by atomic force microscopy (AFM), optical and Raman spectroscopies. A blue shift of the absorption edge was observed in optical absorption spectra, and a decrease of the optical phonon energy at the Brillouin zone centre was detected by Raman scattering. Early stages of nanocrystalline film formation on mica and HOPG substrates were studied by AFM. Mechanism of nanocrystal growth on substrate is discussed. in here

Electrodeposition of Nanocrystalline Co-P Coatings as a Hard Chrome Alternative

DTIC Science & Technology

2009-09-02

Electrodeposition  of Nanocrystalline Co‐P  Coatings as a Hard Chrome Alternative Report Documentation Page Form ApprovedOMB No. 0704-0188 Public reporting burden...AND SUBTITLE Electrodeposition of Nanocrystalline Co‐P Coatings as a Hard Chrome Alternative 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c...Defense Conference – 2 September 2009 Conventional  Electrodeposits Polycrystalline (10‐100 µm) Electrodeposited Nanocrystalline Materials Pulsed

Method for producing nanocrystalline multicomponent and multiphase materials

DOEpatents

Eastman, J.A.; Rittner, M.N.; Youngdahl, C.J.; Weertman, J.R.

1998-03-17

A process for producing multi-component and multiphase nanophase materials is provided wherein a plurality of elements are vaporized in a controlled atmosphere, so as to facilitate thorough mixing, and then condensing and consolidating the elements. The invention also provides for a multicomponent and multiphase nanocrystalline material of specified elemental and phase composition having component grain sizes of between approximately 1 nm and 100 nm. This material is a single element in combination with a binary compound. In more specific embodiments, the single element in this material can be a transition metal element, a non-transition metal element, a semiconductor, or a semi-metal, and the binary compound in this material can be an intermetallic, an oxide, a nitride, a hydride, a chloride, or other compound. 6 figs.

Structural, optical and magnetic behaviour of nanocrystalline Volborthite

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

Arvind, Hemant K., E-mail: hemantarvind@gmail.com; Kumar, Sudhish, E-mail: skmlsu@gmail.com; Kalal, Sangeeta

2016-05-06

Nanocrystalline sample of Volborthite (Copper Pyrovanadate: Cu{sub 3}V{sub 2} (OH){sub 2}O{sub 7}.2H{sub 2}O) has been synthesized using wet chemical route and characterized by XRD, SEM, FTIR, UV-Vis-NIR spectroscopic and magnetization measurements. Room temperature X-ray diffraction analysis confirms the single phase monoclinic structure and nanocrystalline nature of Volborthite. The UV-Visible optical absorption spectrum displays two broad absorption peaks in the range of 200-350 nm and 400-1000 nm. The direct band gap is found to be E{sub g}= ∼2.74 eV. Bulk Volborthite was reported to be a natural frustrated antiferromagnet, however our nanocrystalline Volborthite display week ferromagnetic hysteresis loop with very small coercivity andmore » retentivity at room temperature.« less

Alkyne–Aldehyde Reductive C–C Coupling through Ruthenium-Catalyzed Transfer Hydrogenation: Direct Regio- and Stereoselective Carbonyl Vinylation to Form Trisubstituted Allylic Alcohols in the Absence of Premetallated Reagents

PubMed Central

Leung, Joyce C.; Patman, Ryan L.; Sam, Brannon

2011-01-01

Nonsymmetric 1,2-disubstituted alkynes engage in reductive coupling to a variety of aldehydes under the conditions of ruthenium-catalyzed transfer hydrogenation by employing formic acid as the terminal reductant and delivering the products of carbonyl vinylation with good to excellent levels of regioselectivity and with complete control of olefin stereochemistry. As revealed in an assessment of the ruthenium counterion, iodide plays an essential role in directing the regioselectivity of C–C bond formation. Isotopic labeling studies corroborate reversible catalytic propargyl C–H oxidative addition in advance of the C–C coupling, and demonstrate that the C–C coupling products do not experience reversible dehydrogenation by way of enone intermediates. This transfer hydrogenation protocol enables carbonyl vinylation in the absence of stoichiometric metallic reagents. PMID:21953608

Photoexpulsion of Surface-Grafted Ruthenium Complexes and Subsequent Release of Cytotoxic Cargos to Cancer Cells from Mesoporous Silica Nanoparticles

PubMed Central

Frasconi, Marco; Liu, Zhichang; Lei, Juying; Wu, Yilei; Strekalova, Elena; Malin, Dmitry; Ambrogio, Michael W.; Chen, Xinqi; Botros, Youssry Y.; Cryns, Vincent L.; Sauvage, Jean-Pierre; Stoddart, J. Fraser

2014-01-01

Ruthenium(II) polypyridyl complexes have emerged both as promising probes of DNA structure and as anticancer agents because of their unique photophysical and cytotoxic properties. A key consideration in the administration of those therapeutic agents is the optimization of their chemical reactivities to allow facile attack on the target sites, yet avoid unwanted side effects. Here, we present a drug delivery platform technology, obtained by grafting the surface of mesoporous silica nanoparticles (MSNPs) with ruthenium(II) dipyridophenazine (dppz) complexes. This hybrid nanomaterial displays enhanced luminescent properties relative to that of the ruthenium(II) dppz complex in a homogeneous phase. Since the coordination between the ruthenium(II) complex and a monodentate ligand linked covalently to the nanoparticles can be cleaved under irradiation with visible light, the ruthenium complex can be released from the surface of the nanoparticles by selective substitution of this ligand with a water molecule. Indeed, the modified MSNPs undergo rapid cellular uptake, and after activation with light, the release of an aqua ruthenium(II) complex is observed. We have delivered, in combination, the ruthenium(II) complex and paclitaxel, loaded in the mesoporous structure, to breast cancer cells. This hybrid material represents a promising candidate as one of the so-called theranostic agents that possess both diagnostic and therapeutic functions. PMID:23815127

Photoexpulsion of surface-grafted ruthenium complexes and subsequent release of cytotoxic cargos to cancer cells from mesoporous silica nanoparticles.

PubMed

Frasconi, Marco; Liu, Zhichang; Lei, Juying; Wu, Yilei; Strekalova, Elena; Malin, Dmitry; Ambrogio, Michael W; Chen, Xinqi; Botros, Youssry Y; Cryns, Vincent L; Sauvage, Jean-Pierre; Stoddart, J Fraser

2013-08-07

Ruthenium(II) polypyridyl complexes have emerged both as promising probes of DNA structure and as anticancer agents because of their unique photophysical and cytotoxic properties. A key consideration in the administration of those therapeutic agents is the optimization of their chemical reactivities to allow facile attack on the target sites, yet avoid unwanted side effects. Here, we present a drug delivery platform technology, obtained by grafting the surface of mesoporous silica nanoparticles (MSNPs) with ruthenium(II) dipyridophenazine (dppz) complexes. This hybrid nanomaterial displays enhanced luminescent properties relative to that of the ruthenium(II) dppz complex in a homogeneous phase. Since the coordination between the ruthenium(II) complex and a monodentate ligand linked covalently to the nanoparticles can be cleaved under irradiation with visible light, the ruthenium complex can be released from the surface of the nanoparticles by selective substitution of this ligand with a water molecule. Indeed, the modified MSNPs undergo rapid cellular uptake, and after activation with light, the release of an aqua ruthenium(II) complex is observed. We have delivered, in combination, the ruthenium(II) complex and paclitaxel, loaded in the mesoporous structure, to breast cancer cells. This hybrid material represents a promising candidate as one of the so-called theranostic agents that possess both diagnostic and therapeutic functions.

[Raman studies of nanocrystalline BaTiO3 ceramics].

PubMed

Xiao, Chang-jiang; Jin, Chang-qing; Wang, Xiao-hui

2008-12-01

High pressure can significantly increase the densification. Further, during the high pressure assisted sintering, the nucleation rate is increased due to reduced energy barrier and the growth rate is suppressed due to the decreased diffusivity. Thus high pressure enables the specimen to be fabricated with relatively lower temperature and shorter sintering period that assures to obtain dense nanocrystalline ceramics. Dense nanocrystalline BaTiO3 ceramics with uniform grain sizes of 60 and 30 nm, respectively, were obtained by pressure assisted sintering. The crystal structure and phase transitions were investigated by Raman scattering at temperatures ranging from -190 to 200 degrees C. The Raman results indicated that the evolution of Raman spectrum with grain size is characterized by an intensity decrease, a broadening of the line width, a frequency shift, and the disappearance of the Raman mode. With increasing temperature, similar to 3 mm BaTiO3 normal ceramics, the successive phase transitions from rhombohedral to orthorhombic, orthorhombic to tetragonal, and tetragonal to cubic were also observed in nanocrystalline BaTiO3 ceramics. In addition, when particle size is reduced to the nanoscale, one will find some unusual physical properties in nanocrystalline ceramics, compared with those of coarse-grained BaTiO3 ceramics. The different coexistences of multiphase were found at different temperature. Especially, the ferroelectric tetragonal and orthorhombic phase can coexist at room temperature in nanocrystalline BaTiO3 ceramics. The phenomenon can be explained by the internal stress. The coexistences of different ferroelectric phases at room temperature indicate that the critical grain size for the disappearance of ferroelectricity in nanocrystalline BaTiO3 ceramics fabricated by pressure assisted sintering is below 30 nm.

Characterization of nanocrystalline ZnO:Al films by sol-gel spin coating method

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

Gareso, P. L., E-mail: pgareso@gmail.com; Rauf, N., E-mail: pgareso@gmail.com; Juarlin, E., E-mail: pgareso@gmail.com

2014-09-25

Nanocrystalline ZnO films doped with aluminium by sol-gel spin coating method have been investigated using optical transmittance UV-Vis and X-ray diffraction (X-RD) measurements. ZnO films were prepared using zinc acetate dehydrate (Zn(CH{sub 3}COO){sub 2}@@‡2H{sub 2}O), ethanol, and diethanolamine (DEA) as a starting material, solvent, and stabilizer, respectively. For doped films, AlCl{sub 3} was added to the mixture. The ZnO:Al films were deposited on a transparent conductive oxide (TCO) substrate using spin coating technique at room temperature with a rate of 3000 rpm in 30 sec. The deposited films were annealed at various temperatures from 400°C to 600°C during 60 minutes.more » The transmittance UV-Vis measurement results showed that after annealing at 400°C, the energy band gap profile of nanocrystalline ZnO:Al film was a blue shift. This indicated that the band gap of ZnO:Al increased after annealing due to the increase of crystalline size. As the annealing temperature increased the bandgap energy was a constant. In addition to this, there was a small oscillation occurring after annealing compared to the as–grown samples. In the case of X-RD measurements, the crystalinity of the films were amorphous before annealing, and after annealing the crystalinity became enhance. Also, X-RD results showed that structure of nanocrystalline ZnO:Al films were hexagonal polycrystalline with lattice parameters are a = 3.290 Å and c = 5.2531 Å.« less

Excited-state redox properties of ruthenium(II) phthalocyanine from electron-transfer quenching

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

Prasad, D.R.; Ferraudi, G.

1982-09-30

Electron-transfer reactions between the lowest-lying triplet state, /sup 3/..pi pi../sup */, of ruthenium (phthalocyanine)(pyridine)/sub 2/ and various nitroaromatic compounds have been studied by laser and conventional flash photolysis. Quenching rate constants determined for the oxidation of the excited state have been treated according to the Marcus-Hush theory. A self-exchange rate constant K approx. 10/sup 7/ M/sup -1/ x/sup -1/ was determined for the self-exchange reaction between the /sup 3/..pi pi../sup */ and radical cation, Ru(ph)(py)/sub 2//sup +/. Such a value indicates that the major component to the Franck-Condon reorganizational energy is the outer-sphere contribution. The photochemical properties of the phthalocyaninesmore » are discussed in terms of the redox potentials estimate for various excited states.« less

Relationship of microstructure properties to oxygen impurities in nanocrystalline silicon photovoltaic materials

NASA Astrophysics Data System (ADS)

Xu, H.; Wen, C.; Liu, H.; Li, Z. P.; Shen, W. Z.

2013-03-01

We have fully investigated the correlation of microstructure properties and oxygen impurities in hydrogenated nanocrystalline silicon photovoltaic films. The achievement has been realized through a series of different hydrogen dilution ratio treatment by plasma enhanced chemical vapor deposition system. Raman scattering, x-ray diffraction, and ultraviolet-visible transmission techniques have been employed to characterize the physical structural characterization and to elucidate the structure evolution. The bonding configuration of the oxygen impurities was investigated by x-ray photoelectron spectroscopy and the Si-O stretching mode of infrared-transmission, indicating that the films were well oxidized in SiO2 form. Based on the consistence between the proposed structure factor and the oxygen content, we have demonstrated that there are two dominant disordered structure regions closely related to the post-oxidation contamination: plate-like configuration and clustered microvoids.

A Theoretical Study of Methanol Oxidation on RuO 2(110): Bridging the Pressure Gap

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

Latimer, Allegra A.; Abild-Pedersen, Frank; Norskov, Jens K.

Partial oxidation catalysis is often fraught with selectivity problems, largely because there is a tendency of oxidation products to be more reactive than the starting material. One industrial process that has successfully overcome this problem is partial oxidation of methanol to formaldehyde. This process has become a global success, with an annual production of 30 million tons. Although ruthenium catalysts have not shown activity as high as the current molybdena or silver-based industrial standards, the study of ruthenium systems has the potential to elucidate which catalyst properties facilitate the desired partial oxidation reaction as opposed to deep combustion due tomore » a pressure-dependent selectivity “switch” that has been observed in ruthenium-based catalysts. In this work, we find that we are able to successfully rationalize this “pressure gap” using near-ab initio steady-state microkinetic modeling on RuO 2(110). We obtain molecular desorption prefactors from experiment and determine all other energetics using density functional theory. We show that, under ambient pressure conditions, formaldehyde production is favored on RuO 2(110), whereas under ultrahigh vacuum pressure conditions, full combustion to CO 2 takes place. We glean from our model several insights regarding how coverage effects, oxygen activity, and rate-determining steps influence selectivity and activity. As a result, we believe the understanding gained in this work might advise and inspire the greater partial oxidation community and be applied to other catalytic processes which have not yet found industrial success.« less

A Theoretical Study of Methanol Oxidation on RuO 2(110): Bridging the Pressure Gap

DOE PAGES

Latimer, Allegra A.; Abild-Pedersen, Frank; Norskov, Jens K.

2017-05-26

Partial oxidation catalysis is often fraught with selectivity problems, largely because there is a tendency of oxidation products to be more reactive than the starting material. One industrial process that has successfully overcome this problem is partial oxidation of methanol to formaldehyde. This process has become a global success, with an annual production of 30 million tons. Although ruthenium catalysts have not shown activity as high as the current molybdena or silver-based industrial standards, the study of ruthenium systems has the potential to elucidate which catalyst properties facilitate the desired partial oxidation reaction as opposed to deep combustion due tomore » a pressure-dependent selectivity “switch” that has been observed in ruthenium-based catalysts. In this work, we find that we are able to successfully rationalize this “pressure gap” using near-ab initio steady-state microkinetic modeling on RuO 2(110). We obtain molecular desorption prefactors from experiment and determine all other energetics using density functional theory. We show that, under ambient pressure conditions, formaldehyde production is favored on RuO 2(110), whereas under ultrahigh vacuum pressure conditions, full combustion to CO 2 takes place. We glean from our model several insights regarding how coverage effects, oxygen activity, and rate-determining steps influence selectivity and activity. As a result, we believe the understanding gained in this work might advise and inspire the greater partial oxidation community and be applied to other catalytic processes which have not yet found industrial success.« less

Nanocrystalline Ce 1- xY xO 2- x/2 (0≤ x≤0.35) Oxides via Carbonate Precipitation: Synthesis and Characterization

NASA Astrophysics Data System (ADS)

Li, Ji-Guang; Ikegami, Takayasu; Wang, Yarong; Mori, Toshiyuki

2002-10-01

A novel carbonate (co)precipitation method, employing nitrates as the starting salts and ammonium carbonate as the precipitant, has been used to synthesize nanocrystalline CeO 2 and Ce 1- xY xO 2- x/2 ( x≤0.35) solid-solutions. The resultant powders are characterized by elemental analysis, differential thermal analysis/thermogravimetry (DTA/TG), X-ray diffractometry (XRD), Brunauer-Emmett-Teller (BET) analysis, and high-resolution scanning electron microscopy (HRSEM). Due to the direct formation of carbonate solid-solutions during precipitation, Ce 1- xY xO 2- x/2 solid-solution oxides are formed directly during calcination at a very low temperature of ˜300°C for 2 h. The thus-produced oxide nanopowders are essentially non-agglomerated, as revealed by BET in conjunction with XRD analysis. The solubility of YO 1.5 in CeO 2 is determined via XRD to be somewhere in the range from 27 to 35 mol%, from which a Y 2O 3-related type-C phase appears in the final product. Y 3+-doping promotes the formation of spherical nanoparticles, retards thermal decomposition of the precursors, and suppresses significantly crystallite coarsening of the oxides during calcination. The activation energy for crystallite coarsening increases gradually from 68.7 kJ mol -1 for pure CeO 2 to 138.6 kJ mol -1 for CeO 2 doped with 35 mol% YO 1.5. The dopant effects on crystallite coarsening is elaborated from the view point of solid-state chemistry.

Mesoporous nanocrystalline film architecture for capacitive storage devices

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

Dunn, Bruce S.; Tolbert, Sarah H.; Wang, John

A mesoporous, nanocrystalline, metal oxide construct particularly suited for capacitive energy storage that has an architecture with short diffusion path lengths and large surface areas and a method for production are provided. Energy density is substantially increased without compromising the capacitive charge storage kinetics and electrode demonstrates long term cycling stability. Charge storage devices with electrodes using the construct can use three different charge storage mechanisms immersed in an electrolyte: (1) cations can be stored in a thin double layer at the electrode/electrolyte interface (non-faradaic mechanism); (2) cations can interact with the bulk of an electroactive material which then undergoesmore » a redox reaction or phase change, as in conventional batteries (faradaic mechanism); or (3) cations can electrochemically adsorb onto the surface of a material through charge transfer processes (faradaic mechanism).« less

Nanocrystalline Aluminum Truss Cores for Lightweight Sandwich Structures

NASA Astrophysics Data System (ADS)

Schaedler, Tobias A.; Chan, Lisa J.; Clough, Eric C.; Stilke, Morgan A.; Hundley, Jacob M.; Masur, Lawrence J.

2017-12-01

Substitution of conventional honeycomb composite sandwich structures with lighter alternatives has the potential to reduce the mass of future vehicles. Here we demonstrate nanocrystalline aluminum-manganese truss cores that achieve 2-4 times higher strength than aluminum alloy 5056 honeycombs of the same density. The scalable fabrication approach starts with additive manufacturing of polymer templates, followed by electrodeposition of nanocrystalline Al-Mn alloy, removal of the polymer, and facesheet integration. This facilitates curved and net-shaped sandwich structures, as well as co-curing of the facesheets, which eliminates the need for extra adhesive. The nanocrystalline Al-Mn alloy thin-film material exhibits high strength and ductility and can be converted into a three-dimensional hollow truss structure with this approach. Ultra-lightweight sandwich structures are of interest for a range of applications in aerospace, such as fairings, wings, and flaps, as well as for the automotive and sports industries.

Photochromic ruthenium sulfoxide complexes: evidence for isomerization through a conical intersection.

PubMed

McClure, Beth Anne; Mockus, Nicholas V; Butcher, Dennis P; Lutterman, Daniel A; Turro, Claudia; Petersen, Jeffrey L; Rack, Jeffrey J

2009-09-07

The complexes [Ru(bpy)(2)(OS)](PF(6)) and [Ru(bpy)(2)(OSO)](PF(6)), where bpy is 2,2'-bipyridine, OS is 2-methylthiobenzoate, and OSO is 2-methylsulfinylbenzoate, have been studied. The electrochemical and photochemical reactivity of [Ru(bpy)(2)(OSO)](+) is consistent with an isomerization of the bound sulfoxide from S-bonded (S-) to O-bonded (O-) following irradiation or electrochemical oxidation. Charge transfer excitation of [Ru(bpy)(2)(OSO)](+) in MeOH results in the appearance of two new metal-to-ligand charge transfer (MLCT) maxima at 355 and 496 nm, while the peak at 396 nm diminishes in intensity. The isomerization is reversible at room temperature in alcohol or propylene carbonate solution. In the absence of light, solutions of O-[Ru(bpy)(2)(OSO)](+) revert to S-[Ru(bpy)(2)(OSO)](+). Kinetic analysis reveals a biexponential decay with rate constants of 5.66(3) x 10(-4) s(-1) and 3.1(1) x 10(-5) s(-1). Cyclic voltammograms of S-[Ru(bpy)(2)(OSO)](+) are consistent with electron-transfer-triggered isomerization of the sulfoxide. Analysis of these voltammograms reveal E(S)(o)' = 0.86 V and E(O)(o)' = 0.49 V versus Ag/Ag(+) for the S- and O-bonded Ru(3+/2+) couples, respectively, in propylene carbonate. We found k(S-->O) = 0.090(15) s(-1) in propylene carbonate and k(S-->O) = 0.11(3) s(-1) in acetonitrile on Ru(III), which is considerably slower than has been reported for other sulfoxide isomerizations on ruthenium polypyridyl complexes following oxidation. The photoisomerization quantum yield (Phi(S-->O) = 0.45, methanol) is quite large, indicating a rapid excited state isomerization rate constant. The kinetic trace at 500 nm is monoexponential with tau = 150 ps, which is assigned to the excited S-->O isomerization rate. There is no spectroscopic or kinetic evidence for an O-bonded (3)MLCT excited state in the spectral evolution of S-[Ru(bpy)(2)(OSO)](+) to O-[Ru(bpy)(2)(OSO)](+). Thus, isomerization occurs nonadiabatically from an S-bonded (or eta(2

Three-dimensional analysis by electron diffraction methods of nanocrystalline materials.

PubMed

Gammer, Christoph; Mangler, Clemens; Karnthaler, Hans-Peter; Rentenberger, Christian

2011-12-01

To analyze nanocrystalline structures quantitatively in 3D, a novel method is presented based on electron diffraction. It allows determination of the average size and morphology of the coherently scattering domains (CSD) in a straightforward way without the need to prepare multiple sections. The method is applicable to all kinds of bulk nanocrystalline materials. As an example, the average size of the CSD in nanocrystalline FeAl made by severe plastic deformation is determined in 3D. Assuming ellipsoidal CSD, it is deduced that the CSD have a width of 19 ± 2 nm, a length of 18 ± 1 nm, and a height of 10 ± 1 nm.

Photoinduced oxidation of a water-soluble manganese(III) porphyrin

PubMed Central

Maliyackel, Anthony C.; Otvos, John W.; Spreer, Larry O.; Calvin, Melvin

1986-01-01

The photoinduced oxidation of tetra(N-methyl-4-pyridyl)porphyrinmanganese(III) has been achieved in homogeneous solution. The manganese porphyrin was used as an electron donor in a three-component system with tris-(2,2′-bipyridine)ruthenium(II) as the photosensitizer and chloropentaamminecobalt(III) as the electron acceptor. The photooxidized manganese porphyrin is unstable in aqueous solution, reverting to the starting manganese(III) porphyrin. The oxidation of manganese(III) porphyrin and the subsequent reduction of the oxidized porphyrin can be cycled repeatedly. PMID:16593699

Nanocrystalline copper films are never flat

NASA Astrophysics Data System (ADS)

Zhang, Xiaopu; Han, Jian; Plombon, John J.; Sutton, Adrian P.; Srolovitz, David J.; Boland, John J.

2017-07-01

We used scanning tunneling microscopy to study low-angle grain boundaries at the surface of nearly planar copper nanocrystalline (111) films. The presence of grain boundaries and their emergence at the film surface create valleys composed of dissociated edge dislocations and ridges where partial dislocations have recombined. Geometric analysis and simulations indicated that valleys and ridges were created by an out-of-plane grain rotation driven by reduction of grain boundary energy. These results suggest that in general, it is impossible to form flat two-dimensional nanocrystalline films of copper and other metals exhibiting small stacking fault energies and/or large elastic anisotropy, which induce a large anisotropy in the dislocation-line energy.

Syntheses of nanocrystalline BaTiO3 and their optical properties

NASA Astrophysics Data System (ADS)

Yu, J.; Chu, J.; Zhang, M.

Stoichiometric and titanium-excess nanocrystalline barium titanates were synthesized using a hydrothermal process at various hydrothermal temperatures and with further heat treatment at 500 °C and 900 °C. Owing to the different process conditions, the excess titanium exists in different states and configurations within the nanocrystalline BaTiO3 matrix; this was demonstrated by X-ray diffraction, Raman scattering, and photoluminescence. In these nanocrystalline BaTiO3, the 590, 571, 543 and 694 nm light emission bands were observed; mechanisms leading to such emissions were also discussed.

Vapor Synthesis and Thermal Modification of Supportless Platinum–Ruthenium Nanotubes and Application as Methanol Electrooxidation Catalysts

DOE PAGES

Atkinson III, Robert W.; Unocic, Raymond R.; Unocic, Kinga A.; ...

2015-04-23

Metallic, mixed-phase, and alloyed bimetallic Pt-Ru nanotubes were synthesized by a novel route based on the sublimation of metal acetylacetonate precursors and their subsequent vapor deposition within anodic alumina templates. Nanotube architectures were tuned by thermal annealing treatments. As-synthesized nanotubes are composed of nanoparticulate, metallic platinum and hydrous ruthenium oxide whose respective thicknesses depend on the sample chemical composition. The Pt-decorated, hydrous Ru oxide nanotubes may be thermally annealed to promote a series of chemical and physical changes to the nanotube structures including alloy formation, crystallite growth and morphological evolution. Annealed Pt-Ru alloy nanotubes and their as-synthesized analogs demonstrate relativelymore » high specific activities for the oxidation of methanol. As-synthesized, mixed-phase Pt-Ru nanotubes (0.39 mA/cm2) and metallic alloyed Pt64Ru36NTs (0.33 mA/cm2) have considerably higher area-normalized activities than PtRu black (0.22 mA/cm2) at 0.65 V vs. RHE.« less

Distinctive glial and neuronal interfacing on nanocrystalline diamond.

PubMed

Bendali, Amel; Agnès, Charles; Meffert, Simone; Forster, Valérie; Bongrain, Alexandre; Arnault, Jean-Charles; Sahel, José-Alain; Offenhäusser, Andreas; Bergonzo, Philippe; Picaud, Serge

2014-01-01

Direct electrode/neuron interfacing is a key challenge to achieve high resolution of neuronal stimulation required for visual prostheses. Neuronal interfacing on biomaterials commonly requires the presence of glial cells and/or protein coating. Nanocrystalline diamond is a highly mechanically stable biomaterial with a remarkably large potential window for the electrical stimulation of tissues. Using adult retinal cell cultures from rats, we found that glial cells and retinal neurons grew equally well on glass and nanocrystalline diamond. The use of a protein coating increased cell survival, particularly for glial cells. However, bipolar neurons appeared to grow even in direct contact with bare diamond. We investigated whether the presence of glial cells contributed to this direct neuron/diamond interface, by using purified adult retinal ganglion cells to seed diamond and glass surfaces with and without protein coatings. Surprisingly, these fully differentiated spiking neurons survived better on nanocrystalline diamond without any protein coating. This greater survival was indicated by larger cell numbers and the presence of longer neurites. When a protein pattern was drawn on diamond, neurons did not grow preferentially on the coated area, by contrast to their behavior on a patterned glass. This study highlights the interesting biocompatibility properties of nanocrystalline diamond, allowing direct neuronal interfacing, whereas a protein coating was required for glial cell growth.

Distinctive Glial and Neuronal Interfacing on Nanocrystalline Diamond

PubMed Central

Bendali, Amel; Agnès, Charles; Meffert, Simone; Forster, Valérie; Bongrain, Alexandre; Arnault, Jean-Charles; Sahel, José-Alain; Offenhäusser, Andreas; Bergonzo, Philippe; Picaud, Serge

2014-01-01

Direct electrode/neuron interfacing is a key challenge to achieve high resolution of neuronal stimulation required for visual prostheses. Neuronal interfacing on biomaterials commonly requires the presence of glial cells and/or protein coating. Nanocrystalline diamond is a highly mechanically stable biomaterial with a remarkably large potential window for the electrical stimulation of tissues. Using adult retinal cell cultures from rats, we found that glial cells and retinal neurons grew equally well on glass and nanocrystalline diamond. The use of a protein coating increased cell survival, particularly for glial cells. However, bipolar neurons appeared to grow even in direct contact with bare diamond. We investigated whether the presence of glial cells contributed to this direct neuron/diamond interface, by using purified adult retinal ganglion cells to seed diamond and glass surfaces with and without protein coatings. Surprisingly, these fully differentiated spiking neurons survived better on nanocrystalline diamond without any protein coating. This greater survival was indicated by larger cell numbers and the presence of longer neurites. When a protein pattern was drawn on diamond, neurons did not grow preferentially on the coated area, by contrast to their behavior on a patterned glass. This study highlights the interesting biocompatibility properties of nanocrystalline diamond, allowing direct neuronal interfacing, whereas a protein coating was required for glial cell growth. PMID:24664111

Decarboxylation of cinnamic acids using a ruthenium sawhorse

USDA-ARS?s Scientific Manuscript database

The ruthenium sawhorse has proven effective in the conversion of trans-cinnamic acid, and substituted trans-cinnamic acids, giving an effective source of biobased styrene and styrene analogues. The reaction is especially versatile, as it achieves product without utilising co-reagents. However, the o...

Extreme creep resistance in a microstructurally stable nanocrystalline alloy

NASA Astrophysics Data System (ADS)

Darling, K. A.; Rajagopalan, M.; Komarasamy, M.; Bhatia, M. A.; Hornbuckle, B. C.; Mishra, R. S.; Solanki, K. N.

2016-09-01

Nanocrystalline metals, with a mean grain size of less than 100 nanometres, have greater room-temperature strength than their coarse-grained equivalents, in part owing to a large reduction in grain size. However, this high strength generally comes with substantial losses in other mechanical properties, such as creep resistance, which limits their practical utility; for example, creep rates in nanocrystalline copper are about four orders of magnitude higher than those in typical coarse-grained copper. The degradation of creep resistance in nanocrystalline materials is in part due to an increase in the volume fraction of grain boundaries, which lack long-range crystalline order and lead to processes such as diffusional creep, sliding and rotation. Here we show that nanocrystalline copper-tantalum alloys possess an unprecedented combination of properties: high strength combined with extremely high-temperature creep resistance, while maintaining mechanical and thermal stability. Precursory work on this family of immiscible alloys has previously highlighted their thermo-mechanical stability and strength, which has motivated their study under more extreme conditions, such as creep. We find a steady-state creep rate of less than 10-6 per second—six to eight orders of magnitude lower than most nanocrystalline metals—at various temperatures between 0.5 and 0.64 times the melting temperature of the matrix (1,356 kelvin) under an applied stress ranging from 0.85 per cent to 1.2 per cent of the shear modulus. The unusual combination of properties in our nanocrystalline alloy is achieved via a processing route that creates distinct nanoclusters of atoms that pin grain boundaries within the alloy. This pinning improves the kinetic stability of the grains by increasing the energy barrier for grain-boundary sliding and rotation and by inhibiting grain coarsening, under extremely long-term creep conditions. Our processing approach should enable the development of

Luminescence and related properties of nanocrystalline porous silicon

NASA Astrophysics Data System (ADS)

Koshida, N.

This document is part of subvolume C3 'Optical Properties' of volume 34 'Semiconductor quantum structures' of Landolt-Börnstein, Group III, Condensed Matter, on the optical properties of quantum structures based on group IV semiconductors. It discusses luminescence and related properties of nanocrystalline porous silicon. Topics include an overview of nanostructured silicon, its fabrication technology, and properties of nanocrystalline porous silicon such as confinement effects, photoluminescence, electroluminesce, carrier charging effects, ballistic transport and emission, and thermally induced acoustic emission.

Gigacycle fatigue behavior by ultrasonic nanocrystalline surface modification.

PubMed

Ahn, D G; Amanov, A; Cho, I S; Shin, K S; Pyoun, Y S; Lee, C S; Park, I G

2012-07-01

Nanocrystalline surface layer up to 84 microm in thick is produced on a specimen made of Al6061-T6 alloy by means of surface treatment called ultrasonic nanocrystalline surface modification (UNSM) technique. The refined grain size is produced in the top-layer and it is increased with increasing depth from the top surface. Vickers microhardness measurement for each nanocrystalline surface layer is performed and measurement results showed that the microhardness is increased from 116 HV up to 150 HV, respectively. In this study, fatigue behavior of Al6061-T6 alloy was studied up to 10(7)-10(9) cycles by using a newly developed ultrasonic fatigue testing (UFT) rig. The fatigue results of the UNSM-treated Al6061-T6 alloy specimens were compared with those of the untreated specimens. The microstructure of the untreated and UNSM-treated specimens was characterized by means of scanning electron microscopey (SEM) and transmission electron microscopey (TEM).

Improvement of ruthenium based decarboxylation of carboxylic acids

USDA-ARS?s Scientific Manuscript database

The removal of oxygen atoms from biobased carboxylic acids is an attractive route to provide the drop in replacement feedstocks that industry needs to continue to provide high performance products. Through the use of ruthenium catalysis, an efficient method where this process can be accomplished on ...

Synthesis of Mesoporous Nanocrystalline Zirconia by Surfactant-Assisted Hydrothermal Approach.

PubMed

Nath, Soumav; Biswas, Ashik; Kour, Prachi P; Sarma, Loka S; Sur, Ujjal Kumar; Ankamwar, Balaprasad G

2018-08-01

In this paper, we have reported the chemical synthesis of thermally stable mesoporous nanocrystalline zirconia with high surface area using a surfactant-assisted hydrothermal approach. We have employed different type of surfactants such as CTAB, SDS and Triton X-100 in our synthesis. The synthesized nanocrystalline zirconia multistructures exhibit various morphologies such as rod, mortar-pestle with different particle sizes. We have characterized the zirconia multistructures by X-ray diffraction study, Field emission scanning electron microscopy, Attenuated total refection infrared spectroscopy, UV-Vis spectroscopy and photoluminescence spectroscopy. The thermal stability of as synthesized zirconia multistructures was studied by thermo gravimetric analysis, which shows the high thermal stability of nanocrystalline zirconia around 900 °C temperature.

Covalent attachment and growth of nanocrystalline films of photocatalytic TiOF2

NASA Astrophysics Data System (ADS)

Zhu, Jian; Lv, Fujian; Xiao, Shengxiong; Bian, Zhenfeng; Buntkowsky, Gerd; Nuckolls, Colin; Li, Hexing

2014-11-01

This manuscript describes a synthesis of nanocrystalline TiOF2 film. The nanocrystalline TiOF2 becomes chemically attached to the surface of the glass slide. These films are robust and can be recycled as photocatalysts for the degradation of organic dyes and solvents. These films also have significant antibacterial properties upon irradiation.This manuscript describes a synthesis of nanocrystalline TiOF2 film. The nanocrystalline TiOF2 becomes chemically attached to the surface of the glass slide. These films are robust and can be recycled as photocatalysts for the degradation of organic dyes and solvents. These films also have significant antibacterial properties upon irradiation. Electronic supplementary information (ESI) available: Methods for sample preparation, characterization and Fig. S1-S8. See DOI: 10.1039/c4nr05598e

Biologically inspired rosette nanotubes and nanocrystalline hydroxyapatite hydrogel nanocomposites as improved bone substitutes

NASA Astrophysics Data System (ADS)

Zhang, Lijie; Rodriguez, Jose; Raez, Jose; Myles, Andrew J.; Fenniri, Hicham; Webster, Thomas J.

2009-04-01

Today, bone diseases such as bone fractures, osteoporosis and bone cancer represent a common and significant public health problem. The design of biomimetic bone tissue engineering materials that could restore and improve damaged bone tissues provides exciting opportunities to solve the numerous problems associated with traditional orthopedic implants. Therefore, the objective of this in vitro study was to create a biomimetic orthopedic hydrogel nanocomposite based on the self-assembly properties of helical rosette nanotubes (HRNs), the osteoconductive properties of nanocrystalline hydroxyapatite (HA), and the biocompatible properties of hydrogels (specifically, poly(2-hydroxyethyl methacrylate), pHEMA). HRNs are self-assembled nanomaterials that are formed from synthetic DNA base analogs in water to mimic the helical nanostructure of collagen in bone. In this study, different geometries of nanocrystalline HA were controlled by either hydrothermal or sintering methods. 2 and 10 wt% nanocrystalline HA particles were well dispersed into HRN hydrogels using ultrasonication. The nanocrystalline HA and nanocrystalline HA/HRN hydrogels were characterized by x-ray diffraction, transmission electron microscopy, and scanning electron microscopy. Mechanical testing studies revealed that the well dispersed nanocrystalline HA in HRN hydrogels possessed improved mechanical properties compared to hydrogel controls. In addition, the results of this study provided the first evidence that the combination of either 2 or 10 wt% nanocrystalline HA and 0.01 mg ml-1 HRNs in hydrogels greatly increased osteoblast (bone-forming cell) adhesion up to 236% compared to hydrogel controls. Moreover, this study showed that HRNs stimulated HA nucleation and mineralization along their main axis in a way that is very reminiscent of the HA/collagen assembly pattern in natural bone. In summary, the presently observed excellent properties of the biomimetic nanocrystalline HA/HRN hydrogel composites

Mononuclear ruthenium(III) complexes containing chelating thiosemicarbazones: Synthesis, characterization and catalytic property

NASA Astrophysics Data System (ADS)

Raja, N.; Ramesh, R.

2010-02-01

Mononuclear ruthenium(III) complexes of the type [RuX(EPh 3) 2(L)] (E = P or As; X = Cl or Br; L = dibasic terdentate dehydroacetic acid thiosemicarbazones) have been synthesized from the reaction of thiosemicarbazone ligands with ruthenium(III) precursors, [RuX 3(EPh 3) 3] (where E = P, X = Cl; E = As, X = Cl or Br) and [RuBr 3(PPh 3) 2(CH 3OH)] in benzene. The compositions of the complexes have been established by elemental analysis, magnetic susceptibility measurement, FT-IR, UV-vis and EPR spectral data. These complexes are paramagnetic and show intense d-d and charge transfer transitions in dichloromethane. The complexes show rhombic EPR spectra at LNT which are typical of low-spin distorted octahedral ruthenium(III) species. All the complexes are redox active and display an irreversible metal centered redox processes. Complex [RuCl(PPh 3) 2(DHA-PTSC)] ( 5) was used as catalyst for transfer hydrogenation of ketones in the presence of isopropanol/KOH and was found to be the active species.

Electrical impedance spectroscopy of neutron-irradiated nanocrystalline silicon carbide (3C-SiC)

NASA Astrophysics Data System (ADS)

Huseynov, Elchin M.

2018-01-01

It the present work, impedance spectra of nanocrystalline 3C-SiC particles have been comparatively analyzed before and after neutron irradiation. Resonance states and shifts were observed at the impedance spectra of nanocrystalline 3C-SiC particles after neutron irradiation. Relaxation time has been calculated from interdependence of real and imaginary parts of impedance of nanocrystalline 3C-SiC particles. Calculated relaxation times have been investigated as a function of neutron irradiation period. Neutron transmutation (31P isotopes production) effects on the impedance spectra and relaxation times have been studied. Moreover, influence of agglomeration and amorphous transformation to the impedance spectra and relaxation times of nanocrystalline 3C-SiC particles have been investigated.

New ruthenium carboxylate complexes having a 1-5-. eta. sup 5 -cyclooctadienyl ligand

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

Osakada, Kohtaro; Grohmann, A.; Yamamoto, Akio

1990-07-01

Reaction of 3-butenoic acid with Ru(cod)(cot) (cod) = 1-2-{eta}{sup 2}:5-6-{eta}{sup 2}-cyclooctadiene; cot = 1-6-{eta}{sup 6}-cyclooctatriene in the presence of PMe{sub 3} gives a new ruthenium(II) complex formulated as Ru(1-5-{eta}{sup 5}-C{sub 8}H{sub 11}){eta}{sup 1}(O),{eta}{sup 2}(C,C{prime}-OCOCH{sub 2}CH{double bond}CH{sub 2})(PMe{sub 3}) (1). X-ray crystallography revealed its structure as having a piano-stool coordination around the ruthenium center. Crystals of 1 are tetragonal, space group P4{sub 3}2{sub 1}2, with a = 12.559 (3) {angstrom}, c = 20.455 (4) {angstrom}, and Z = 8. {sup 1}H and {sup 13}C({sup 1}H) NMR spectra of 1 agree well for the structure with the allyl entity of the carboxylatemore » {pi}-bonded through the C{double bond}C double bond to ruthenium.« less

Silver film on nanocrystalline TiO{sub 2} support: Photocatalytic and antimicrobial ability

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

Vukoje, Ivana D., E-mail: ivanav@vinca.rs; Tomašević-Ilić, Tijana D., E-mail: tommashev@gmail.com; Zarubica, Aleksandra R., E-mail: zarubica2000@yahoo.com

Highlights: • Simple photocatalytic rout for deposition of Ag on nanocrystalline TiO{sub 2} films. • High antibactericidal efficiency of deposited Ag on TiO{sub 2} support. • Improved photocatalytic performance of TiO{sub 2} films in the presence of deposited Ag. - Abstract: Nanocrystalline TiO{sub 2} films were prepared on glass slides by the dip coating technique using colloidal solutions consisting of 4.5 nm particles as a precursor. Photoirradiation of nanocrystalline TiO{sub 2} film modified with alanine that covalently binds to the surface of TiO{sub 2} and at the same time chelate silver ions induced formation of metallic silver film. Optical andmore » morphological properties of thin silver films on nanocrystalline TiO{sub 2} support were studied by absorption spectroscopy and atomic force microscopy. Improvement of photocatalytic performance of nanocrystalline TiO{sub 2} films after deposition of silver was observed in degradation reaction of crystal violet. Antimicrobial ability of deposited silver films on nanocrystalline TiO{sub 2} support was tested in dark as a function of time against Escherichia coli, Staphylococcus aureus, and Candida albicans. The silver films ensured maximum cells reduction of both bacteria, while the fungi reduction reached satisfactory 98.45% after 24 h of contact.« less

Direct Coating of Nanocrystalline Diamond on Steel

NASA Astrophysics Data System (ADS)

Tsugawa, Kazuo; Kawaki, Shyunsuke; Ishihara, Masatou; Hasegawa, Masataka

2012-09-01

Nanocrystalline diamond films have been successfully deposited on stainless steel substrates without any substrate pretreatments to promote diamond nucleation, including the formation of interlayers. A low-temperature growth technique, 400 °C or lower, in microwave plasma chemical vapor deposition using a surface-wave plasma has cleared up problems in diamond growth on ferrous materials, such as the surface graphitization, long incubation time, substrate softening, and poor adhesion. The deposited nanocrystalline diamond films on stainless steel exhibit good adhesion and tribological properties, such as a high wear resistance, a low friction coefficient, and a low aggression strength, at room temperature in air without lubrication.

Molecular Models of Ruthenium(II) Organometallic Complexes

ERIC Educational Resources Information Center

Coleman, William F.

2007-01-01

This article presents the featured molecules for the month of March, which appear in the paper by Ozerov, Fafard, and Hoffman, and which are related to the study of the reactions of a number of "piano stool" complexes of ruthenium(II). The synthesis of compound 2a offers students an alternative to the preparation of ferrocene if they are only…

Structural characterization of nanocrystalline cadmium sulphide powder prepared by solvent evaporation technique

NASA Astrophysics Data System (ADS)

Pandya, Samir; Tandel, Digisha; Chodavadiya, Nisarg

2018-05-01

CdS is one of the most important compounds in the II-VI group of semiconductor. There are numerous applications of CdS in the form of nanoparticles and nanocrystalline. Semiconductors nanoparticles (also known as quantum dots), belong to state of matter in the transition region between molecules and solids, have attracted a great deal of attention because of their unique electrical and optical properties, compared to bulk materials. In the field of optoelectronic, nanocrystalline form utilizes mostly in the field of catalysis and fluid technology. Considering these observations, presented work had been carried out, i.e. based on the nanocrystalline material preparation. In the present work CdS nano-crystalline powder was synthesized by a simple and cost effective chemical technique to grow cadmium sulphide (CdS) nanoparticles at 200 °C with different concentrations of cadmium. The synthesis parameters were optimized. The synthesized powder was structurally characterized by X-ray diffraction and particle size analyzer. In the XRD analysis, Micro-structural parameters such as lattice strain, dislocation density and crystallite size were analysed. The broadened diffraction peaks indicated nanocrystalline particles of the film material. In addition to that the size of the prepared particles was analyzed by particle size analyzer. The results show the average size of CdS particles ranging from 80 to 100 nm. The overall conclusion of the work can be very useful in the synthesis of nanocrystalline CdS powder.

Hydrogenation of Carbon Dioxide to Methane by Ruthenium Nanoparticles in Ionic Liquid.

PubMed

Melo, Catarina I; Szczepańska, Anna; Bogel-Łukasik, Ewa; Nunes da Ponte, Manuel; Branco, Luís C

2016-05-23

The efficient transformation of carbon dioxide into fuels can be an excellent alternative to sequestration. In this work, we describe CO2 hydrogenation to methane in imidazolium-based ionic liquid media, using ruthenium nanoparticles prepared in situ as catalyst. The best yield of methane (69 %) was achieved using 0.24 mol % ruthenium catalyst (in [omim][NTf2 ], 1-octyl-3-methylimidazolium bistrifluoromethanesulfonylimide, at 40 bar of hydrogen pressure plus 40 bar of CO2 pressure, and at 150 °C. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bulk Nanocrystalline Metals: Review of the Current State of the Art and Future Opportunities for Copper and Copper Alloys

DTIC Science & Technology

2014-05-13

nanocrystalline materials using mechanical alloying, the alloy development and synthesis process for stabilizing these materials at elevated temperatures, and...the physical and mechanical properties of nanocrystalline materials with a focus throughout on nanocrystalline copper and a nanocrystalline Cu-Ta...approaches as well as experimental results for grain growth, grain boundary processes, and deformation mechanisms in nanocrystalline copper are

Electrode characteristics of nanocrystalline AB{sub 5} compounds prepared by mechanical alloying

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

Chen, Z.; Chen, Z.; Zhou, D.

1998-10-01

Nanocrystalline LaNi{sub 5} and LaNi{sub 4.5}Si{sub 0.5} synthesized by mechanical alloying were used as negative materials for Ni-MH batteries. It was found that the electrodes prepared with the nanocrystalline powders had similar discharge capacities, better activation behaviors, and longer cycle lifetimes, compared with the negative electrode prepared with polycrystalline coarse-grained LaNi{sub 5} alloy. The properties of the electrodes prepared with these nanocrystalline materials were attributed to the structural characteristics of the compounds caused by mechanical alloying.

Synthesis of nanocrystalline ZnO thin films by electron beam evaporation

NASA Astrophysics Data System (ADS)

Kondkar, V.; Rukade, D.; Bhattacharyya, V.

2018-05-01

Nanocrystalline ZnO thin films have potential for applications in variety of optoelectronic devices. In the present study, nanocrystalline thin films of ZnO are grown on fused silica substrate using electron beam (e-beam) evaporation technique. Phase identification is carried out using Glancing angle X-ray diffraction (GAXRD) and Raman spectroscopy. Ultraviolet-Visible (UV-Vis) spectroscopic analysis is carried out to calculate energy band gap of the ZnO film. Surface morphology of the film is investigated using atomic force microscopy (AFM) and field emission scanning electron microscopy (FESEM). Highly quality nanocrystalline thin films of hexagonal wurtzite ZnO are synthesized using e-beam evaporation technique.

CO2 Sensors Based on Nanocrystalline SnO2 Doped with CuO

NASA Technical Reports Server (NTRS)

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

2008-01-01

Nanocrystalline tin oxide (SnO2) doped with copper oxide (CuO) has been found to be useful as an electrical-resistance sensory material for measuring the concentration of carbon dioxide in air. SnO2 is an n-type semiconductor that has been widely used as a sensing material for detecting such reducing gases as carbon monoxide, some of the nitrogen oxides, and hydrocarbons. Without doping, SnO2 usually does not respond to carbon dioxide and other stable gases. The discovery that the electrical resistance of CuO-doped SnO2 varies significantly with the concentration of CO2 creates opportunities for the development of relatively inexpensive CO2 sensors for detecting fires and monitoring atmospheric conditions. This discovery could also lead to research that could alter fundamental knowledge of SnO2 as a sensing material, perhaps leading to the development of SnO2-based sensing materials for measuring concentrations of oxidizing gases. Prototype CO2 sensors based on CuO-doped SnO2 have been fabricated by means of semiconductor-microfabrication and sol-gel nanomaterial-synthesis batch processes that are amendable to inexpensive implementation in mass production.

Tribochemistry of contact interfaces of nanocrystalline molybdenum carbide films

NASA Astrophysics Data System (ADS)

Kumar, D. Dinesh; Kumar, N.; Panda, Kalpataru; Kamalan Kirubaharan, A. M.; Kuppusami, P.

2018-07-01

Transition metal carbides (TMC) are known for their improved tribological properties and are sensitive to the tribo-atmospheric environment. Nanocrystalline molybdenum carbide (MoC) thin films were deposited by DC magnetron sputtering technique using reactive CH4 gas. The friction and wear resistance properties of MoC thin films were significantly improved in humid-atmospheric condition as compared to high-vacuum tribo-condition. A comprehensive chemical analysis of deformed contact interfaces was carried out by X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray spectroscopy (EDX) and Raman spectroscopy. XPS and Raman spectroscopy showed the formation of stable molybdenum-oxide (MoO), molybdenum carbide (MoC) and amorphous carbon (a-C) tribo-phases. Moreover, during the sliding in humid-atmospheric condition, these phases were extensively deposited on the sliding steel ball counter body which significantly protected against undesirable friction and wear.

Syntheses and Characterization of Ruthenium(II) Tetrakis(pyridine)complexes: An Advanced Coordination Chemistry Experiment or Mini-Project

ERIC Educational Resources Information Center

Coe, Benjamin J.

2004-01-01

An experiment for third-year undergraduate a student is designed which provides synthetic experience and qualitative interpretation of the spectroscopic properties of the ruthenium complexes. It involves the syntheses and characterization of several coordination complexes of ruthenium, the element found directly beneath iron in the middle of the…

Deposition and characterization of ZnSe nanocrystalline thin films

NASA Astrophysics Data System (ADS)

Temel, Sinan; Gökmen, F. Özge; Yaman, Elif; Nebi, Murat

2018-02-01

ZnSe nanocrystalline thin films were deposited at different deposition times by using the Chemical Bath Deposition (CBD) technique. Effects of deposition time on structural, morphological and optical properties of the obtained thin films were characterized. X-ray diffraction (XRD) analysis was used to study the structural properties of ZnSe nanocrystalline thin films. It was found that ZnSe thin films have a cubic structure with a preferentially orientation of (111). The calculated average grain size value was about 28-30 nm. The surface morphology of these films was studied by the Field Emission Scanning Electron Microscope (FESEM). The surfaces of the thin films were occurred from small stacks and nano-sized particles. The band gap values of the ZnSe nanocrystalline thin films were determined by UV-Visible absorption spectrum and the band gap values were found to be between 2.65-2.86 eV.

Detailed electrochemical studies of the tetraruthenium polyoxometalate water oxidation catalyst in acidic media: identification of an extended oxidation series using Fourier transformed alternating current voltammetry.

PubMed

Lee, Chong-Yong; Guo, Si-Xuan; Murphy, Aidan F; McCormac, Timothy; Zhang, Jie; Bond, Alan M; Zhu, Guibo; Hill, Craig L; Geletii, Yurii V

2012-11-05

The electrochemistry of the water oxidation catalyst, Rb(8)K(2)[{Ru(4)O(4)(OH)(2)(H(2)O)(4)}(γ-SiW(10)O(36))(2)] (Rb(8)K(2)-1(0)) has been studied in the presence and absence of potassium cations in both hydrochloric and sulfuric acid solutions by transient direct current (dc) cyclic voltammetry, a steady state dc method in the rotating disk configuration and the kinetically sensitive technique of Fourier transformed large-amplitude alternating current (ac) voltammetry. In acidic media, the presence of potassium ions affects the kinetics (apparent rate of electron transfer) and thermodynamics (reversible potentials) of the eight processes (A'/A to H/H') that are readily detected under dc voltammetric conditions. The six most positive processes (A'/A to F/F'), each involve a one electron ruthenium based charge transfer step (A'/A, B'/B are Ru(IV/V) oxidation and C/C' to F/F' are Ru(IV/III) reduction). The apparent rate of electron transfer of the ruthenium centers in sulfuric acid is higher than in hydrochloric acid. The addition of potassium cations increases the apparent rates and gives rise to a small shift of reversible potential. Simulations of the Fourier transformed ac voltammetry method show that the B'/B, E/E', and F/F' processes are quasi-reversible, while the others are close to reversible. A third Ru(IV/V) oxidation process is observed just prior to the positive potential limit via dc methods. Importantly, the ability of the higher harmonic components of the ac method to discriminate against the irreversible background solvent process allows this (process I) as well as an additional fourth reversible ruthenium based process (J) to be readily identified. The steady-state rotating disk electrode (RDE) method confirmed that all four Ru-centers in Rb(8)K(2)-1(0) are in oxidation state IV. The dc and ac data indicate that reversible potentials of the four ruthenium centers are evenly spaced, which may be relevant to understanding of the water oxidation

New insight into singlet oxygen generation at surface modified nanocrystalline TiO2--the effect of near-infrared irradiation.

PubMed

Buchalska, Marta; Labuz, Przemysław; Bujak, Łukasz; Szewczyk, Grzegorz; Sarna, Tadeusz; Maćkowski, Sebastian; Macyk, Wojciech

2013-07-14

The generation of singlet oxygen in aqueous colloids of nanocrystalline TiO2 (anatase) modified by organic chelating ligands forming surface Ti(IV) complexes was studied. Detailed studies revealed a plausible and to date unappreciated influence of near-infrared irradiation on singlet oxygen generation at the surface of TiO2. To detect (1)O2, direct and indirect methods have been applied: a photon counting technique enabling time-resolved measurements of (1)O2 phosphorescence, and fluorescence measurements of a product of singlet oxygen interaction with Singlet Oxygen Sensor Green (SOSG). Both methods proved the generation of (1)O2. Nanocrystalline TiO2 modified with salicylic acid appeared to be the most efficient photosensitizer among the tested materials. The measured quantum yield reached the value of 0.012 upon irradiation at 355 nm, while unmodified TiO2 colloids appeared to be substantially less efficient generators of singlet oxygen with the corresponding quantum yield of ca. 0.003. A photocatalytic degradation of 4-chlorophenol, proceeding through oxidation by OH˙, was also monitored. The influence of irradiation conditions (UV, vis, NIR or any combination of these spectral ranges) on the generation of both singlet oxygen and hydroxyl radicals has been tested and discussed. Simultaneous irradiation with visible and NIR light did not accelerate OH˙ formation; however, for TiO2 modified with catechol it influenced (1)O2 generation. Singlet oxygen is presumably formed according to Nosaka's mechanism comprising O2˙(-) oxidation with a strong oxidant (hole, an oxidized ligand); however, the energy transfer from NIR-excited titanium(iii) centers (trapped electrons) plays also a plausible role.

Spectroscopic Characterization of the Water Oxidation Intermediates in the Blue Dimer Ru-Based Catalyst for Artificial Photosynthesis

NASA Astrophysics Data System (ADS)

Moonshiram, Dooshaye; Pushkar, Yulia; Jurss, Jonah; Concepcion, Javier; Meyer, Thomas; Zakharova, Taisiya; Alperovich, Igor

2012-02-01

Utilization of sunlight requires solar capture, light-to-energy conversion and storage. One effective way to store energy is to convert it into chemical energy by fuel-forming reactions, such as water splitting into hydrogen and oxygen. Ruthenium complexes are among few molecular-defined catalysts capable of water splitting. Mechanistic insights about such catalysts can be acquired by spectroscopic analysis of short-lived intermediates of catalytic water oxidation. Use of techniques such as EPR and X-ray absorption spectroscopy (XAS) are used to determine electronic requirements of catalytic water oxidation. About 30 years ago Meyer and coworkers reported first ruthenium-based catalyst for water oxidation, the ``blue dimer''. We performed EPR studies and characterized structures and electronic configurations of intermediates of water oxidation by the ``blue dimer''. Intermediates were prepared chemically by oxidation of Ru-complexes with defined number of Ce (IV) equivalents and freeze-quenched at controlled times. Changes in oxidation state of Ru atom were detected by XANES at Ru K-edges. K-edges are sensitive to changes in Ru oxidation state for Blue Dimer [3,3]^4+, [3,4]^4+, [3,4]'^4+ and [4,5]^3+ allowing a clear assignment of Ru oxidation state in intermediates. EXAFS demonstrated structural changes.

"Bulk" Nanocrystalline Metals: Review of the Current State of the Art and Future Opportunities for Copper and Copper Alloys

NASA Astrophysics Data System (ADS)

Tschopp, M. A.; Murdoch, H. A.; Kecskes, L. J.; Darling, K. A.

2014-06-01

It is a new beginning for innovative fundamental and applied science in nanocrystalline materials. Many of the processing and consolidation challenges that have haunted nanocrystalline materials are now more fully understood, opening the doors for bulk nanocrystalline materials and parts to be produced. While challenges remain, recent advances in experimental, computational, and theoretical capability have allowed for bulk specimens that have heretofore been pursued only on a limited basis. This article discusses the methodology for synthesis and consolidation of bulk nanocrystalline materials using mechanical alloying, the alloy development and synthesis process for stabilizing these materials at elevated temperatures, and the physical and mechanical properties of nanocrystalline materials with a focus throughout on nanocrystalline copper and a nanocrystalline Cu-Ta system, consolidated via equal channel angular extrusion, with properties rivaling that of nanocrystalline pure Ta. Moreover, modeling and simulation approaches as well as experimental results for grain growth, grain boundary processes, and deformation mechanisms in nanocrystalline copper are briefly reviewed and discussed. Integrating experiments and computational materials science for synthesizing bulk nanocrystalline materials can bring about the next generation of ultrahigh strength materials for defense and energy applications.

Electrical conductivity studies of graphene wrapped nanocrystalline LiMnPO{sub 4} composite

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

Cheruku, Rajesh; D, Surya Bhaskaram; Govindaraj, G., E-mail: ggraj-7@yahoo.com

Nanocrystalline LiMnPO{sub 4} material was synthesized by template free sucrose assisted hydrothermal method. The material possesses the orthorhombic crystal structure with Pnma, space group having four formula units. The GO was prepared by the hummer’s method and it was reduced graphene oxide (rGO) with hydrazine hydrate in the presence of nitrogen atmosphere. LiMnPO{sub 4} material was wrapped by the rGO to increase its conductivity. The structural characterization was accomplished through X-ray diffraction, FT-IR and Raman spectroscopy. Morphology was identified by the SEM, Electrical characterization was done through impedance spectroscopy and the results were reported.

Impedance spectroscopy study on graphene wrapped nanocrystalline V{sub 2}O{sub 5}

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

Bhaskaram, D. Surya, E-mail: dsurya.b@gmail.com; Govindaraj, G.; Cheruku, Rajesh

2016-05-23

Nanocrystalline V{sub 2}O{sub 5} was synthesized by solvothermal technique, which has potential application as electrode material in supercapacitors. The graphene oxide (GO) was prepared by modified Hummer’s method. The V{sub 2}O{sub 5}/ reduced graphene oxide (RGO) composite was synthesized using surfactant free hydrothermal technique to enhance the functionality in terms of conductivity and surface area of V{sub 2}O{sub 5}. The structural characterization was accomplished through X-ray diffraction and Raman spectroscopy. Morphology was identified by SEM and surface area of VRGO was enhanced by 8 times in comparison with V{sub 2}O{sub 5} nano particles, as confirmed through BET surface area analysis.more » Electrical characterization was done through impedance spectroscopy and the results showed decrease in sample resistance after wrapping V{sub 2}O{sub 5} with RGO.« less

Synthesis and room temperature photo-induced electron transfer in biologically active bis(terpyridine)ruthenium(II)-cytochrome c bioconjugates and the effect of solvents on the bioconjugation of cytochrome c.

PubMed

Peterson, Joshua R; Smith, Trevor A; Thordarson, Pall

2010-01-07

Photo-active bis(terpyridine)ruthenium(ii) chromophores were synthesised and attached to the redox enzyme iso-1 cytochrome c in a mixed solvent system to form photo-induced bioconjugates in greater than 40% yield after purification. The effects of up to 20% (v/v) of acetonitrile, tetrahydrofuran, dimethylformamide, or dimethyl sulfoxide at 4, 25 and 35 degrees C on the stability and biological activity of cytochrome c and its reactivity towards the model compound 4,4'-dithiodipyridine (DTDP) was measured. The second-order rate constant for the DTDP reaction was found to range between k = 2.5-4.3 M(-1) s(-1) for reactions with 5% organic solvent added compared to k = 5.6 M(-1) s(-1) in pure water at 25 degrees C. Use of 20% solvent generally results in significant protein oxidation, and 20% acetonitrile and tetrahydrofuran in particular result in significant protein dimerization, which competes with the bioconjugation reaction. Cyclic voltammetry studies indicated that the rate of electron transfer to the heme in solution was reduced in the bis(terpyridine)ruthenium(ii) cytochrome c bioconjugates compared to unmodified cytochrome c. Steady-state fluorescence studies on these bioconjugates showed that energy or electron transfer is taking place between the bis(terpyridine)ruthenium(ii) chromophores and cytochrome c. The bis(terpyridine)ruthenium(ii) cytochrome c bioconjugates demonstrate room temperature photo-activated electron transfer from the bis(terpyridine)ruthenium(ii) donor to the protein acceptor. Two sacrificial donors were used; in 50% glycerol, the bioconjugates were reduced in about 15 min while in 20 mM EDTA the bioconjugates were fully reduced in less than 5 min upon irradiation with a xenon lamp source. Under these conditions, the reduction of the non-covalent mixture of cytochrome c and bis(terpyridine)ruthenium(ii) mixtures took over 30 min. Control experiments showed that the photo-induced reduction of cytochrome c only occurs in the absence of

Parameters governing ruthenium sawhorse-based decarboxylation of oleic acid

USDA-ARS?s Scientific Manuscript database

Ruthenium-catalyzed decarboxylation of 9-cisoctadecenoic is a path to produce biobased olefins. Here, a mechanistic study of this reaction was undertaken utilizing a closed reaction system and a pressure reactor. The proposed mechanism of an isomerization followed by a decarboxylation reaction was c...

Growth characteristics of nanocrystalline silicon films fabricated by using chlorinated precursors at low temperatures.

PubMed

Huang, Rui; Ding, Honglin; Song, Jie; Guo, Yanqing; Wang, Xiang; Lin, Xuanying

2010-11-01

We employed plasma enhanced chemical vapor deposition technique to fabricate nanocrystalline Si films at a low temperature of 250 degrees C by using SiCl4 and H2 as source gases. The evolution of microstructure of the films with deposition periods shows that nanocrystalline Si can be directly grown on amorphous substrate at the initial growth process, which is in contrast to the growth behavior observed in the SiH4/H2 system. Furthermore, it is interesting to find that the area density of nanocrystalline Si as well as grain size can be controlled by modulating the concentration of SiCl4. By decreasing the SiCl4 concentration, the area density of nanocrystalline Si can be enhanced up to 10(11) cm(-2), while the grain size is shown to decrease down to 10 nm. It is suggested that Cl plays an important role in the low-temperature growth of nanocrystalline Si.

A facile one-pot synthesis of ruthenium hydroxide nanoparticles on magnetic silica: Aqueous hydration of nitriles to amides

EPA Science Inventory

One-pot synthesis of ruthenium hydroxide nanoparticles on magnetic silica is described which involve the in situ generation of magnetic silica (Fe3O4@ SiO2) and ruthenium hydroxide immobilization; the hydration of nitriles occurs in high yield and excellent selectivity using this...

Grain Size Threshold for Enhanced Irradiation Resistance in Nanocrystalline and Ultrafine Tungsten

DOE PAGES

El Atwani, Osman; Hinks, Jonathan; Greaves, Graeme; ...

2017-02-21

Nanocrystalline metals are considered highly radiation-resistant materials due to their large grain boundary areas. Here, the existence of a grain size threshold for enhanced irradiation resistance in high-temperature helium-irradiated nanocrystalline and ultrafine tungsten is demonstrated. Average bubble density, projected bubble area and the corresponding change in volume were measured via transmission electron microscopy and plotted as a function of grain size for two ion fluences. Nanocrystalline grains of less than 35 nm size possess ~10–20 times lower change in volume than ultrafine grains and this is discussed in terms of the grain boundaries defect sink efficiency.

Half-sandwich ruthenium(II) biotin conjugates as biological vectors to cancer cells.

PubMed

Babak, Maria V; Plażuk, Damian; Meier, Samuel M; Arabshahi, Homayon John; Reynisson, Jóhannes; Rychlik, Błażej; Błauż, Andrzej; Szulc, Katarzyna; Hanif, Muhammad; Strobl, Sebastian; Roller, Alexander; Keppler, Bernhard K; Hartinger, Christian G

2015-03-23

Ruthenium(II)-arene complexes with biotin-containing ligands were prepared so that a novel drug delivery system based on tumor-specific vitamin-receptor mediated endocytosis could be developed. The complexes were characterized by spectroscopic methods and their in vitro anticancer activity in cancer cell lines with various levels of major biotin receptor (COLO205, HCT116 and SW620 cells) was tested in comparison with the ligands. In all cases, coordination of ruthenium resulted in significantly enhanced cytotoxicity. The affinity of Ru(II) -biotin complexes to avidin was investigated and was lower than that of unmodified biotin. Hill coefficients in the range 2.012-2.851 suggest strong positive cooperation between the complexes and avidin. To estimate the likelihood of binding to the biotin receptor/transporter, docking studies with avidin and streptavidin were conducted. These explain, to some extent, the in vitro anticancer activity results and support the conclusion that these novel half-sandwich ruthenium(II)-biotin conjugates may act as biological vectors to cancer cells, although no clear relationship between the cellular Ru content, the cytotoxicity, and the presence of the biotin moiety was observed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanocrystalline Iron-Ore-Based Catalysts for Fischer-Tropsch Synthesis.

PubMed

Yong, Seok; Park, Ji Chan; Lee, Ho-Tae; Yang, Jung-Il; Hong, SungJun; Jung, Heon; Chun, Dong Hyun

2016-02-01

Nanocrystalline iron ore particles were fabricated by a wet-milling process using an Ultra Apex Mill, after which they were used as raw materials of iron-based catalysts for low-temperature Fischer-Tropsch synthesis (FTS) below 280 degrees C, which usually requires catalysts with a high surface area, a large pore volume, and a small crystallite size. The wet-milling process using the Ultra Apex Mill effectively destroyed the initial crystallite structure of the natural iron ores of several tens to hundreds of nanometers in size, resulting in the generation of nanocrystalline iron ore particles with a high surface area and a large pore volume. The iron-ore-based catalysts prepared from the nanocrystalline iron ore particles effectively catalyzed the low-temperature FTS, displaying a high CO conversion (about 90%) and good C5+ hydrocarbon productivity (about 0.22 g/g(cat)(-h)). This demonstrates the feasibility of using the iron-ore-based catalysts as inexpensive and disposable catalysts for the low-temperature FTS.

Mesoporous Transition Metal Oxides for Supercapacitors.

PubMed

Wang, Yan; Guo, Jin; Wang, Tingfeng; Shao, Junfeng; Wang, Dong; Yang, Ying-Wei

2015-10-14

Recently, transition metal oxides, such as ruthenium oxide (RuO₂), manganese dioxide (MnO₂), nickel oxides (NiO) and cobalt oxide (Co₃O₄), have been widely investigated as electrode materials for pseudo-capacitors. In particular, these metal oxides with mesoporous structures have become very hot nanomaterials in the field of supercapacitors owing to their large specific surface areas and suitable pore size distributions. The high specific capacities of these mesoporous metal oxides are resulted from the effective contacts between electrode materials and electrolytes as well as fast transportation of ions and electrons in the bulk of electrode and at the interface of electrode and electrolyte. During the past decade, many achievements on mesoporous transition metal oxides have been made. In this mini-review, we select several typical nanomaterials, such as RuO₂, MnO₂, NiO, Co₃O₄ and nickel cobaltite (NiCo₂O₄), and briefly summarize the recent research progress of these mesoporous transition metal oxides-based electrodes in the field of supercapacitors.

Complex of transferrin with ruthenium for medical applications. [Ru 97, Ru 103

DOEpatents

Richards, P.; Srivastava, S.C.; Meinken, G.E.

1980-11-03

A novel Ruthenium-transferrin complex, prepared by reacting iron-free human transferrin dissolved in a sodium acetate solution at pH 7 with ruthenium by heating at about 40/sup 0/C for about 2 hours, and purifying said complex by means of gel chromatography with pH 7 sodium acetate as eluent. The mono- or di-metal complex produced can be used in nuclear medicine in the diagnosis and/or treatment of tumors and abscesses. Comparitive results with Ga-67-citrate, which is the most widely used tumor-localizing agent in nuclear medicine, indicate increased sensitivity of detection and greater tumor uptake with the Ru-transferrin complex.

Structural, optical and photo-catalytic activity of nanocrystalline NiO thin films

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

Al-Ghamdi, Attieh A.; Abdel-wahab, M. Sh., E-mail: mshabaan90@yahoo.com; Materials Science and Nanotechnology Department, Faculty of Postgraduate Studies for Advanced Sciences, Beni-Suef University, Beni-Suef

2016-03-15

Highlights: • Synthesis of nanocrystalline NiO thin films with different thicknesses using DC magnetron sputtering technique. • Effect of film thickness and particle size on photo-catalytic degradation of methyl green dye under UV light was studied. • The deposited NiO thin films are efficient, stable and possess high photo-catalytic activity upon reuse. - Abstract: Physical deposition of nanocrystalline nickel oxide (NiO) thin films with different thickness 30, 50 and 80 nm have been done on glass substrate by DC magnetron sputtering technique and varying the deposition time from 600, 900 to 1200 s. The results of surface morphology and opticalmore » characterization of these films obtained using different characterization techniques such as X-ray diffraction (XRD), field emission scanning electron microscope (FESEM), photoluminescence (PL) and UV–vis spectrophotometry provide important information like formation of distinct nanostructures in different films and its effect on their optical band gap which has decreased from 3.74 to 3.37 eV as the film thickness increases. Most importantly these films have shown very high stability and a specialty to be recycled without much loss of their photo-catalytic activity, when tested as photo-catalysts for the degradation of methyl green dye (MG) from the wastewater under the exposure of 18 W energy of UV lamp.« less

Nanocrystalline copper films are never flat.

PubMed

Zhang, Xiaopu; Han, Jian; Plombon, John J; Sutton, Adrian P; Srolovitz, David J; Boland, John J

2017-07-28

We used scanning tunneling microscopy to study low-angle grain boundaries at the surface of nearly planar copper nanocrystalline (111) films. The presence of grain boundaries and their emergence at the film surface create valleys composed of dissociated edge dislocations and ridges where partial dislocations have recombined. Geometric analysis and simulations indicated that valleys and ridges were created by an out-of-plane grain rotation driven by reduction of grain boundary energy. These results suggest that in general, it is impossible to form flat two-dimensional nanocrystalline films of copper and other metals exhibiting small stacking fault energies and/or large elastic anisotropy, which induce a large anisotropy in the dislocation-line energy. Copyright © 2017 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.

Hot pressing of nanocrystalline tantalum using high frequency induction heating and pulse plasma sintering

NASA Astrophysics Data System (ADS)

Jakubowicz, J.; Adamek, G.; Sopata, M.; Koper, J. K.; Siwak, P.

2017-12-01

The paper presents the results of nanocrystalline powder tantalum consolidation using hot pressing. The authors used two different heating techniques during hot pressing: high-frequency induction heating (HFIH) and pulse plasma sintering (PPS). A comparison of the structure, microstructure, mechanical properties and corrosion resistance of the bulk nanocrystalline tantalum obtained in both techniques was performed. The nanocrystalline powder was made to start from the microcrystalline one using the high-energy ball milling process. The nanocrystalline powder was hot-pressed at 1000 °C, whereas, for comparison, the microcrystalline powder was hot pressed up to 1500 °C for proper consolidation. The authors found that during hot pressing, the powder partially reacts with the graphite die covered by boron nitride, which facilitated punches and powder displacement in the die during densification. Tantalum carbide and boride in the nanocrystalline material was found, which can improve the mechanical properties. The hardness of the HFIH and PPS nanocrystalline tantalum was as high as 625 and 615 HV, respectively. The microstructure was more uniform in the PPS nanomaterial. The corrosion resistance in both cases deteriorated, in comparison to the microcrystalline material, while the PPS material corrosion resistance was slightly better than that of the HFIH one.

Microstructures and mechanical properties of nanocrystalline NiTi intermetallics formed by mechanosynthesis

NASA Astrophysics Data System (ADS)

Arunkumar, S.; Kumaravel, P.; Velmurugan, C.; Senthilkumar, V.

2018-01-01

The formulation of nanocrystalline NiTi shape memory alloys has potential effects in mechanical stimulation and medical implantology. The present work elucidates the effect of milling time on the product's structural characteristics, chemical composition, and microhardness for NiTi synthesized by mechanical alloying for different milling durations. Increasing the milling duration led to the formation of a nanocrystalline NiTi intermetallic at a higher level. The formation of nanocrystalline materials was directed through cold fusion, fracturing, and the development of a steady state, which were influenced by the accumulation of strain energy. In the morphological study, uninterrupted cold diffusion and fracturing were visualized using transmission electron microscopy. Particle size analysis revealed that the mean particle size was reduced to 93 μm after 20 h of milling. The mechanical strength was enhanced by the formation of a nanocrystalline intermetallic phase at longer milling time, which was confirmed by the results of Vickers hardness analyses.

Platinum-ruthenium-palladium alloys for use as a fuel cell catalyst

DOEpatents

Gorer, Alexander

2002-01-01

A noble metal alloy composition for a fuel cell catalyst, a ternary alloy composition containing platinum, ruthenium and palladium. The alloy shows increased activity as compared to well-known catalysts.

Precise ruthenium fission product isotopic analysis using dynamic reaction cell inductively coupled plasma mass spectrometry (DRC-ICP-MS)

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

Brown, Christopher F.; Dresel, P. Evan; Geiszler, Keith N.

2006-05-09

99Tc is a subsurface contaminant of interest at numerous federal, industrial, and international facilities. However, as a mono-isotopic fission product, 99Tc lacks the ability to be used as a signature to differentiate between the different waste disposal pathways that could have contributed to subsurface contamination at these facilities. Ruthenium fission-product isotopes are attractive analogues for the characterization of 99Tc sources because of their direct similarity to technetium with regard to subsurface mobility, and their large fission yields and low natural background concentrations. We developed an inductively coupled plasma mass spectrometry (ICP-MS) method capable of measuring ruthenium isotopes in groundwater samplesmore » and extracts of vadose zone sediments. Samples were analyzed directly on a Perkin Elmer ELAN DRC II ICP-MS after a single pass through a 1-ml bed volume of Dowex AG 50W-X8 100-200 mesh cation exchange resin. Precise ruthenium isotopic ratio measurements were achieved using a low-flow Meinhard-type nebulizer and long sample acquisition times (150,000 ms). Relative standard deviations of triplicate replicates were maintained at less than 0.5% when the total ruthenium solution concentration was 0.1 ng/ml or higher. Further work was performed to minimize the impact caused by mass interferences using the dynamic reaction cell (DRC) with O2 as the reaction gas. The aqueous concentrations of 96Mo and 96Zr were reduced by more than 99.7% in the reaction cell prior to injection of the sample into the mass analyzer quadrupole. The DRC was used in combination with stable-mass correction to quantitatively analyze samples containing up to 2-orders of magnitude more zirconium and molybdenum than ruthenium. The analytical approach documented herein provides an efficient and cost-effective way to precisely measure ruthenium isotopes and quantitate total ruthenium (natural vs. fission-product) in aqueous matrixes.« less

LEAD SORPTION ON RUTHENIUM OXIDE: A MACROSCOPIC AND SPECTROSCOPIC STUDY

EPA Science Inventory

Metal oxide phases play an important role in governing the sorption and desorption mechanisms of metals in water, soils, and sediments. Many researchers have examined the efficiency of Pb sorption on Mn, Fe, Al, Ti, and Si oxide surfaces. Most studies concluded that adsorption ...

COMPLEX RUTHENIUM ACIDO-NITROS COMPOUNDS (in Russian)

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

Zvyagintsev, O.E.; Starostin, S.M.

1961-06-01

The chemical nature of the water in the complex ruthenium acidonitroso compounds is studied by measuring certain acid properties, reactions, and behaviors of the compounds in aqueous solution. The dependence of molecular electrical conductivity on time and dilution, variations of specific electroconductivity, the optical density, and the light absorption of the compounds at 200 to 800 m mu wave range were investigated and the dissociation constants were calculated. (R.V.J.)

Ruthenium Catalyzed Hydrohydroxyalkylation of Acrylates with Diols and α-Hydroxycarbonyl Compounds to Form Spiro- and α-Methylene-γ-Butyrolactones

PubMed Central

McInturff, Emma L.; Mowat, Jeffrey; Waldeck, Andrew R.; Krische, Michael J.

2013-01-01

Under the conditions of ruthenium(0) catalyzed hydrohydroxyalkylation, vicinal diols 1a–1l and methyl acrylate 2a are converted to the corresponding lactones 3a–3l in good to excellent yield. The reaction of methyl acrylate 2a with hydrobenzoin 1f, benzoin didehydro-1f, and benzil tetradehydro-1f form the same lactone 3f product, demonstrating that this process may be deployed in a redox level-independent manner. A variety of substituted acrylic esters 2a–2h participate in spirolactone formation, as illustrated in the conversion of N-benzyl-3-hydroxyoxindole 1o to cycloadducts 4a–4h. Hydrohydroxyalkylation of hydroxyl-substituted methacrylate 2i with diols 1b, 1f, 1j and 1l forms α-exo-methylene-γ-butyrolactones 5b, 5f, 5j and 5l in moderate to good yield. A catalytic cycle involving 1,2-dicarbonyl-acrylate oxidative coupling to form oxaruthenacyclic intermediates is postulated. A catalytically competent mononuclear ruthenium(II) complex was characterized by single crystal X-ray diffraction. The influence of electronic effects on regioselectivity in reactions of nonsymmetric diols were probed using para-substituted 1-phenyl-1,2-propanediols 1g, 1m and 1n and density functional theory (DFT) calculations. PMID:24187991

Endoresection with adjuvant ruthenium brachytherapy for selected uveal melanoma patients - the Tuebingen experience.

PubMed

Süsskind, Daniela; Dürr, Carina; Paulsen, Frank; Kaulich, Theodor; Bartz-Schmidt, Karl U

2017-12-01

To evaluate the treatment of selected patients with uveal melanoma with endoresection and adjuvant ruthenium brachytherapy. Thirty-five patients with uveal melanoma not suitable for ruthenium plaque monotherapy were treated with endoresection and adjuvant ruthenium brachytherapy between January 2001 and October 2013. Recurrence-free survival, globe retention, course of visual acuity (VA), occurrence of therapy-related complications and metastasis-free and overall survival were analysed retrospectively. Eight patients (22.9%) had a tumour recurrence after a median follow-up of 49.5 months (range: 21-134 months). Enucleation was necessary in eight patients. Thirty-two patients (91%) had a loss of VA with a median loss of nine lines (range: 0 to -39 lines); VA was stable in three patients and no patients had a gain in VA. Four patients (11.4%) developed radiation retinopathy. Metastases were detected in seven patients (20.0%) during follow-up. The occurrence of metastasis was significantly associated with monosomy 3 (p < 0.0001). Twenty-four patients (68.6%) were alive at the end of follow-up. Five patients (14.3%) died because of uveal melanoma (UM) metastasis. Endoresection with adjuvant ruthenium brachytherapy is an option for selected patients with UM who cannot be treated with brachytherapy as monotherapy. About two-thirds of eyes can be retained long term without recurrences. Visual acuity cannot be maintained in most cases, and may even decrease considerably. Radiation complications are comparatively rare and not a significant problem. © 2016 Acta Ophthalmologica Scandinavica Foundation. Published by John Wiley & Sons Ltd.

Framework Stability of Nanocrystalline NaY in Aqueous Solution at Varying pH

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

Petushkov, Anton; Freeman, Jasmine; Larsen, Sarah C.

Nanocrystalline zeolites (with crystal sizes of less than 50 nm) are versatile, porous nanomaterials with potential applications in a broad range of areas including bifunctional catalysis, drug delivery, environmental protection, and sensing, to name a few. The characterization of the properties of nanocrystalline zeolites on a fundamental level is critical to the realization of these innovative applications. Nanocrystalline zeolites have unique surface chemistry that is distinct from conventional microcrystalline zeolite materials and that will result in novel applications. In the proposed work, magnetic resonance techniques (solid state nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR)) will be used tomore » elucidate the structure and reactivity of nanocrystalline zeolites and to motivate bifunctional applications. Density functional theory (DFT) calculations will enhance data interpretation through chemical shift, quadrupole coupling constant, g-value and hyperfine calculations.« less

Electrodeposition of Nanocrystalline Cobalt Phosphorous Coatings as a Hard Chrome Alternative

DTIC Science & Technology

2014-11-01

1 ASETSDefense 2014 Electrodeposition of Nanocrystalline Cobalt Phosphorous Coatings as a Hard Chrome Alternative Ruben A. Prado, CEF...COVERED 00-00-2014 to 00-00-2014 4. TITLE AND SUBTITLE Electrodeposition of Nanocrystalline Cobalt Phosphorous Coatings as a Hard Chrome Alternative...coatings as a Hard Chrome (EHC) electroplating alternative for DoD manufacturing and repair. – Fully define deposition parameters and properties

Model for temperature-dependent magnetization of nanocrystalline materials

NASA Astrophysics Data System (ADS)

Bian, Q.; Niewczas, M.

2015-01-01

A magnetization model of nanocrystalline materials incorporating intragrain anisotropies, intergrain interactions, and texture effects has been extended to include the thermal fluctuations. The method relies on the stochastic Landau-Lifshitz-Gilbert theory of magnetization dynamics and permits to study the magnetic properties of nanocrystalline materials at arbitrary temperature below the Currie temperature. The model has been used to determine the intergrain exchange constant and grain boundary anisotropy constant of nanocrystalline Ni at 100 K and 298 K. It is found that the thermal fluctuations suppress the strength of the intergrain exchange coupling and also reduce the grain boundary anisotropy. In comparison with its value at 2 K, the interparticle exchange constant decreases by 16% and 42% and the grain boundary anisotropy constant decreases by 28% and 40% at 100 K and 298 K, respectively. An application of the model to study the grain size-dependent magnetization indicates that when the thermal activation energy is comparable to the free energy of grains, the decrease in the grain size leads to the decrease in the magnetic permeability and saturation magnetization. The mechanism by which the grain size influences the magnetic properties of nc-Ni is discussed.

Calcium manganese(IV) oxides: biomimetic and efficient catalysts for water oxidation.

PubMed

Najafpour, Mohammad Mahdi; Pashaei, Babak; Nayeri, Sara

2012-04-28

CaMnO(3) and Ca(2)Mn(3)O(8) were synthesized and characterized by SEM, XRD, FTIR and BET. Both oxides showed oxygen evolution activity in the presence of oxone, cerium(IV) ammonium nitrate and H(2)O(2). Oxygen evolution from water during irradiation with visible light (λ > 400 nm) was also observed upon adding these manganese oxides to an aqueous solution containing tris(2,2'-bipyridyl) ruthenium(II), as photosensitizer, and chloro pentaammine cobalt(III) chloride, as electron acceptor, in an acetate buffer. The amounts of dissolved manganese and calcium from CaMnO(3) and Ca(2)Mn(3)O(8) in the oxygen evolving reactions were reported and compared with other (calcium) manganese oxides. Proposed mechanisms of oxygen evolution and proposed roles for the calcium ions are also considered. This journal is © The Royal Society of Chemistry 2012

Structure-reactivity relationships in the hydrogenation of carbon dioxide with ruthenium complexes bearing pyridinylazolato ligands.

PubMed

Muller, Keven; Sun, Yu; Heimermann, Andreas; Menges, Fabian; Niedner-Schatteburg, Gereon; van Wüllen, Christoph; Thiel, Werner R

2013-06-10

Pyridinylazolato (N-N') ruthenium(II) complexes of the type [(N-N')RuCl(PMe3)3] have been obtained in high yields by treating the corresponding functionalised azolylpyridines with [RuCl2 (PMe3)4] in the presence of a base. (15)N NMR spectroscopy was used to elucidate the electronic influence of the substituents attached to the azolyl ring. The findings are in agreement with slight differences in the bond lengths of the ruthenium complexes. Furthermore, the electronic nature of the azolate moiety modulates the catalytic activity of the ruthenium complexes in the hydrogenation of carbon dioxide under supercritical conditions and in the transfer hydrogenation of acetophenone. DFT calculations were performed to shed light on the mechanism of the hydrogenation of carbon dioxide and to clarify the impact of the electronic nature of the pyridinylazolate ligands. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Multifunctionality of nanocrystalline lanthanum ferrite

NASA Astrophysics Data System (ADS)

Rai, Atma; Thakur, Awalendra K.

2016-05-01

Nanocrystalline lanthanum ferrite has been synthesized by adopting modified Pechini route. No evidence of impurity or secondary phase has been detected up to the detection of error limit of X-ray diffractometer (XRD). Rietveld refinement of X-ray diffraction pattern reveals orthorhombic crystal system with space group Pnma (62).Crystallite size and lattice strain was found to be ˜42.8nm and 0.306% respectively. Optical band gap was found to be 2.109 eV, by UV-Visible diffused reflectance spectrum (DRS). Brunauer-Emmet-Teller (BET) surface area was found to be ˜3.45 m2/g. Magnetization-hysteresis (M-H) loop was recorded at room temperature (300K) reveals weak ferromagnetism in Nanocrystalline lanthanum ferrite. The weak ferromagnetism in lanthanum ferrite is due to the uncompensated antiferromagnetic spin ordering. Ferroelectric loop hysteresis observed at room temperature at 100Hz depicts the presence of ferroelectric ordering in LaFeO3.Simultanious presence of magnetic and ferroelectric ordering at room temperature makes it suitable candidate of Multiferroic family.

Multifunctionality of nanocrystalline lanthanum ferrite

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

Rai, Atma, E-mail: atma@iitp.ac.in; Thakur, Awalendra K.; Centre for Energy and Environment, Indian Institute of Technology Patna 800013 India

2016-05-06

Nanocrystalline lanthanum ferrite has been synthesized by adopting modified Pechini route. No evidence of impurity or secondary phase has been detected up to the detection of error limit of X-ray diffractometer (XRD). Rietveld refinement of X-ray diffraction pattern reveals orthorhombic crystal system with space group Pnma (62).Crystallite size and lattice strain was found to be ∼42.8nm and 0.306% respectively. Optical band gap was found to be 2.109 eV, by UV-Visible diffused reflectance spectrum (DRS). Brunauer-Emmet-Teller (BET) surface area was found to be ∼3.45 m{sup 2}/g. Magnetization-hysteresis (M-H) loop was recorded at room temperature (300K) reveals weak ferromagnetism in Nanocrystalline lanthanummore » ferrite. The weak ferromagnetism in lanthanum ferrite is due to the uncompensated antiferromagnetic spin ordering. Ferroelectric loop hysteresis observed at room temperature at 100Hz depicts the presence of ferroelectric ordering in LaFeO{sub 3}.Simultanious presence of magnetic and ferroelectric ordering at room temperature makes it suitable candidate of Multiferroic family.« less

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

Photocatalytic oxidation of organic compounds in a hybrid system composed of a molecular catalyst and visible light-absorbing semiconductor.

PubMed

Zhou, Xu; Li, Fei; Li, Xiaona; Li, Hua; Wang, Yong; Sun, Licheng

2015-01-14

Photocatalytic oxidation of organic compounds proceeded efficiently in a hybrid system with ruthenium aqua complexes as catalysts, BiVO4 as a light absorber, [Co(NH3)5Cl](2+) as a sacrificial electron acceptor and water as an oxygen source. The photogenerated holes in the semiconductor are used to oxidize molecular catalysts into the high-valent Ru(IV)=O intermediates for 2e(-) oxidation.

Nanocarbon Allotropes-Graphene and Nanocrystalline Diamond-Promote Cell Proliferation.

PubMed

Verdanova, Martina; Rezek, Bohuslav; Broz, Antonin; Ukraintsev, Egor; Babchenko, Oleg; Artemenko, Anna; Izak, Tibor; Kromka, Alexander; Kalbac, Martin; Hubalek Kalbacova, Marie

2016-05-01

Two profoundly different carbon allotropes - nanocrystalline diamond and graphene - are of considerable interest from the viewpoint of a wide range of biomedical applications including implant coating, drug and gene delivery, cancer therapy, and biosensing. Osteoblast adhesion and proliferation on nanocrystalline diamond and graphene are compared under various conditions such as differences in wettability, topography, and the presence or absence of protein interlayers between cells and the substrate. The materials are characterized in detail by means of scanning electron microscopy, atomic force microscopy, photoelectron spectroscopy, Raman spectroscopy, and contact angle measurements. In vitro experiments have revealed a significantly higher degree of cell proliferation on graphene than on nanocrystalline diamond and a tissue culture polystyrene control material. Proliferation is promoted, in particular, by hydrophobic graphene with a large number of nanoscale wrinkles independent of the presence of a protein interlayer, i.e., substrate fouling is not a problematic issue in this respect. Nanowrinkled hydrophobic graphene, thus, exhibits superior characteristics for those biomedical applications where high cell proliferation is required under differing conditions. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Influence of voids distribution on the deformation behavior of nanocrystalline palladium

NASA Astrophysics Data System (ADS)

Bachurin, D. V.

2018-07-01

Uniaxial deformation of three-dimensional nanocrystalline palladium containing porosity in the form of voids was investigated by means of molecular dynamics method. Simulations were performed at temperature of 300 K and at a constant strain rate of 108s-1. Two cases of voids distribution were considered: random and at triple or quadrupole junctions. It has been revealed that both the voids distribution and subsequent annealing at elevated temperature influence the deformation behavior of nanocrystalline palladium. In particular, the presence of voids at grain junctions results in a reduction of the Young's modulus and more pronounced softening effect during plastic deformation. The subsequent annealing evokes shrinkage of voids and strengthening effect. Contribution of grain boundary accommodation processes into both elastic and plastic deformation of nanocrystalline materials is discussed.

Ternary and coupled binary zinc tin oxide nanopowders: Synthesis, characterization, and potential application in photocatalytic processes

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

Ivetić, T.B., E-mail: tamara.ivetic@df.uns.ac.rs; Finčur, N.L.; Đačanin, Lj. R.

2015-02-15

Highlights: • Mechanochemically synthesized nanocrystalline zinc tin oxide (ZTO) powders. • Photocatalytic degradation of alprazolam in the presence of ZTO water suspensions. • Coupled binary ZTO exhibits enhanced photocatalytic activity compared to ternary ZTO. - Abstract: In this paper, ternary and coupled binary zinc tin oxide nanocrystalline powders were prepared via simple solid-state mechanochemical method. X-ray diffraction, scanning electron microscopy, Raman and reflectance spectroscopy were used to study the structure and optical properties of the obtained powder samples. The thermal behavior of zinc tin oxide system was examined through simultaneous thermogravimetric-differential scanning calorimetric analysis. The efficiencies of ternary (Zn{sub 2}SnO{submore » 4} and ZnSnO{sub 3}) and coupled binary (ZnO/SnO{sub 2}) zinc tin oxide water suspensions in the photocatalytic degradation of alprazolam, short-acting anxiolytic of the benzodiazepine class of psychoactive drugs, under UV irradiation were determined and compared with the efficiency of pure ZnO and SnO{sub 2}.« less

Electrode characteristics of nanocrystalline (Zr, Ti)(V, Cr, Ni) 2.41 compound

NASA Astrophysics Data System (ADS)

Majchrzycki, W.; Jurczyk, M.

The electrochemical properties of nanocrystalline Zr 0.35Ti 0.65V 0.85Cr 0.26Ni 1.30 alloy, which has the hexagonal C14 type structure, have been investigated. This material has been prepared using mechanical alloying (MA) followed by annealing. The amorphous phase forms directly from the starting mixture of the elements, without other phase formation. Heating the MA samples at 1070 K for 0.5 h resulted in the creation of ordered alloy. This alloy was used as negative electrode for Ni-MH x battery. The electrochemical results show very little difference between the nanocrystalline and polycrystalline powders, as compared with the substantial difference between these and the amorphous powder. In the annealed nanocrystalline Zr 0.35Ti 0.65V 0.85Cr 0.26Ni 1.30 powders discharging capacities up to 150 mA h g -1 (at 160 mA g -1 discharging current) have been measured. The properties of nanocrystalline electrode were attributed to the structural characteristics of the compound caused by mechanical alloying.

Investigation of Ruthenium Dissolution in Advanced Membrane Electrode Assemblies for Direct Methanol Based Fuel Cell Stacks

NASA Technical Reports Server (NTRS)

Valdez, Thomas I.; Firdosy, S.; Koel, B. E.; Narayanan, S. R.

2005-01-01

Dissolution of ruthenium was observed in the 80-cell stack. Duration testing was performed in single cell MEAs to determine the pathway of cell degradation. EDAX analysis on each of the single cell MEAs has shown that the Johnson Matthey commercial catalyst is stable in DMFC operation for 250 hours, no ruthenium dissolution was observed. Changes in the hydrophobicity of the cathode backing papers was minimum. Electrode polarization analysis revealed that the MEA performance loss is attributed to changes in the cathode catalyst layer. Ruthenium migration does not seem to occur during cell operation but can occur when methanol is absent from the anode compartment, the cathode compartment has access to air, and the cells in the stack are electrically connected to a load (Shunt Currents). The open-to-air cathode stack design allowed for: a) The MEAs to have continual access to oxygen; and b) The stack to sustain shunt currents. Ruthenium dissolution in a DMFC stack can be prevented by: a) Developing an internally manifolded stacks that seal reactant compartments when not in operation; b) Bringing the cell voltages to zero quickly when not in operation; and c) Limiting the total number of cells to 25 in an effort to limit shunt currents.

Probing the structural evolution of ruthenium doped germanium clusters: Photoelectron spectroscopy and density functional theory calculations

PubMed Central

Jin, Yuanyuan; Lu, Shengjie; Hermann, Andreas; Kuang, Xiaoyu; Zhang, Chuanzhao; Lu, Cheng; Xu, Hongguang; Zheng, Weijun

2016-01-01

We present a combined experimental and theoretical study of ruthenium doped germanium clusters, RuGen− (n = 3–12), and their corresponding neutral species. Photoelectron spectra of RuGen− clusters are measured at 266 nm. The vertical detachment energies (VDEs) and adiabatic detachment energies (ADEs) are obtained. Unbiased CALYPSO structure searches confirm the low-lying structures of anionic and neutral ruthenium doped germanium clusters in the size range of 3 ≤ n ≤ 12. Subsequent geometry optimizations using density functional theory (DFT) at PW91/LANL2DZ level are carried out to determine the relative stability and electronic properties of ruthenium doped germanium clusters. It is found that most of the anionic and neutral clusters have very similar global features. Although the global minimum structures of the anionic and neutral clusters are different, their respective geometries are observed as the low-lying isomers in either case. In addition, for n > 8, the Ru atom in RuGen−/0 clusters is absorbed endohedrally in the Ge cage. The theoretically predicted vertical and adiabatic detachment energies are in good agreement with the experimental measurements. The excellent agreement between DFT calculations and experiment enables a comprehensive evaluation of the geometrical and electronic structures of ruthenium doped germanium clusters. PMID:27439955

Dot size effects of nanocrystalline germanium on charging dynamics of memory devices

PubMed Central

2013-01-01

The dot size of nanocrystalline germanium (NC Ge) which impacts on the charging dynamics of memory devices has been theoretically investigated. The calculations demonstrate that the charge stored in the NC Ge layer and the charging current at a given oxide voltage depend on the dot size especially on a few nanometers. They have also been found to obey the tendency of initial increase, then saturation, and lastly, decrease with increasing dot size at any given charging time, which is caused by a compromise between the effects of the lowest conduction states and the capacitance of NC Ge layer on the tunneling. The experimental data from literature have also been used to compare and validate the theoretical analysis. PMID:23305228

A facile one-pot synthesis of ruthenium hydroxide nanoparticles on magnetic silica: aqueous hydration of nitriles to amides.

PubMed

Baig, R B Nasir; Varma, Rajender S

2012-06-25

One-pot synthesis of ruthenium hydroxide nanoparticles on magnetic silica is described which involves the in situ generation of magnetic silica (Fe(3)O(4)@SiO(2)) and ruthenium hydroxide immobilization; the hydration of nitriles occurs in high yield and excellent selectivity using this catalyst which proceeds exclusively in aqueous medium under neutral conditions.

Nanocrystalline High-Entropy Alloys: A New Paradigm in High-Temperature Strength and Stability.

PubMed

Zou, Yu; Wheeler, Jeffrey M; Ma, Huan; Okle, Philipp; Spolenak, Ralph

2017-03-08

Metals with nanometer-scale grains or nanocrystalline metals exhibit high strengths at ambient conditions, yet their strengths substantially decrease with increasing temperature, rendering them unsuitable for usage at high temperatures. Here, we show that a nanocrystalline high-entropy alloy (HEA) retains an extraordinarily high yield strength over 5 GPa up to 600 °C, 1 order of magnitude higher than that of its coarse-grained form and 5 times higher than that of its single-crystalline equivalent. As a result, such nanostructured HEAs reveal strengthening figures of merit-normalized strength by the shear modulus above 1/50 and strength-to-density ratios above 0.4 MJ/kg, which are substantially higher than any previously reported values for nanocrystalline metals in the same homologous temperature range, as well as low strain-rate sensitivity of ∼0.005. Nanocrystalline HEAs with these properties represent a new class of nanomaterials for high-stress and high-temperature applications in aerospace, civilian infrastructure, and energy sectors.

Surface Properties of a Nanocrystalline Fe-Ni-Nb-B Alloy After Neutron Irradiation

NASA Astrophysics Data System (ADS)

Pavùk, Milan; Sitek, Jozef; Sedlačková, Katarína

2014-09-01

The effect of neutron radiation on the surface properties of the nanocrystalline (Fe0.25Ni0.75)81Nb7B12 alloy was studied. Firstly, amorphous (Fe0.25Ni0.75)81Nb7B12 ribbon was brought by controlled annealing to the nanocrystalline state. After annealing, the samples of the nanocrystalline ribbon were irradiated in a nuclear reactor with neutron fluences of 1×1016cm-2 and 1 × 1017cm-2 . By utilizing the magnetic force microscopy (MFM), topography and a magnetic domain structure were recorded at the surface of the ribbon-shaped samples before and after irradiation with neutrons. The results indicate that in terms of surface the nanocrystalline (Fe0.25Ni0.75)81Nb7B12 alloy is radiation-resistant up to a neutron fluence of 1 × 1017cm-2 . The changes in topography observed for both irradiated samples are discussed

Grain growth in nanocrystalline iron and Fe-Al alloys

NASA Astrophysics Data System (ADS)

Mirzadeh, Hamed; Zomorodian, Amir

2010-02-01

The effects of the annealing temperature and time, cryomilling in liquid nitrogen, and the addition of aluminum powder on the thermal stability and grain growth behavior of nanocrystalline iron were modeled using the Artificial Neural Network (ANN) technique. The developed model can be used as a guide for the quantification of the grain growth by considering the effects of annealing temperature and time. The model also quantified the effect of Al on the thermal stability of cryomilled nanocrystalline Fe. The model results showed that the cryomilling of Fe has a tangible effect on the stabilization of the nanostructure.

The Application of Metal Oxide Nanomaterials for Chemical Sensor Development

NASA Technical Reports Server (NTRS)

Xu, Jennifer C.; Hunter, Gary W.; Evans, Laura J.; VanderWal, Randy L.; Berger, Gordon M.

2007-01-01

NASA Glenn Research Center (GRC) has been developing miniature chemical sensors for a variety of applications including fire detection, emissions monitoring, fuel leak detection, and environmental monitoring. Smart Lick and Stick sensor technology which integrates a sensor array, electronics, telemetry, and power into one microsystem are being developed. These microsystems require low power consumption for long-term aerospace applications. One approach to decreasing power consumption is the use of nanotechnology. Nanocrystalline tin oxide (SnO2) carbon monoxide (CO) sensors developed previously by this group have been successfully used for fire detection and emissions monitoring. This presentation will briefly review the overall NASA GRC chemical sensor program and discuss our further effort in nanotechnology applications. New carbon dioxide (CO2) sensing material using doped nanocrystalline SnO2 will be discussed. Nanocrystalline SnO2 coated solid electrolyte CO2 sensors and SnO2 nanorod and nanofiber hydrogen (H2) sensors operated at reduced or room temperatures will also be discussed.

In Vitro Effects of Novel Ruthenium Complexes in Neospora caninum and Toxoplasma gondii Tachyzoites

PubMed Central

Barna, Fabienne; Debache, Karim; Küster, Tatiana

2013-01-01

Upon the screening of 16 antiproliferative compounds against Toxoplasma gondii and Neospora caninum, two hydrolytically stable ruthenium complexes (compounds 16 and 18) exhibited 50% inhibitory concentrations of 18.7 and 41.1 nM (T. gondii) and 6.7 and 11.3 nM (N. caninum). To achieve parasiticidal activity with compound 16, long-term treatment (22 to 27 days at 80 to 160 nM) was required. Transmission electron microscopy demonstrated the rapid impact on and ultrastructural alterations in both parasites. These preliminary findings suggest that the potential of ruthenium-based compounds should thus be further exploited. PMID:23979747

Mesoporous Transition Metal Oxides for Supercapacitors

PubMed Central

Wang, Yan; Guo, Jin; Wang, Tingfeng; Shao, Junfeng; Wang, Dong; Yang, Ying-Wei

2015-01-01

Recently, transition metal oxides, such as ruthenium oxide (RuO2), manganese dioxide (MnO2), nickel oxides (NiO) and cobalt oxide (Co3O4), have been widely investigated as electrode materials for pseudo-capacitors. In particular, these metal oxides with mesoporous structures have become very hot nanomaterials in the field of supercapacitors owing to their large specific surface areas and suitable pore size distributions. The high specific capacities of these mesoporous metal oxides are resulted from the effective contacts between electrode materials and electrolytes as well as fast transportation of ions and electrons in the bulk of electrode and at the interface of electrode and electrolyte. During the past decade, many achievements on mesoporous transition metal oxides have been made. In this mini-review, we select several typical nanomaterials, such as RuO2, MnO2, NiO, Co3O4 and nickel cobaltite (NiCo2O4), and briefly summarize the recent research progress of these mesoporous transition metal oxides-based electrodes in the field of supercapacitors. PMID:28347088

Metastable tantalum oxide formation during the devitrification of amorphous tantalum thin films

DOE PAGES

Donaldson, Olivia K.; Hattar, Khalid; Trelewicz, Jason R.

2016-07-04

Microstructural evolution during the devitrification of amorphous tantalum thin films synthesized via pulsed laser deposition was investigated using in situ transmission electron microscopy (TEM) combined with ex situ isothermal annealing, bright-field imaging, and electron-diffraction analysis. The phases formed during crystallization and their stability were characterized as a function of the chamber pressure during deposition, devitrification temperature, and annealing time. A range of metastable nanocrystalline tantalum oxides were identified following devitrification including multiple orthorhombic oxide phases, which often were present with, or evolved to, the tetragonal TaO 2 phase. While the appearance of these phases indicated the films were evolving tomore » the stable form of tantalum oxide—monoclinic tantalum pentoxide—it was likely not achieved for the conditions considered due to an insufficient amount of oxygen present in the films following deposition. Nevertheless, the collective in situ and ex situ TEM analysis applied to thin film samples enabled the isolation of a number of metastable tantalum oxides. As a result, new insights were gained into the transformation sequence and stability of these nanocrystalline phases, which presents opportunities for the development of advanced tantalum oxide-based dielectric materials for novel memristor designs.« less

Thermal conductivity of amorphous and nanocrystalline silicon films prepared by hot-wire chemical-vapor deposition

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

Jugdersuren, B.; Kearney, B. T.; Queen, D. R.

We report 3..omega.. thermal conductivity measurements of amorphous and nanocrystalline silicon thin films from 85 to 300 K prepared by hot-wire chemical-vapor deposition, where the crystallinity of the films is controlled by the hydrogen dilution during growth. The thermal conductivity of the amorphous silicon film is in agreement with several previous reports of amorphous silicon prepared by a variety of deposition techniques. The thermal conductivity of the as-grown nanocrystalline silicon film is 70% higher and increases 35% more after an anneal at 600 degrees C. They all have similarly weak temperature dependence. Structural analysis shows that the as-grown nanocrystalline siliconmore » is approximately 60% crystalline, nanograins and grain boundaries included. The nanograins, averaging 9.1 nm in diameter in the as-grown film, are embedded in an amorphous matrix. The grain size increases to 9.7 nm upon annealing, accompanied by the disappearance of the amorphous phase. We extend the models of grain boundary scattering of phonons with two different non-Debye dispersion relations to explain our result of nanocrystalline silicon, confirming the strong grain size dependence of heat transport for nanocrystalline materials. However, the similarity in thermal conductivity between amorphous and nanocrystalline silicon suggests the heat transport mechanisms in both structures may not be as dissimilar as we currently understand.« less

Synthesis and Catalytic Activity of Ruthenium-Indenylidene Complexes for Olefin Metathesis: Microscale Experiments for the Undergraduate Inorganic or Organometallic Laboratories

ERIC Educational Resources Information Center

Pappenfus, Ted M.; Hermanson, David L.; Ekerholm, Daniel P.; Lilliquist, Stacie L.; Mekoli, Megan L.

2007-01-01

A series of experiments for undergraduate laboratory courses (e.g., inorganic, organometallic or advanced organic) have been developed. These experiments focus on understanding the design and catalytic activity of ruthenium-indenylidene complexes for olefin metathesis. Included in the experiments are the syntheses of two ruthenium-indenylidene…

Three dimensional graphene foam supported platinum-ruthenium bimetallic nanocatalysts for direct methanol and direct ethanol fuel cell applications

NASA Astrophysics Data System (ADS)

Kung, Chih-Chien; Lin, Po-Yuan; Xue, Yuhua; Akolkar, Rohan; Dai, Liming; Yu, Xiong; Liu, Chung-Chiun

2014-06-01

A novel composite material of hierarchically structured platinum-ruthenium (PtRu) nanoparticles grown on large surface area three dimensional graphene foam (3D GF) is reported. 3D GF was incorporated with PtRu bimetallic nanoparticles as an electrochemical nanocatalyst for methanol and ethanol oxidation. PtRu/3D GF nanocatalyst showed a higher tolerance to poisoning by CO and exhibited improved catalytic activity for both methanol oxidation reaction (MOR) and ethanol oxidation reaction (EOR). Cyclic voltammetry (CV) results and long-term cycling stability tests demonstrated that GF provided a promising platform for the development of electrochemical nanocatalysts. Specifically, PtRu/3D GF nanocatalyst showed excellent catalytic activity toward MOR and EOR compared with PtRu/Graphene (Commercial graphene), PtRu/C (Vulcan XC-72R carbon), and PtRu alone. The crystal size of PtRu on 3D GF was reduced to 3.5 nm and its active surface area was enhanced to 186.2 m2 g-1. Consequently, the MOR and EOR rates were nearly doubled on PtRu/3D GF compared to those on PtRu/Graphene.

In vitro and in vivo antiproliferative and trypanocidal activities of ruthenium NO donors

PubMed Central

Silva, J J N; Osakabe, A L; Pavanelli, W R; Silva, J S; Franco, D W

2007-01-01

Background and purpose: Many compounds liberating NO (NO donors) have been used as therapeutic agents. Here we test two ruthenium nitrosyls, which release NO when activated by biological reducing agents, for their effects in vitro and in vivo against Trypanasoma cruzi, the agent responsible for the American trypanosomiasis (Chagas' disease). Experimental approach: Ruthenium NO donors were incubated with a partially drug-resistant strain of T. cruzi and the anti-proliferative and trypanocidal activities evaluated. In a mouse model of acute Chagas' disease, trypanocidal activity was evaluated by measuring parasitemia, survival rate of infected mice and elimination of amastigotes in myocardial tissue. Key results: In vitro, the observed anti-proliferative and trypanocidal activities of trans-[Ru(NO)(NH3)4isn](BF4)3 and trans-[Ru(NO)(NH3)4imN](BF4)3 were due to NO liberated upon reduction of these nitrosyls. Ru(NO)isn had a lower IC50epi (67 μM) than the NO donor, sodium nitroprusside (IC50epi=244 μM) and Ru(NO)imN (IC50try=52 μM) was more potent than gentian violet (IC50try=536 μM), currently used in the treatment of blood. Both ruthenium nitrosyls eliminated, in vivo, extracellular as well as intracellular forms of T. cruzi in the bloodstream and myocardial tissue and allowed survival of up to 80% of infected mice at a dose (100 nmol kg−1 day−1) much lower than the optimal dose for benznidazole (385 μmol kg−1 day−1). Conclusions and implications: Our data strongly suggest that NO liberated is responsible for the anti-proliferative and trypanocidal activities of the ruthenium NO donors and that these compounds are promising leads for novel and effective anti-parasitic drugs. PMID:17603548

Conversion Reaction-Based Oxide Nanomaterials for Lithium Ion Battery Anodes.

PubMed

Yu, Seung-Ho; Lee, Soo Hong; Lee, Dong Jun; Sung, Yung-Eun; Hyeon, Taeghwan

2016-04-27

Developing high-energy-density electrodes for lithium ion batteries (LIBs) is of primary importance to meet the challenges in electronics and automobile industries in the near future. Conversion reaction-based transition metal oxides are attractive candidates for LIB anodes because of their high theoretical capacities. This review summarizes recent advances on the development of nanostructured transition metal oxides for use in lithium ion battery anodes based on conversion reactions. The oxide materials covered in this review include oxides of iron, manganese, cobalt, copper, nickel, molybdenum, zinc, ruthenium, chromium, and tungsten, and mixed metal oxides. Various kinds of nanostructured materials including nanowires, nanosheets, hollow structures, porous structures, and oxide/carbon nanocomposites are discussed in terms of their LIB anode applications. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Influence of the UV radiation on the screen-printed pH-sensitive layers based on graphene and ruthenium dioxide

NASA Astrophysics Data System (ADS)

Pepłowski, A.; Grudziński, D.; Raczyński, T.; Wróblewski, G.; Janczak, D.; Jakubowska, M.

2017-08-01

Electrodes for measuring pH of the solution were fabricated by the means of screen-printing technology. Potentiometric sensors' layers comprised of composite with polymer matrix and graphene nanoplatelets/ruthenium (IV) oxide nanopowder as functional phase. Transceivers were printed on the elastic PMMA foil. Regarding potential application of the sensors in the wearable devices, dynamic response of the electrodes to changing ultraviolet radiation levels was assessed, since RuO2 is reported to be UV-sensitive. Observed changes of the electrodes' potential were of sub-millivolt magnitude, being comparable to simultaneously observed signal drift. Given this stability under varying UV conditions and previously verified good flexibility, fabricated sensors meet the requirements for wearable applications.

Ruthenium-catalyzed regioselective allylic amination of 2,3,3-trifluoroallylic carbonates.

PubMed

Isobe, Shin-Ichi; Terasaki, Shou; Hanakawa, Taisyun; Mizuno, Shota; Kawatsura, Motoi

2017-04-05

We demonstrated the ruthenium-catalyzed allylic amination of 2,3,3-trifluoroallylic carbonates with several types of amines. The reactions proceeded with several types of amines, and succeeded in obtaining polyfluorinated terminal alkenes possessing branched allylic amines as a single regioisomer.

Ionic Conduction in Nanocrystalline Materials

DTIC Science & Technology

2000-02-10

In the following, we review studies performed films prepared by a polymer precursor process on on stabilized zirconia ceramics with grain sizes alumina ... titania , is reviewed. While it remains too early to make firm conclusions, the following observations are made. Additives which contribute to ion blocking...Keywords: Ionic conductivity; Nanocrystalline; Zirconia; Ceria; Titania ; Defects 1. Introduction tivity by nearly two orders of magnitude [6]. Given the

Ceria-supported ruthenium nanoparticles as highly active and long-lived catalysts in hydrogen generation from the hydrolysis of ammonia borane.

PubMed

Akbayrak, Serdar; Tonbul, Yalçın; Özkar, Saim

2016-07-05

Ruthenium(0) nanoparticles supported on ceria (Ru(0)/CeO2) were in situ generated from the reduction of ruthenium(iii) ions impregnated on ceria during the hydrolysis of ammonia borane. Ru(0)/CeO2 was isolated from the reaction solution by centrifugation and characterized by ICP-OES, BET, XRD, TEM, SEM-EDS and XPS techniques. All the results reveal that ruthenium(0) nanoparticles were successfully supported on ceria and the resulting Ru(0)/CeO2 is a highly active, reusable and long-lived catalyst for hydrogen generation from the hydrolysis of ammonia borane with a turnover frequency value of 361 min(-1). The reusability tests reveal that Ru(0)/CeO2 is still active in the subsequent runs of hydrolysis of ammonia borane preserving 60% of the initial catalytic activity even after the fifth run. Ru(0)/CeO2 provides a superior catalytic lifetime (TTO = 135 100) in hydrogen generation from the hydrolysis of ammonia borane at 25.0 ± 0.1 °C before deactivation. The work reported here includes the formation kinetics of ruthenium(0) nanoparticles. The rate constants for the slow nucleation and autocatalytic surface growth of ruthenium(0) nanoparticles were obtained using hydrogen evolution as a reporter reaction. An evaluation of rate constants at various temperatures enabled the estimation of activation energies for both the reactions, Ea = 60 ± 7 kJ mol(-1) for the nucleation and Ea = 47 ± 2 kJ mol(-1) for the autocatalytic surface growth of ruthenium(0) nanoparticles, as well as the activation energy of Ea = 51 ± 2 kJ mol(-1) for the catalytic hydrolysis of ammonia borane.

Efficient Light-Driven Water Oxidation Catalysis by Dinuclear Ruthenium Complexes.

PubMed

Berardi, Serena; Francàs, Laia; Neudeck, Sven; Maji, Somnath; Benet-Buchholz, Jordi; Meyer, Franc; Llobet, Antoni

2015-11-01

Mastering the light-induced four-electron oxidation of water to molecular oxygen is a key step towards the achievement of overall water splitting to produce alternative solar fuels. In this work, we report two rugged molecular pyrazolate-based diruthenium complexes that efficiently catalyze visible-light-driven water oxidation. These complexes were fully characterized both in the solid state (by X-ray diffraction analysis) and in solution (spectroscopically and electrochemically). Benchmark performances for homogeneous oxygen production have been obtained for both catalysts in the presence of a photosensitizer and a sacrificial electron acceptor at pH 7, and a turnover frequency of up to 11.1 s(-1) and a turnover number of 5300 were obtained after three successive catalytic runs. Under the same experimental conditions with the same setup, the pyrazolate-based diruthenium complexes outperform other well-known water oxidation catalysts owing to both electrochemical and mechanistic aspects. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Characteristics of W Doped Nanocrystalline Carbon Films Prepared by Unbalanced Magnetron Sputtering.

PubMed

Park, Yong Seob; Park, Chul Min; Kim, Nam-Hoon; Kim, Jae-Moon

2016-05-01

Nanocrystalline tungsten doped carbon (WC) films were prepared by unbalanced magnetron sputtering. Tungsten was used as the doping material in carbon thin films with the aim of application as a contact strip in an electric railway. The structural, physical, and electrical properties of the fabricated WC films with various DC bias voltages were investigated. The films had a uniform and smooth surface. Hardness and frication characteristics of the films were improved, and the resistivity and sheet resistance decreased with increasing negative DC bias voltage. These results are associated with the nanocrystalline WC phase and sp(2) clusters in carbon networks increased by ion bombardment enhanced with increasing DC bias voltage. Consequently, the increase of sp(2) clusters containing WC nanocrystalline in the carbon films is attributed to the improvement in the physical and electrical properties.

Selective oxidation of methanol and ethanol on supported ruthenium oxide clusters at low temperatures

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

Liu, Haichao; Iglesia, Enrique

RuO2 domains supported on SnO2, ZrO2, TiO2, Al2O3, and SiO2 catalyze the oxidative conversion of methanol to formaldehyde, methylformate, and dimethoxymethane with unprecedented rates and high combined selectivity (>99 percent) and yield at low temperatures (300-400 K). Supports influence turnover rates and the ability of RuO2 domains to undergo redox cycles required for oxidation turnovers. Oxidative dehydrogenation turnover rates and rates of stoichiometric reduction of RuO2 in H2 increased in parallel when RuO2 domains were dispersed on more reducible supports. These support effects, the kinetic effects of CH3OH and O2 on reaction rates, and the observed kinetic isotope effects withmore » CH3OD and CD3OD reactants are consistent with a sequence of elementary steps involving kinetically relevant H-abstraction from adsorbed methoxide species using lattice oxygen atoms and with methoxide formation in quasi-equilibrated CH3OH dissociation on nearly stoichiometric RuO2 surfaces. Anaerobic transient experiments confirmed that CH3OH oxidation to HCHO requires lattice oxygen atoms and that selectivities are not influenced by the presence of O2. Residence time effects on selectivity indicate that secondary HCHO-CH3OH acetalization reactions lead to hemiacetal or methoxymethanol intermediates that convert to dimethoxymethane in reactions with CH3OH on support acid sites or dehydrogenate to form methylformate on RuO2 and support redox sites. These conclusions are consistent with the tendency of Al2O3 and SiO2 supports to favor dimethoxymethane formation, while SnO2, ZrO2, and TiO2 preferentially form methylformate. These support effects on secondary reactions were confirmed by measured CH3OH oxidation rates and selectivities on physical mixtures of supported RuO2 catalysts and pure supports. Ethanol also reacts on supported RuO2 domains to form predominately acetaldehyde and diethoxyethane at 300-400 K. The bifunctional nature of these reaction pathways and the

Isolation of bacterial cellulose nanocrystalline from pineapple peel waste: Optimization of acid concentration in the hydrolysis method

NASA Astrophysics Data System (ADS)

Anwar, Budiman; Rosyid, Nurul Huda; Effendi, Devi Bentia; Nandiyanto, Asep Bayu Dani; Mudzakir, Ahmad; Hidayat, Topik

2016-02-01

Isolation of needle-shaped bacterial cellulose nanocrystalline with a diameter of 16-64 nm, a fiber length of 258-806 nm, and a degree of crystallinity of 64% from pineapple peel waste using an acid hydrolysis process was investigated. Experimental showed that selective concentration of acid played important roles in isolating the bacterial cellulose nanocrystalline from the cellulose source. To achieve the successful isolation of bacterial cellulose nanocrystalline, various acid concentrations were tested. To confirm the effect of acid concentration on the successful isolation process, the reaction conditions were fixed at a temperature of 50°C, a hydrolysis time of 30 minutes, and a bacterial cellulose-to-acid ratio of 1:50. Pineapple peel waste was used as a model for a cellulose source because to the best of our knowledge, there is no report on the use of this raw material for producing bacterial cellulose nanocrystalline. In fact, this material can be used as an alternative for ecofriendly and cost-free cellulose sources. Therefore, understanding in how to isolate bacterial cellulose nanocrystalline from pineapple peel waste has the potential for large-scale production of inexpensive cellulose nanocrystalline.

Tracking the Oxygen Status in the Cell Nucleus with a Hoechst-Tagged Phosphorescent Ruthenium Complex.

PubMed

Hara, Daiki; Umehara, Yui; Son, Aoi; Asahi, Wataru; Misu, Sotaro; Kurihara, Ryohsuke; Kondo, Teruyuki; Tanabe, Kazuhito

2018-05-04

Molecular oxygen in living cells is distributed and consumed inhomogeneously, depending on the activity of each organelle. Therefore, tractable methods that can be used to monitor the oxygen status in each organelle are needed to understand cellular function. Here we report the design of a new oxygen-sensing probe for use in the cell nucleus. We prepared "Ru-Hoechsts", each consisting of a phosphorescent ruthenium complex linked to a Hoechst 33258 moiety, and characterized their properties as oxygen sensors. The Hoechst unit shows strong DNA-binding properties in the nucleus, and the ruthenium complex shows oxygen-dependent phosphorescence. Thus, Ru-Hoechsts accumulated in the cell nucleus and showed oxygen-dependent signals that could be monitored. Of the Ru-Hoechsts prepared in this study, Ru-Hoechst b, in which the ruthenium complex and the Hoechst unit were linked through a hexyl chain, showed the most suitable properties for monitoring the oxygen status. Ru-Hoechsts are probes with high potential for visualizing oxygen fluctuations in the nucleus. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and characterization of nanocrystalline mesoporous zirconia using supercritical drying.

PubMed

Tyagi, Beena; Sidhpuria, Kalpesh; Shaik, Basha; Jasra, Raksh Vir

2006-06-01

Synthesis of nano-crystalline zirconia aerogel was done by sol-gel technique and supercritical drying using n-propanol solvent at and above supercritical temperature (235-280 degrees C) and pressure (48-52 bar) of n-propanol. Zirconia xerogel samples have also been prepared by conventional thermal drying method to compare with the super critically dried samples. Crystalline phase, crystallite size, surface area, pore volume, and pore size distribution were determined for all the samples in detail to understand the effect of gel drying methods on these properties. Supercritical drying of zirconia gel was observed to give thermally stable, nano-crystalline, tetragonal zirconia aerogels having high specific surface area and porosity with narrow and uniform pore size distribution as compared to thermally dried zirconia. With supercritical drying, zirconia samples show the formation of only mesopores whereas in thermally dried samples, substantial amount of micropores are observed along with mesopores. The samples prepared using supercritical drying yield nano-crystalline zirconia with smaller crystallite size (4-6 nm) as compared to higher crystallite size (13-20 nm) observed with thermally dried zirconia.

Antiproliferative effects of ruthenium-based nucleolipidic nanoaggregates in human models of breast cancer in vitro: insights into their mode of action

PubMed Central

Irace, Carlo; Misso, Gabriella; Capuozzo, Antonella; Piccolo, Marialuisa; Riccardi, Claudia; Luchini, Alessandra; Caraglia, Michele; Paduano, Luigi; Montesarchio, Daniela; Santamaria, Rita

2017-01-01

Looking for new metal-based anticancer treatments, in recent years many ruthenium complexes have been proposed as effective and safe potential drugs. In this context we have recently developed a novel approach for the in vivo delivery of Ru(III) complexes, preparing stable ruthenium-based nucleolipidic nanoaggregates endowed with significant antiproliferative activity. Herein we describe the cellular response to our ruthenium-containing formulations in selected models of human breast cancer. By in vitro bioscreens in the context of preclinical studies, we have focused on their ability to inhibit breast cancer cell proliferation by the activation of the intrinsic apoptotic pathway, possibly via mitochondrial perturbations involving Bcl-2 family members and predisposing to programmed cell death. In addition, the most efficient ruthenium-containing cationic nanoaggregates we have hitherto developed are able to elicit both extrinsic and intrinsic apoptosis, as well as autophagy. To limit chemoresistance and counteract uncontrolled proliferation, multiple cell death pathways activation by metal-based chemotherapeutics is a challenging, yet very promising strategy for targeted therapy development in aggressive cancer diseases, such as triple-negative breast cancer with limited treatment options. These outcomes provide valuable, original knowledge on ruthenium-based candidate drugs and new insights for future optimized cancer treatment protocols. PMID:28349991

Formation of polycyclic lactones through a ruthenium-catalyzed ring-closing metathesis/hetero-Pauson-Khand reaction sequence.

PubMed

Finnegan, David F; Snapper, Marc L

2011-05-20

Processes that form multiple carbon-carbon bonds in one operation can generate molecular complexity quickly and therefore be used to shorten syntheses of desirable molecules. We selected the hetero-Pauson-Khand (HPK) cycloaddition and ring-closing metathesis (RCM) as two unique carbon-carbon bond-forming reactions that could be united in a tandem ruthenium-catalyzed process. In doing so, complex polycyclic products can be obtained in one reaction vessel from acyclic precursors using a single ruthenium additive that can catalyze sequentially two mechanistically distinct transformations.

Self-composite comprised of nanocrystalline diamond and a non-diamond component useful for thermoelectric applications

DOEpatents

Gruen, Dieter M.

2012-09-04

One provides nanocrystalline diamond material that comprises a plurality of substantially ordered diamond crystallites that are sized no larger than about 10 nanometers. One then disposes a non-diamond component within the nanocrystalline diamond material. By one approach this non-diamond component comprises an electrical conductor that is formed at the grain boundaries that separate the diamond crystallites from one another. The resultant nanowire is then able to exhibit a desired increase with respect to its ability to conduct electricity while also preserving the thermal conductivity behavior of the nanocrystalline diamond material.

Self-composite comprised of nanocrystalline diamond and a non-diamond component useful for thermoelectric applications

DOEpatents

Gruen, Dieter M [Downers Grove, IL

2009-08-11

One provides nanocrystalline diamond material that comprises a plurality of substantially ordered diamond crystallites that are sized no larger than about 10 nanometers. One then disposes a non-diamond component within the nanocrystalline diamond material. By one approach this non-diamond component comprises an electrical conductor that is formed at the grain boundaries that separate the diamond crystallites from one another. The resultant nanowire is then able to exhibit a desired increase with respect to its ability to conduct electricity while also preserving the thermal conductivity behavior of the nanocrystalline diamond material.

Restricting the high-temperature growth of nanocrystalline tin oxide

NASA Astrophysics Data System (ADS)

Savin, S.; Chadwick, A. V.

2003-01-01

The sensitivity of tin oxide is dependent on various factors, one of which is the grain size. Three methods have been investigated with the aim of stabilising the grain size in the nanometer range, namely; (i) encapsulation within a silica matrix, (ii) coating the crystallites with hexamethyldisilazane and (iii) pinning the grain boundaries with a second metal oxide nanocrystal. The resulting materials have been characterised by X-ray powder diffraction (XRPD), Extended X-ray absorption fine structure (EXAFS) and conductivity measurements.

Characterization of screen-printed dye-sensitized nanocrystalline TiO2 solar cells

NASA Astrophysics Data System (ADS)

Gupta, Tapan K.; Cirignano, Leonard J.; Shah, Kanai S.; Moy, Larry P.; Kelly, David J.; Squillante, Michael R.; Entine, Gerald; Smestad, Greg P.

1999-10-01

Titanium dioxide (TiO2) films have been deposited on SnO2 coated glass substrates by screen-printing. Film morphology and structure have been characterized by scanning electron microscopy, x-ray diffraction and BET analysis. Dye-sensitized TiO2 photoelectrochemical cells have been assembled and characterized. Cells sensitized with anthocyanin and a ruthenium complex have been investigated. A 0.77 cm2 ruthenium dye sensitized cell with 6.1% power conversion efficiency under Air Mass (AM1.5) conditions was obtained. Results obtained with a pure anthocyanin dye and dye extracted from blackberries were compared. Finally, a natural gel was found to improve the stability of anthocyanin sensitized cells.

Electron transfer across multiple hydrogen bonds: the case of ureapyrimidinedione-substituted vinyl ruthenium and osmium complexes.

PubMed

Pichlmaier, Markus; Winter, Rainer F; Zabel, Manfred; Zális, Stanislav

2009-04-08

Ruthenium and osmium complexes 2a,b and 3a,b featuring the N-4,6-dioxo-5,5-dibutyl- or the N-4,6-dioxo-5,5-di-(2-propenyl)-1,4,5,6-tetrahydropyrimidin-2-yl-N'(4-ethenylphenyl)-urea ligand dimerize by a self-complementary quadruply hydrogen-bonding donor/donor/acceptor/acceptor (DDAA) motif. We provide evidence that the dimeric structures are maintained in nonpolar solvents and in 0.1 M NBu(4)PF(6)/CH(2)Cl(2) supporting electrolyte solution. All complexes are reversibly oxidized in two consecutive two-electron oxidations (DeltaE(1/2) approximately = 500 mV) without any discernible potential splitting for the oxidation of the individual hydrogen-bridged redox active moieties. IR and UV/vis/NIR spectroelectrochemistry show a one-step conversion of the neutral to the dication without any discernible features of an intermediate monooxidized radical cation. Oxidation-induced IR changes of the NH and CO groups that are involved in hydrogen bonding are restricted to the styryl-bonded urea NH function. IR band assignments are aided by quantum chemical calculations. Our experimental findings clearly show that, at least in the present systems, the ureapyrimidinedione (Upy) DDAA hydrogen-bonding motif does not support electron transfer. The apparent reason is that neither of the hydrogen-bonding functionalities contributes to the occupied frontier levels. This results in nearly degenerate pairs of MOs representing the in-phase and out-of-phase combinations of the individual monomeric building blocks.

Polyvinylpyrrolidone stabilized-Ru nanoclusters loaded onto reduced graphene oxide as high active catalyst for hydrogen evolution

NASA Astrophysics Data System (ADS)

Zhang, Jiao; Hao, Jinghao; Ma, Qianli; Li, Chuanqi; Liu, Yushan; Li, Baojun; Liu, Zhongyi

2017-06-01

Ruthenium/reduced graphene oxide nanocomposites (Ru/rGO NCs) were synthesized via an electrostatic self-assembly approach. Polyvinylpyrrolidone (PVP) stabilized and positively charged metallic ruthenium nanoclusters about 1.2 nm were synthesized and uniformly loaded onto negatively charged graphene oxide (GO) sheets via strong electrostatic interactions. The as-prepared Ru/rGO NCs exhibited superior performance in catalytic hydrolysis of sodium borohydride (NaBH4) to generate H2. The hydrogen generation rate was up to 14.87 L H2 min-1 gcat -1 at 318 K with relatively low activation energy of 38.12 kJ mol-1. Kinetics study confirmed that the hydrolysis of NaBH4 was first order with respect to concentration of catalysts. Besides, the conversion of NaBH4 remained at 97% and catalytic activity retained more than 70% after 5 reaction cycles at room temperature. These results suggested that the Ru/rGO NCs have a promising prospect in the field of clean energy.

Production of Nanocrystalline Ni-20Cr Coatings for High-Temperature Applications

NASA Astrophysics Data System (ADS)

Kumar, Manoj; Singh, Harpreet; Singh, Narinder

2014-04-01

Presynthesized nanocrystalline Ni-20Cr powder was deposited on SA 516 and T91 boiler steels by a high-velocity oxy-fuel spraying process. Ni-20Cr powder was synthesized by the ball milling approach. The high-temperature oxidation behavior of bare and coated samples was then studied under cyclic isothermal conditions at 900 °C for 50 cycles. The kinetics of oxidation was established using weight change measurements for the bare and coated boiler steels. Uncoated and coated samples of T91 steel were exposed to the superheated zone of a power plant boiler at 750 °C under cyclic conditions for 15 cycles. Each cycle consisted of 100 h of heating followed by 1 h of cooling. Attempts were made to study the kinetics of erosion-corrosion using weight change and thickness loss data for the samples. Different characterization techniques were used to study the oxidized and eroded-corroded samples, including x-ray diffraction, scanning electron microscopy/energy-dispersive spectroscopy, and x-ray mapping analyses. The Ni-20Cr alloy powder coating was found to offer excellent oxidation resistance to the base steels and was successful in reducing the weight gain of SA 516 steel by 98.5 % and that of T91 steel by 65 %. The coating was observed to reduce the erosion-corrosion rate of T91 steel by 86 % in terms of thickness loss. This indicates that the investigated nanostructured coating can be a better choice over conventional coating for erosion-corrosion control of boiler tubes.

Nanocrystalline CuNi alloys: improvement of mechanical properties and thermal stability

NASA Astrophysics Data System (ADS)

Nogues, Josep; Varea, A.; Pellicer, E.; Sivaraman, K. M.; Pane, S.; Nelson, B. J.; Surinach, S.; Baro, M. D.; Sort, J.

2014-03-01

Nanocrystalline metallic films are known to benefit from novel and enhanced physical and chemical properties. In spite of these outstanding properties, nanocrystalline metals typically show relatively poor thermal stability which leads to deterioration of the properties due to grain coarsening. We have studied nanocrystalline Cu1-xNix (0.56 < x < 1) thin films (3 μm-thick) electrodeposited galvanostatically onto Cu/Ti/Si (100) substrates. CuNi thin films exhibit large values of hardness (6.15 < H < 7.21 GPa), which can be tailored by varying the composition. However, pure Ni films (x = 1) suffer deterioration of their mechanical and magnetic properties after annealing during 3 h at relatively low temperatures (TANN > 475 K) due to significant grain growth. Interestingly, alloying Ni with Cu clearly improves the thermal stability of the material because grain coarsening is delayed due to segregation of a Cu-rich phase at grain boundaries, thus preserving both the mechanical and magnetic properties up to higher TANN.

Transition from Irradiation-Induced Amorphization to Crystallization in Nanocrystalline Silicon Carbide

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

Jiang, Weilin; Jiao, Liang; Wang, Haiyan

2011-12-01

Response to irradiation of nanocrystalline 3C-SiC is studied using 2 MeV Au+ ions near the critical temperature for amorphization and is compared to the behavior of its monocrystalline counterpart under the identical irradiation conditions. The irradiated samples have been characterized using in-situ ion channeling, ex-situ x-ray diffraction, and helium ion microscopy. Compared to monocrystalline 3C-SiC, a faster amorphization process in the nanocrystalline material (average grain size = 3.3 nm) is observed at 500 K. However, the nanograin grows with increasing ion fluence at 550 K and the grain size tends to saturate at high fluences. The striking contrast demonstrates amore » sharp transition from irradiation-induced interface-driven amorphization at 500 K to crystallization at 550 K. The results could show potential impacts of nanocrystalline SiC on nuclear fuel cladding and structural components of next-generation nuclear energy systems.« less

Ruthenium-cobalt nanoalloys encapsulated in nitrogen-doped graphene as active electrocatalysts for producing hydrogen in alkaline media

NASA Astrophysics Data System (ADS)

Su, Jianwei; Yang, Yang; Xia, Guoliang; Chen, Jitang; Jiang, Peng; Chen, Qianwang

2017-04-01

The scalable production of hydrogen could conveniently be realized by alkaline water electrolysis. Currently, the major challenge confronting hydrogen evolution reaction (HER) is lacking inexpensive alternatives to platinum-based electrocatalysts. Here we report a high-efficient and stable electrocatalyst composed of ruthenium and cobalt bimetallic nanoalloy encapsulated in nitrogen-doped graphene layers. The catalysts display remarkable performance with low overpotentials of only 28 and 218 mV at 10 and 100 mA cm-2, respectively, and excellent stability of 10,000 cycles. Ruthenium is the cheapest platinum-group metal and its amount in the catalyst is only 3.58 wt.%, showing the catalyst high activity at a very competitive price. Density functional theory calculations reveal that the introduction of ruthenium atoms into cobalt core can improve the efficiency of electron transfer from alloy core to graphene shell, beneficial for enhancing carbon-hydrogen bond, thereby lowing ΔGH* of HER.

Structure, Morphology, and Optical Properties of Amorphous and Nanocrystalline Gallium Oxide Thin Films

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

Kumar, S. Sampath; Rubio, E. J.; Noor-A-Alam, M.

Ga2O3 thin films were produced by sputter deposition by varying the substrate temperature (Ts) in a wide range (Ts=25-800 oC). The structural characteristics and optical properties of Ga2O3 films were evaluated using X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectrometry (EDS), Rutherford backscattering spectrometry (RBS) and spectrophotometric measurements. The effect of growth temperature is significant on the chemistry, crystal structure and morphology of Ga2O3 films. XRD and SEM analyses indicate that the Ga2O3 films grown at lower temperatures were amorphous while those grown at Ts≥500 oC were nanocrystalline. RBS measurements indicate the well-maintained stoichiometry of Ga2O3 films atmore » Ts=300-700 oC. The spectral transmission of the films increased with increasing temperature. The band gap of the films varied from 4.96 eV to 5.17 eV for a variation in Ts in the range 25-800 oC. A relationship between microstructure and optical property is discussed.« less

Long-Range Intramolecular Electronic Communication in a Trinuclear Ruthenium Tropolonate Complex.

PubMed

Yoshida, Jun; Kuwahara, Kyohei; Suzuki, Kota; Yuge, Hidetaka

2017-02-20

Dinuclear and trinuclear ruthenium complexes, [Ru(trop) 2 (C 2 trop)Ru(dppe)Cp] [2b; trop = tropolonato, C 2 trop = ethynyltropolonato, dppe = 1,2-bis(diphenylphosphino)ethane] and [Ru(trop){(C 2 trop)Ru(dppe)Cp} 2 ] (3), were synthesized, and their electronic and electrochemical properties were investigated in comparison with our previously reported complex [Ru(acac) 2 (C 2 trop)Ru(dppe)Cp] (2a). The electron-donating Ru II (dppe)Cp unit and electron-accepting Ru III O 6 unit are connected by C 2 trop in these complexes. 2a incorporates acetylacetonate as an ancillary ligand, while 2b and 3 incorporate tropolonate as an ancillary ligand. Every complex, 2a, 2b, and 3, exhibits similar UV-vis-near-IR (NIR) absorption spectra, demonstrating the lack of explicit intramolecular electronic communication between the units at least in the neutral state. The weak NIR absorption in 2a further diminished upon electrochemical oxidation, indicating almost no electronic communication between the units. In contrast, 2b and 3 exhibit broad NIR absorptions upon oxidation. Additionally, 3 exhibits four stepwise redox couples in the electrochemical study, which are formally attributed to [Ru II (trop) 3 ] - /[Ru III (trop) 3 ], two [Ru II (dppe)Cp]/[Ru III (dppe)Cp] + , and [Ru III (trop) 3 ]/[Ru IV (trop) 3 ] + couples. Clear separation of the redox couples attributed to the two terminal [Ru(dppe)Cp] units demonstrates the thermodynamic stability of the intermediate oxidation states with respect to disproportionation. Further electrochemical studies using an electrolyte including perfluorinated weakly coordinating anions and density functional theory/time-dependent density functional theory calculations confirmed the effect of ancillary ligands, acetylacetonate and tropolonate. In the case of 2a, electronic delocalization over the whole complex, especially over the [Ru(acac) 2 (trop)] unit, appears to be small. In contrast, the electronic communication between [Ru(dppe)Cp] and [Ru

Nanocrystalline SnO2:F thin films for liquid petroleum gas sensors.

PubMed

Chaisitsak, Sutichai

2011-01-01

This paper reports the improvement in the sensing performance of nanocrystalline SnO(2)-based liquid petroleum gas (LPG) sensors by doping with fluorine (F). Un-doped and F-doped tin oxide films were prepared on glass substrates by the dip-coating technique using a layer-by-layer deposition cycle (alternating between dip-coating a thin layer followed by a drying in air after each new layer). The results showed that this technique is superior to the conventional technique for both improving the film thickness uniformity and film transparency. The effect of F concentration on the structural, surface morphological and LPG sensing properties of the SnO(2) films was investigated. Atomic Force Microscopy (AFM) and X-ray diffraction pattern measurements showed that the obtained thin films are nanocrystalline SnO(2) with nanoscale-textured surfaces. Gas sensing characteristics (sensor response and response/recovery time) of the SnO(2):F sensors based on a planar interdigital structure were investigated at different operating temperatures and at different LPG concentrations. The addition of fluorine to SnO(2) was found to be advantageous for efficient detection of LPG gases, e.g., F-doped sensors are more stable at a low operating temperature (300 °C) with higher sensor response and faster response/recovery time, compared to un-doped sensor materials. The sensors based on SnO(2):F films could detect LPG even at a low level of 25% LEL, showing the possibility of using this transparent material for LPG leak detection.

Nanocrystalline SnO2:F Thin Films for Liquid Petroleum Gas Sensors

PubMed Central

Chaisitsak, Sutichai

2011-01-01

This paper reports the improvement in the sensing performance of nanocrystalline SnO2-based liquid petroleum gas (LPG) sensors by doping with fluorine (F). Un-doped and F-doped tin oxide films were prepared on glass substrates by the dip-coating technique using a layer-by-layer deposition cycle (alternating between dip-coating a thin layer followed by a drying in air after each new layer). The results showed that this technique is superior to the conventional technique for both improving the film thickness uniformity and film transparency. The effect of F concentration on the structural, surface morphological and LPG sensing properties of the SnO2 films was investigated. Atomic Force Microscopy (AFM) and X-ray diffraction pattern measurements showed that the obtained thin films are nanocrystalline SnO2 with nanoscale-textured surfaces. Gas sensing characteristics (sensor response and response/recovery time) of the SnO2:F sensors based on a planar interdigital structure were investigated at different operating temperatures and at different LPG concentrations. The addition of fluorine to SnO2 was found to be advantageous for efficient detection of LPG gases, e.g., F-doped sensors are more stable at a low operating temperature (300 °C) with higher sensor response and faster response/recovery time, compared to un-doped sensor materials. The sensors based on SnO2:F films could detect LPG even at a low level of 25% LEL, showing the possibility of using this transparent material for LPG leak detection. PMID:22164007

Nanocrystalline coating design for extreme applications based on the concept of complex adaptive behavior

NASA Astrophysics Data System (ADS)

Fox-Rabinovich, G. S.; Veldhuis, S. C.; Dosbaeva, G. K.; Yamamoto, K.; Kovalev, A. I.; Wainstein, D. L.; Gershman, I. S.; Shuster, L. S.; Beake, B. D.

2008-04-01

The development of effective hard coatings for high performance dry machining, which is associated with high stress/temperatures during friction, is a major challenge. Newly developed synergistically alloyed nanocrystalline adaptive Ti0.2Al0.55Cr0.2Si0.03Y0.02N plasma vapor deposited hard coatings exhibit excellent tool life under conditions of high performance dry machining of hardened steel, especially under severe and extreme cutting conditions. The coating is capable of sustaining cutting speeds as high as 600 m/min. Comprehensive investigation of the microstructure and properties of the coating was performed. The structure of the coating before and after service has been characterized by high resolution transmission electron microscopy. Micromechanical characteristics of the coating have been investigated at elevated temperatures. Oxidation resistance of the coating has been studied by using thermogravimetry within a temperature range of 25-1100 °C in air. The coefficient of friction of the coatings was studied within a temperature range of 25-1200 °C. To determine the causes of excellent tool life and improved wear behavior of the TiAlCrSiYN coatings, its surface structure characteristics after service have been investigated by using x-ray photoelectron spectroscopy and extended energy-loss fine spectroscopy. One of the major features of this coating is the dynamic formation of the protective tribo-oxide films (dissipative structures) on the surface during friction with a sapphire and mullite crystal structure. Aluminum- and silicon-rich tribofilms with dangling bonds form on the surface as well. These tribofilms act in synergy and protect the surface so efficiently that it is able to sustain extreme operating conditions. Moreover, the Ti0.2Al0.55Cr0.2Si0.03Y0.02N coating possesses some features of a complex adaptive behavior because it has a number of improved characteristics (tribological adaptability, ultrafine nanocrystalline structure, hot hardness and

Characteristics of a promising new thermoelectric material - Ruthenium silicide

NASA Technical Reports Server (NTRS)

Ohta, Toshitaka; Vining, Cronin B.; Allevato, Camillo E.

1991-01-01

A preliminary study on arc-melted samples has indicated that ruthenium silicide has the potential to obtain figure-of-merit values four times higher than that of conventional silicon-germanium material. In order to realize the high figure-of-merit values, high-quality crystal from the melt is needed. A Bridgman-like method has been employed and has realized much better crystals than arc-melted ones.

Catalytic transformation of carbon dioxide and methane into syngas over ruthenium and platinum supported hydroxyapatites

NASA Astrophysics Data System (ADS)

Rêgo De Vasconcelos, Bruna; Zhao, Lulu; Sharrock, Patrick; Nzihou, Ange; Pham Minh, Doan

2016-12-01

This work focused on the catalytic transformation of methane (CH4) and carbon dioxide (CO2) into syngas (mixture of CO and H2). Ruthenium- and platinum-based catalysts were prepared using hydroxyapatite (HAP) as catalyst support. Different methods for metal deposition were used including incipient wetness impregnation (IWI), excess liquid phase impregnation (LIM), and cationic exchange (CEX). Metal particle size varied in large range from less than 1 nm to dozens nm. All catalysts were active at 400-700 °C but only Pt catalyst prepared by IWI method (Pt/HAP IWI) was found stable. The catalytic performance of Pt/HAP IWI could be comparable with the literature data on noble metal-based catalysts, prepared on metal oxide supports. For the first time, water was experimentally quantified as a by-product of the reaction. This helped to correctly buckle the mass balance of the process.

High Temperature Stable Nanocrystalline SiGe Thermoelectric Material

NASA Technical Reports Server (NTRS)

Yang, Sherwin (Inventor); Matejczyk, Daniel Edward (Inventor); Determan, William (Inventor)

2013-01-01

A method of forming a nanocomposite thermoelectric material having microstructural stability at temperatures greater than 1000 C. The method includes creating nanocrystalline powder by cryomilling. The method is particularly useful in forming SiGe alloy powder.

In-situ TEM observation of the response of ultrafine- and nanocrystalline-grained tungsten to extreme irradiation environments

PubMed Central

El-Atwani, O.; Hinks, J. A.; Greaves, G.; Gonderman, S.; Qiu, T.; Efe, M.; Allain, J. P.

2014-01-01

The accumulation of defects, and in particular He bubbles, can have significant implications for the performance of materials exposed to the plasma in magnetic-confinement nuclear fusion reactors. Some of the most promising candidates for deployment into such environments are nanocrystalline materials as the engineering of grain boundary density offers the possibility of tailoring their radiation resistance properties. In order to investigate the microstructural evolution of ultrafine- and nanocrystalline-grained tungsten under conditions similar to those in a reactor, a transmission electron microscopy study with in situ 2 keV He+ ion irradiation at 950°C has been completed. A dynamic and complex evolution in the microstructure was observed including the formation of defect clusters, dislocations and bubbles. Nanocrystalline grains with dimensions less than around 60 nm demonstrated lower bubble density and greater bubble size than larger nanocrystalline (60–100 nm) and ultrafine (100–500 nm) grains. In grains over 100 nm, uniform distributions of bubbles and defects were formed. At higher fluences, large faceted bubbles were observed on the grain boundaries, especially on those of nanocrystalline grains, indicating the important role grain boundaries can play in trapping He and thus in giving rise to the enhanced radiation tolerance of nanocrystalline materials. PMID:24796578

Ruthenium(II) polypyridyl complexes as dual inhibitors of telomerase and topoisomerase.

PubMed

Liao, Guoliang; Chen, Xiang; Wu, Jingheng; Qian, Chen; Wang, Yi; Ji, Liangnian; Chao, Hui

2015-09-14

One novel ruthenium polypyridyl complex, [Ru(bpy)2(icip)](2+) (1), and two previously reported ruthenium polypyridyl complexes, [Ru(bpy)2(pdppz)](2+) ()2 and [Ru(bpy)2(tactp)](2+) (3) (bpy = 2,2'-bipyridine, icip = 2-(indeno[2,1-b]chromen-6-yl)-1H-imidazo[4,5-f][1,10]phenanthroline, pdppz = phenanthro[4,5-abc]dipyrido[3,2-h:2',3'-j]phenazine, tactp = 4,5,9,18-tetraazachryseno[9,10-b]-triphenylene), have been synthesised. As expected, these complexes show inhibition towards telomerase by inducing and stabilising the G-quadruplex structure, and behave as topoisomerase I/II poisons at the same time. Additionally, the acute and chronic cytotoxicities of the complexes are considered. Furthermore, cell apoptosis experiments are used to briefly study the mechanism. Because studies involving multi-target inhibition towards topoisomerase and telomerase of Ru(II) complexes have not been reported previously, the present research may help to develop innovative chemical strategies and therapies.

Evidence of a temperature transition for denuded zone formation in nanocrystalline Fe under He irradiation

DOE PAGES

El-Atwani, Osman; Nathaniel II, James E.; Leff, Asher C.; ...

2016-10-18

Nanocrystalline materials are radiation-tolerant materials’ candidates due to their high defect sink density. Here, nanocrystalline iron films were irradiated with 10 keV helium ions in situ in a transmission electron microscope at elevated temperatures. Grain-size-dependent bubble density changes and denuded zone occurrence were observed at 700 K, but not at 573 K. This transition, attributed to increased helium–vacancy migration at elevated temperatures, suggests that nanocrystalline microstructures are more resistant to swelling at 700 K due to decreased bubble density. Finally, denuded zone formation had no correlation with grain size and misorientation angle under the conditions studied.

Method to grow pure nanocrystalline diamond films at low temperatures and high deposition rates

DOEpatents

Carlisle, John A [Plainfield, IL; Gruen, Dieter M [Downers Grove, IL; Auciello, Orlando [Bolingbrook, IL; Xiao, Xingcheng [Woodridge, IL

2009-07-07

A method of depositing nanocrystalline diamond film on a substrate at a rate of not less than about 0.2 microns/hour at a substrate temperature less than about 500.degree. C. The method includes seeding the substrate surface with nanocrystalline diamond powder to an areal density of not less than about 10.sup.10sites/cm.sup.2, and contacting the seeded substrate surface with a gas of about 99% by volume of an inert gas other than helium and about 1% by volume of methane or hydrogen and one or more of acetylene, fullerene and anthracene in the presence of a microwave induced plasma while maintaining the substrate temperature less than about 500.degree. C. to deposit nanocrystalline diamond on the seeded substrate surface at a rate not less than about 0.2 microns/hour. Coatings of nanocrystalline diamond with average particle diameters of less than about 20 nanometers can be deposited with thermal budgets of 500.degree. C.-4 hours or less onto a variety of substrates such as MEMS devices.

Synthesis and Luminescence Properties of Transparent Nanocrystalline GdF3:Tb Glass-Ceramic Scintillator.

PubMed

Lee, Gyuhyon; Savage, Nicholas; Wagner, Brent; Zhang, Yuelan; Jacobs, Benjamin; Menkara, Hisham; Summers, Christopher; Kang, Zhitao

2014-03-01

Transparent glass-ceramic containing rare-earth doped halide nanocrystals exhibits enhanced luminescence performance. In this study, a glass-ceramic with Tb doped gadolinium fluoride nanocrystals embedded in an aluminosilicate glass matrix is investigated for X-ray imaging applications. The nanocrystalline glass-ceramic scintillator was prepared by a melt-quench method followed by an anneal. The GdF 3 :Tb nanocrystals precipitated within the oxide glass matrix during the processing and their luminescence and scintillation properties were investigated. In this nanocomposite scintillator system, the incorporation of high atomic number Gd compound into the glass matrix increases the X-ray stopping power of the glass scintillator, and effective energy transfer between Gd 3+ and Tb 3+ ions in the nanocrystals enhances the scintillation efficiency.

Synthesis and Luminescence Properties of Transparent Nanocrystalline GdF3:Tb Glass-Ceramic Scintillator

PubMed Central

Lee, Gyuhyon; Savage, Nicholas; Wagner, Brent; Zhang, Yuelan; Jacobs, Benjamin; Menkara, Hisham; Summers, Christopher; Kang, Zhitao

2014-01-01

Transparent glass-ceramic containing rare-earth doped halide nanocrystals exhibits enhanced luminescence performance. In this study, a glass-ceramic with Tb doped gadolinium fluoride nanocrystals embedded in an aluminosilicate glass matrix is investigated for X-ray imaging applications. The nanocrystalline glass-ceramic scintillator was prepared by a melt-quench method followed by an anneal. The GdF3:Tb nanocrystals precipitated within the oxide glass matrix during the processing and their luminescence and scintillation properties were investigated. In this nanocomposite scintillator system, the incorporation of high atomic number Gd compound into the glass matrix increases the X-ray stopping power of the glass scintillator, and effective energy transfer between Gd3+ and Tb3+ ions in the nanocrystals enhances the scintillation efficiency. PMID:24610960

Development of Nanocrystalline Zeolite Materials for the Decontamination of Chemical Warfare Agents

DTIC Science & Technology

2008-11-17

phosphite (CH3O)2P(O)H or DMP. There is -40-20020406080100 In te ns ity ppm a) b) c) d) * ** ** ** * * 33 37 1225 9 Figure 6. 31P MAS NMR spectra...The main objective of this research is to use novel nanocrystalline zeolite materials synthesized in our laboratories for the decontamination of...nanocrystalline zeolite materials. In these studies, we have focused our attention on the decontamination of 2-CEES and DMMP, two simulants for mustard gas

Grain growth behavior at absolute zero during nanocrystalline metal indentation

NASA Astrophysics Data System (ADS)

Sansoz, F.; Dupont, V.

2006-09-01

The authors show using atomistic simulations that stress-driven grain growth can be obtained in the athermal limit during nanocrystalline aluminum indentation. They find that the grain growth results from rotation of nanograins and propagation of shear bands. Together, these mechanisms are shown to lead to the unstable migration of grain boundaries via process of coupled motion. An analytical model is used to explain this behavior based on the atomic-level shear stress acting on the interfaces during the shear band propagation. This study sheds light on the atomic mechanism at play during the abnormal grain coarsening observed at low temperature in nanocrystalline metals.

Nucleophilic addition of amines to ruthenium carbenes: ortho-(alkynyloxy)benzylamine cyclizations towards 1,3-benzoxazines.

PubMed

González-Rodríguez, Carlos; Suárez, José Ramón; Varela, Jesús A; Saá, Carlos

2015-02-23

A new ruthenium-catalyzed cyclization of ortho-(alkynyloxy)benzylamines to dihydro-1,3-benzoxazines is reported. The cyclization is thought to take place via the vinyl ruthenium carbene intermediates which are easily formed from [Cp*RuCl(cod)] and N2 CHSiMe3 . The mild reaction conditions and the efficiency of the procedure allow the easy preparation of a broad range of new 2-vinyl-2-substituted 1,3-benzoxazine derivatives. Rearrangement of an internal C(sp) in the starting material into a tetrasubstituted C(sp(3) ) atom in the final 1,3-benzoxazine is highly remarkable. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanocrystalline sp{sup 2} and sp{sup 3} carbons: CVD synthesis and applications

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

Terranova, M. L.; Rossi, M.; Tamburri, E., E-mail: emanuela.tamburri@uniroma2.it

The design and production of innovative materials based on nanocrystalline sp{sup 2}- and sp{sup 3}-coordinated carbons is presently a focus of the scientific community. We present a review of the nanostructures obtained in our labs using a series of synthetic routes, which make use of chemical vapor deposition (CVD) techniques for the selective production of non-planar graphitic nanostructures, nanocrystalline diamonds, and hybrid two-phase nanostructures.

Fabrication of GaN doped ZnO nanocrystallines by laser ablation.

PubMed

Gopalakrishnan, N; Shin, B C; Bhuvana, K P; Elanchezhiyan, J; Balasubramanian, T

2008-08-01

Here, we present the fabrication of pure and GaN doped ZnO nanocrystallines on Si(111) substrates by KrF excimer laser. The targets for the ablation have been prepared by conventional ceramic method. The fabricated nanocrystallines have been investigated by X-ray diffraction, photoluminescence and atomic force microscopy. The X-ray diffraction analysis shows that the crystalline size of pure ZnO is 36 nm and it is 41 nm while doped with 0.8 mol% of GaN due to best stoichiometry between Zn and O. Photoluminescence studies reveal that intense deep level emissions have been observed for pure ZnO and it has been suppressed for the GaN doped ZnO structures. The images of atomic force microscope show that the rms surface roughness is 27 nm for pure ZnO and the morphology is improved with decrease in rms roughness, 18 nm with fine crystallines while doped with 1 mol% GaN. The improved structural, optical and morphological properties of ZnO nanocrystalline due to GaN dopant have been discussed in detail.

Application of ASTAR(TM)/Precession Electron Diffraction Technique to Quantitatively Study Defects in Nanocrystalline Metallic Materials

NASA Astrophysics Data System (ADS)

Ghamarian, Iman

Nanocrystalline metallic materials have the potential to exhibit outstanding performance which leads to their usage in challenging applications such as coatings and biomedical implant devices. To optimize the performance of nanocrystalline metallic materials according to the desired applications, it is important to have a decent understanding of the structure, processing and properties of these materials. Various efforts have been made to correlate microstructure and properties of nanocrystalline metallic materials. Based on these research activities, it is noticed that microstructure and defects (e.g., dislocations and grain boundaries) play a key role in the behavior of these materials. Therefore, it is of great importance to establish methods to quantitatively study microstructures, defects and their interactions in nanocrystalline metallic materials. Since the mechanisms controlling the properties of nanocrystalline metallic materials occur at a very small length scale, it is fairly difficult to study them. Unfortunately, most of the characterization techniques used to explore these materials do not have the high enough spatial resolution required for the characterization of these materials. For instance, by applying complex profile-fitting algorithms to X-ray diffraction patterns, it is possible to get an estimation of the average grain size and the average dislocation density within a relatively large area. However, these average values are not enough for developing meticulous phenomenological models which are able to correlate microstructure and properties of nanocrystalline metallic materials. As another example, electron backscatter diffraction technique also cannot be used widely in the characterization of these materials due to problems such as relative poor spatial resolution (which is 90 nm) and the degradation of Kikuchi diffraction patterns in severely deformed nano-size grain metallic materials. In this study, ASTAR(TM)/precession electron

Stability of nanocrystalline Ni-based alloys: coupling Monte Carlo and molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Waseda, O.; Goldenstein, H.; Silva, G. F. B. Lenz e.; Neiva, A.; Chantrenne, P.; Morthomas, J.; Perez, M.; Becquart, C. S.; Veiga, R. G. A.

2017-10-01

The thermal stability of nanocrystalline Ni due to small additions of Mo or W (up to 1 at%) was investigated in computer simulations by means of a combined Monte Carlo (MC)/molecular dynamics (MD) two-steps approach. In the first step, energy-biased on-lattice MC revealed segregation of the alloying elements to grain boundaries. However, the condition for the thermodynamic stability of these nanocrystalline Ni alloys (zero grain boundary energy) was not fulfilled. Subsequently, MD simulations were carried out for up to 0.5 μs at 1000 K. At this temperature, grain growth was hindered for minimum global concentrations of 0.5 at% W and 0.7 at% Mo, thus preserving most of the nanocrystalline structure. This is in clear contrast to a pure Ni model system, for which the transformation into a monocrystal was observed in MD simulations within 0.2 μs at the same temperature. These results suggest that grain boundary segregation of low-soluble alloying elements in low-alloyed systems can produce high-temperature metastable nanocrystalline materials. MD simulations carried out at 1200 K for 1 at% Mo/W showed significant grain boundary migration accompanied by some degree of solute diffusion, thus providing additional evidence that solute drag mostly contributed to the nanostructure stability observed at lower temperature.

Surface reactions kinetics between nanocrystalline magnetite and uranyl.

PubMed

Missana, Tiziana; Maffiotte, César; García-Gutiérrez, Miguel

2003-05-01

Magnetite is the most important end member of iron corrosion products under reducing environment, which is the condition expected in a deep geological high level radioactive waste disposal. Nanocrystalline magnetite was synthesized in the laboratory and its physicochemical properties were analyzed in detail. The kinetics of the adsorption of U(VI) and the kinetics of the actinide reduction to a lower oxidation state, in presence of the oxide, were studied by means of batch sorption techniques and X-ray photoelectron spectroscopy (XPS) analysis. The results showed that the uranium sorption and reduction processes on the magnetite surface have very fast kinetics (hours), the reduction process being triggered by sorption. XPS measurements showed that the speciation of uranium at the surface does not show significant changes with time (from 1 day to 3 months), as well as the quantity of uranium detected at the surface. The surface speciation depended on the initial pH of the contact solution. Considering that the Eh of equilibrium between magnetite and the solution, under our experimental conditions, is slightly positive (50-100 mV), the uranium reduction would also be thermodynamically possible within the liquid phase. However, the kinetics of reduction in the liquid occur at a much slower rate which, in turn, has to depend on the attainment of the magnetite/solution equilibrium. The decrease of uranium in solution, observed after the uranyl adsorption stage, and particularly at acidic pH, is most probably due to the precipitation of U(IV) formed in the solution.

FAST TRACK COMMUNICATION: Nanocrystalline silicon film growth morphology control through RF waveform tailoring

NASA Astrophysics Data System (ADS)

Johnson, Erik V.; Verbeke, Thomas; Vanel, Jean-Charles; Booth, Jean-Paul

2010-10-01

We demonstrate the application of RF waveform tailoring to generate an electrical asymmetry in a capacitively coupled plasma-enhanced chemical vapour deposition system, and its use to control the growth mode of hydrogenated amorphous and nanocrystalline silicon thin films deposited at low temperature (150 °C). A dramatic shift in the dc bias potential at the powered electrode is observed when simply inverting the voltage waveform from 'peaks' to 'troughs', indicating an asymmetric distribution of the sheath voltage. By enhancing or suppressing the ion bombardment energy at the substrate (situated on the grounded electrode), the growth of thin silicon films can be switched between amorphous and nanocrystalline modes, as observed using in situ spectroscopic ellipsometry. The effect is observed at pressures sufficiently low that the collisional reduction in average ion bombardment energy is not sufficient to allow nanocrystalline growth (<100 mTorr).

Electrochemical detection of uric acid using ruthenium-dioxide-coated carbon nanotube directly grown onto Si wafer

NASA Astrophysics Data System (ADS)

Shih, Yi-Ting; Lee, Kuei-Yi; Lin, Chung-Kuang

2015-12-01

Carbon nanotubes (CNTs) directly grown onto a Si substrate by thermal chemical vapor deposition were used in uric acid (UA) detection. The process is simple and formation is easy without the need for additional chemical treatments. However, CNTs lack selectivity and sensitivity to UA. To enhance the electrochemical analysis, ruthenium oxide was used as a catalytic mediator in the modification of electrodes. The electrochemical results show that RuO2 nanostructures coated onto CNTs can strengthen the UA signal. The peak currents of RuO2 nanostructures coated onto CNTs linearly increase with increasing UA concentration, meaning that they can work as electrodes for UA detection. The lowest detection limit and highest sensitivity were 55 nM and 4.36 µA/µM, respectively. Moreover, the characteristics of RuO2 nanostructures coated onto CNTs were examined by scanning electron microscopy, transmission electron microscopy, and Raman spectroscopy.

Stacking fault energies and slip in nanocrystalline metals.

PubMed

Van Swygenhoven, H; Derlet, P M; Frøseth, A G

2004-06-01

The search for deformation mechanisms in nanocrystalline metals has profited from the use of molecular dynamics calculations. These simulations have revealed two possible mechanisms; grain boundary accommodation, and intragranular slip involving dislocation emission and absorption at grain boundaries. But the precise nature of the slip mechanism is the subject of considerable debate, and the limitations of the simulation technique need to be taken into consideration. Here we show, using molecular dynamics simulations, that the nature of slip in nanocrystalline metals cannot be described in terms of the absolute value of the stacking fault energy-a correct interpretation requires the generalized stacking fault energy curve, involving both stable and unstable stacking fault energies. The molecular dynamics technique does not at present allow for the determination of rate-limiting processes, so the use of our calculations in the interpretation of experiments has to be undertaken with care.

Direct electron-transfer conduits constructed at the interface between multicopper oxidase and nanocrystalline semiconductive Fe oxides

NASA Astrophysics Data System (ADS)

Nakamura, Ryuhei; Kamiya, Kazuhide; Hashimoto, Kazuhito

2010-10-01

Herein, the electron-transfer reactions occurring at the interface between bilirubin oxidase (BOD) and nanocrystalline hematite (α-Fe 2O 3) were characterized. Cyclic voltammograms indicated that BOD has an affinity for hematite surfaces and establishes a direct electron-transfer (DET) conduit between the primary electron acceptor T1 site and the conduction band of α-Fe 2O 3. DET was also confirmed photo-electrochemically, as cathodic photocurrents were generated when a nanocomposite of BOD and α-Fe 2O 3 was illuminated under oxygenated conditions. A proline residue displayed a high-binding affinity for hematite surfaces and is therefore likely part of an orientation-controlled motif which serves to locate BOD at the T1 site at a suitable distance for DET to α-Fe 2O 3.

Cytotoxic hydrogen bridged ruthenium quinaldamide complexes showing induced cancer cell death by apoptosis.

PubMed

Lord, Rianne M; Allison, Simon J; Rafferty, Karen; Ghandhi, Laura; Pask, Christopher M; McGowan, Patrick C

2016-08-16

This report presents the first known p-cymene ruthenium quinaldamide complexes which are stabilised by a hydrogen-bridging atom, [{(p-cym)Ru(II)X(N,N)}{H(+)}{(N,N)XRu(II)(p-cym)}][PF6] (N,N = functionalised quinaldamide and X = Cl or Br). These complexes are formed by a reaction of [p-cymRu(μ-X)2]2 with a functionalised quinaldamide ligand. When filtered over NH4PF6, and under aerobic conditions the equilibrium of NH4PF6 ⇔ NH3 + HPF6 enables incorporation of HPF6 and the stabilisation of two monomeric ruthenium complexes by a bridging H(+), which are counter-balanced by a PF6 counterion. X-ray crystallographic analysis is presented for six new structures with OO distances of 2.420(4)-2.448(15) Å, which is significant for strong hydrogen bonds. Chemosensitivity studies against HCT116, A2780 and cisplatin-resistant A2780cis human cancer cells showed the ruthenium complexes with a bromide ancillary ligand to be more potent than those with a chloride ligand. The 4'-fluoro compounds show a reduction in potency for both chloride and bromide complexes against all cell lines, but an increase in selectivity towards cancer cells compared to non-cancer ARPE-19 cells, with a selectivity index >1. Mechanistic studies showed a clear correlation between IC50 values and induction of cell death by apoptosis.

Chemiluminescence reactions with cationic, neutral, and anionic ruthenium(II) complexes containing 2,2'-bipyridine and bathophenanthroline disulfonate ligands.

PubMed

Francis, Paul S; Papettas, Dimitra; Zammit, Elizabeth M; Barnett, Neil W

2010-07-15

Ruthenium complexes containing 4,7-diphenyl-1,10-phenanthroline disulfonate (bathophenanthroline disulfonate; BPS) ligands, Ru(BPS)(3)(4-), Ru(BPS)(2)(bipy)(2-) and Ru(BPS)(bipy)(2), were compared to tris(2,2'-bipyridine)ruthenium(II) (Ru(bipy)(3)(2+)), including examination of the wavelengths of maximum absorption and corrected emission intensity, photoluminescence quantum yield, stability of their oxidised ruthenium(III) form, and relative chemiluminescence intensities and signal-to-blank ratios with cerium(IV) sulfate and six analytes (codeine, morphine cocaine, potassium oxalate, furosemide and hydrochlorothiazide) in acidic aqueous solution. The presence of BPS ligands in the complex increased the photoluminescence quantum yield, but decreased the stability of the oxidised form of the reagent. In contrast to previous evidence showing much greater electrochemiluminescence intensities using Ru(BPS)(2)(bipy)(2-) and Ru(BPS)(bipy)(2), these complexes did not provide superior chemiluminescence signals than their homoleptic analogues. Copyright 2010 Elsevier B.V. All rights reserved.

Deformation-induced localized solid-state amorphization in nanocrystalline nickel.

PubMed

Han, Shuang; Zhao, Lei; Jiang, Qing; Lian, Jianshe

2012-01-01

Although amorphous structures have been widely obtained in various multi-component metallic alloys, amorphization in pure metals has seldom been observed and remains a long-standing scientific curiosity and technological interest. Here we present experimental evidence of localized solid-state amorphization in bulk nanocrystalline nickel introduced by quasi-static compression at room temperature. High-resolution electron microscope observations illustrate that nano-scale amorphous structures present at the regions where severe deformation occurred, e.g. along crack paths or surrounding nano-voids. These findings have indicated that nanocrystalline structures are highly desirable for promoting solid-state amorphization, which may provide new insights for understanding the nature of the crystalline-to-amorphous transformation and suggested a potential method to produce elemental metallic glasses that have hardly been available hitherto through rapid solidification.

Deformation-induced localized solid-state amorphization in nanocrystalline nickel

PubMed Central

Han, Shuang; Zhao, Lei; Jiang, Qing; Lian, Jianshe

2012-01-01

Although amorphous structures have been widely obtained in various multi-component metallic alloys, amorphization in pure metals has seldom been observed and remains a long-standing scientific curiosity and technological interest. Here we present experimental evidence of localized solid-state amorphization in bulk nanocrystalline nickel introduced by quasi-static compression at room temperature. High-resolution electron microscope observations illustrate that nano-scale amorphous structures present at the regions where severe deformation occurred, e.g. along crack paths or surrounding nano-voids. These findings have indicated that nanocrystalline structures are highly desirable for promoting solid-state amorphization, which may provide new insights for understanding the nature of the crystalline-to-amorphous transformation and suggested a potential method to produce elemental metallic glasses that have hardly been available hitherto through rapid solidification. PMID:22768383

Grain boundary and triple junction diffusion in nanocrystalline copper

NASA Astrophysics Data System (ADS)

Wegner, M.; Leuthold, J.; Peterlechner, M.; Song, X.; Divinski, S. V.; Wilde, G.

2014-09-01

Grain boundary and triple junction diffusion in nanocrystalline Cu samples with grain sizes, , of ˜35 and ˜44 nm produced by spark plasma sintering were investigated by the radiotracer method using the 63Ni isotope. The measured diffusivities, Deff, are comparable with those determined previously for Ni grain boundary diffusion in well-annealed, high purity, coarse grained, polycrystalline copper, substantiating the absence of a grain size effect on the kinetic properties of grain boundaries in a nanocrystalline material at grain sizes d ≥ 35 nm. Simultaneously, the analysis predicts that if triple junction diffusion of Ni in Cu is enhanced with respect to the corresponding grain boundary diffusion rate, it is still less than 500ṡDgb within the temperature interval from 420 K to 470 K.

Multiphase Nanocrystalline Ceramic Concept for Nuclear Fuel

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

Mecartnery, Martha; Graeve, Olivia; Patel, Maulik

2017-05-25

The goal of this research is to help develop new fuels for higher efficiency, longer lifetimes (higher burn-up) and increased accident tolerance in future nuclear reactors. Multiphase nanocrystalline ceramics will be used in the design of simulated advanced inert matrix nuclear fuel to provide for enhanced plasticity, better radiation tolerance, and improved thermal conductivity

Chemical and Photochemical Water Oxidation Mediated by an Efficient Single-Site Ruthenium Catalyst.

PubMed

Abdel-Magied, Ahmed F; Shatskiy, Andrey; Liao, Rong-Zhen; Laine, Tanja M; Arafa, Wael A A; Siegbahn, Per E M; Kärkäs, Markus D; Åkermark, Björn; Johnston, Eric V

2016-12-20

Water oxidation is a fundamental step in artificial photosynthesis for solar fuels production. In this study, we report a single-site Ru-based water oxidation catalyst, housing a dicarboxylate-benzimidazole ligand, that mediates both chemical and light-driven oxidation of water efficiently under neutral conditions. The importance of the incorporation of the negatively charged ligand framework is manifested in the low redox potentials of the developed complex, which allows water oxidation to be driven by the mild one-electron oxidant [Ru(bpy) 3 ] 3+ (bpy=2,2'-bipyridine). Furthermore, combined experimental and DFT studies provide insight into the mechanistic details of the catalytic cycle. © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Formation of vinyl halides via a ruthenium-catalyzed three-component coupling.

PubMed

Trost, Barry M; Pinkerton, Anthony B

2002-06-26

The ruthenium-catalyzed three-component coupling of an alkyne, an enone, and halide ion to form E- or Z-vinyl halides has been investigated. Through systematic optimization experiments, the conditions effecting the olefin selectivity were examined. In general, more polar solvents such as DMF favored the formation of the E-isomer, and less polar solvents such as acetone favored formation of the Z-isomer. The optimized conditions for the formation of E-vinyl chlorides were found to be the use of cyclopentadienyl ruthenium (II) cyclooctadiene chloride, stannic chloride pentahydrate as a cocatalyst, and for a chloride source, either ammonium chloride in DMF/water mixtures or tetramethylammonium chloride in DMF. A range of several other ruthenium (II) catalysts was also shown to be effective. A wide variety of vinyl chlorides could be formed under these conditions. Substrates with tethered alcohols or ketones either five or six carbons from the alkyne portion gave instead diketone or cyclohexenone products. For formation of vinyl bromides, a catalyst system involving the use of cyclopentadienylruthenium (II) tris(acetonitrile) hexafluorophosphate with stannic bromide as a cocatalyst was found to be most effective. The use of ammonium bromide in DMF/acetone mixtures was optimal for the synthesis of E-vinyl bromides, and the use of lithium bromide in acetone was optimal for formation of the corresponding Z-isomer. Under either set of conditions, a wide range of vinyl bromides could be formed. When alkynes with propargylic substituents are used, enhanced selectivity for formation of the Z-isomer is observed. When aryl acetylenes are used as the coupling partners, complete selectivity for the Z-isomer is obtained. A mechanism involving a cis or trans halometalation is invoked to explain formation of the observed products. The vinyl halides have been shown to be precursors to alpha-hydroxy ketones and cyclopentenones, and as coupling partners in Suzuki-type reactions.

SORPTION OF LEAD ON A RUTHENIUM COMPOUND: A MACROSCOPIC AND MICROSCOPIC STUDY

EPA Science Inventory

The objective of this study was to elucidate the sorption mechanism of Pb on the high-affinity ruthenium compound with time at pH 6 employing batch methods and X-ray absorption fine structure (XAFS) and X-ray diffraction (XRD) spectroscopies. For the spectroscopic studies, Pb so...

SEPARATION OF URANYL AND RUTHENIUM VALUES BY THE TRIBUTYL PHOSPHATE EXTRACTION PROCESS

DOEpatents

Wilson, A.S.

1961-05-01

A process is given for separating uranyl values from ruthenium values contained in an aqueous 3 to 4 M nitric acid solution. After the addition of hydrogen peroxide to obtain a concentration of 0.3 M, the uranium is selectively extracted with kerosene-diluted tributyl phosphate.

Anti-inflammatory activity of nanocrystalline silver-derived solutions in porcine contact dermatitis

PubMed Central

2010-01-01

Background Nanocrystalline silver dressings have anti-inflammatory activity, unlike solutions containing Ag+ only, which may be due to dissolution of multiple silver species. These dressings can only be used to treat surfaces. Thus, silver-containing solutions with nanocrystalline silver properties could be valuable for treating hard-to-dress surfaces and inflammatory conditions of the lungs and bowels. This study tested nanocrystalline silver-derived solutions for anti-inflammatory activity. Methods Inflammation was induced on porcine backs using dinitrochlorobenzene. Negative and positive controls were treated with distilled water. Experimental groups were treated with solutions generated by dissolving nanocrystalline silver in distilled water adjusted to starting pHs of 4 (using CO2), 5.6 (as is), 7, and 9 (using Ca(OH)2). Solution samples were analyzed for total silver. Daily imaging, biopsying, erythema and oedema scoring, and treatments were performed for three days. Biopsies were processed for histology, immunohistochemistry (for IL-4, IL-8, IL-10, TNF-α, EGF, KGF, KGF-2, and apoptotic cells), and zymography (MMP-2 and -9). One-way ANOVAs with Tukey-Kramer post tests were used for statistical analyses. Results Animals treated with pH 7 and 9 solutions showed clear visual improvements. pH 9 solutions resulted in the most significant reductions in erythema and oedema scores. pH 4 and 7 solutions also reduced oedema scores. Histologically, all treatment groups demonstrated enhanced re-epithelialisation, with decreased inflammation. At 24 h, pMMP-2 expression was significantly lowered with pH 5.6 and 9 treatments, as was aMMP-2 expression with pH 9 treatments. In general, treatment with silver-containing solutions resulted in decreased TNF-α and IL-8 expression, with increased IL-4, EGF, KGF, and KGF-2 expression. At 24 h, apoptotic cells were detected mostly in the dermis with pH 4 and 9 treatments, nowhere with pH 5.6, and in both the epidermis and dermis

Effect of FA/O complexing agents and H2O2 on chemical mechanical polishing of ruthenium in weakly alkaline slurry

NASA Astrophysics Data System (ADS)

Bo, Duan; Weijing, An; Jianwei, Zhou; Shuai, Wang

2015-07-01

This paper investigated the effect of FA/O and hydrogen peroxide (H2O2) on ruthenium (Ru) removal rate (RR) and static etching rate (SER). It was revealed that Ru RR and SER first linearly increased then slowly decreaseed with the increasing H2O2 probably due to the formation of uniform Ru oxides on the surface during polishing. Their corrosion behaviors and states of surface oxidation were analyzed. In addition, FA/O could chelate Ru oxides (such as (RuO4)2- and RuO4- changed into soluble amine salts [R(NH3)4] (RuO4)2) and enhance Ru RR. The non-ionic surfactant AD was used to improve the Ru CMP performance. In particular, the addition of AD can lead to significant improvement of the surface roughness. Project supported by the Special Project Items No. 2 in National Long-Term Technology Development Plan (No. 2009ZX02308), the Natural Science Foundation of Hebei Province (No. E2013202247), the Science and Technology Plan Project of Hebei Province (Nos. Z2010112, 10213936), the Hebei Provincial Department of Education Fund (No. 2011128), and the Scientific Research Fund of Hebei Provincial Education (No. QN2014208).

Three-dimensional ruthenium-doped TiO 2 sea urchins for enhanced visible-light-responsive H 2 production

DOE PAGES

Nguyen-Phan, Thuy -Duong; Luo, Si; Vovchok, Dimitriy; ...

2016-05-23

Here, three-dimensional (3D) monodispersed sea urchin-like Ru-doped rutile TiO 2 hierarchical architectures composed of radially aligned, densely-packed TiO 2 nanorods have been successfully synthesized via an acid-hydrothermal method at low temperature without the assistance of any structure-directing agent and post annealing treatment. The addition of a minuscule concentration of ruthenium dopants remarkably catalyzes the formation of the 3D urchin structure and drives the enhanced photocatalytic H 2 production under visible light irradiation, not possible on undoped and bulk rutile TiO 2. Increasing ruthenium doping dosage not only increases the surface area up to 166 m 2 g –1 but alsomore » induces enhanced photoresponse in the regime of visible and near infrared light. The doping introduces defect impurity levels, i.e. oxygen vacancy and under-coordinated Ti 3+, significantly below the conduction band of TiO 2, and ruthenium species act as electron donors/acceptors that accelerate the photogenerated hole and electron transfer and efficiently suppress the rapid charge recombination, therefore improving the visible-light-driven activity.« less

A general higher-order nonlocal couple stress based beam model for vibration analysis of porous nanocrystalline nanobeams

NASA Astrophysics Data System (ADS)

Ebrahimi, Farzad; Barati, Mohammad Reza

2017-12-01

This paper develops a higher order refined beam model with a parabolic shear strain function for vibration analysis of porous nanocrystalline nanobeams based on nonlocal couple stress theory. Nanocrystalline nanobeam is composed from three phases which are nano-grains, nano-voids and interface. Nano-voids or porosities inside the material have a stiffness-softening impact on the nanobeam. Nonlocal elasticity theory of Eringen is applied in analysis of nanocrystalline nanobeams for the first time. Also, modified couple stress theory is employed to capture grains rigid rotations. The governing equations obtained from Hamilton's principle are solved applying an analytical approach which satisfies various boundary conditions. The reliability of present approach is verified by comparing obtained results with those provided in literature. Finally the influences of nonlocal parameter, couple stress, grain size, porosities and shear deformation on the vibration characteristics of nanocrystalline nanobeams are explored.

Determination of ruthenium in pharmaceutical compounds by graphite furnace atomic absorption spectroscopy.

PubMed

Jia, Xiujuan; Wang, Tiebang; Bu, Xiaodong; Tu, Qiang; Spencer, Sandra

2006-04-11

A graphite furnace atomic absorption (GFAA) spectrometric method for the determination of ruthenium (Rh) in solid and liquid pharmaceutical compounds has been developed. Samples are dissolved or diluted in dimethyl sulfoxide (DMSO) without any other treatment before they were analyzed by GFAA with a carefully designed heating program to avoid pre-atomization signal loss and to achieve suitable sensitivity. Various inorganic and organic solvents were tested and compared and DMSO was found to be the most suitable. In addition, ruthenium was found to be stable in DMSO for at least 5 days. Spike recoveries ranged from 81 to 100% and the limit of quantitation (LOQ) was determined to be 0.5 microg g(-1) for solid samples or 0.005 microg ml(-1) for liquid samples based a 100-fold dilution. The same set of samples was also analyzed by ICP-MS with a different sample preparation method, and excellent agreement was achieved.

Enhancement of green electroluminescence from nanocrystalline silicon by wet and dry processes.

PubMed

Sato, Keisuke; Hirakuri, Kenji

2006-01-01

Correlation between defects and luminescence property from electroluminescent (EL) device composed of nanocrystalline silicon (nc-Si) prepared by wet and dry processes such as hydrofluoric (HF) acid solution treatment and annealing have investigated using electron spin resonance and EL measurements. The EL device using HF-treated nc-Si emitted strong red light, because of existence of only P'ce-centers (radiative recombination centers) on the surface vicinity. On the other hand, the EL device using annealed nc-Si above 400 degrees C exhibited green luminescence by the reduction of particle size due to surface oxidation. When the annealing temperature was risen from 400 degrees C up to 600 degrees C, the green luminescence strengthened with increasing the P'ce-centers. These results indicate that the formation of many radiative recombination centers onto the nc-Si surface vicinity lead to the enhancement of green luminescence from the nc-Si based EL device.

Functional materials based on nanocrystalline cellulose

NASA Astrophysics Data System (ADS)

Surov, O. V.; Voronova, M. I.; Zakharov, A. G.

2017-10-01

The data on the synthesis of functional materials based on nanocrystalline cellulose (NCC) published over the past 10 years are analyzed. The liquid-crystal properties of NCC suspensions, methods of investigation of NCC suspensions and films, conditions for preserving chiral nematic structure in the NCC films after removal of the solvent and features of templated sol-gel synthesis of functional materials based on NCC are considered. The bibliography includes 106 references.

Ruthenium films by digital chemical vapor deposition: Selectivity, nanostructure, and work function

NASA Astrophysics Data System (ADS)

Dey, Sandwip K.; Goswami, Jaydeb; Gu, Diefeng; de Waard, Henk; Marcus, Steve; Werkhoven, Chris

2004-03-01

Ruthenium electrodes were selectively deposited on photoresist-patterned HfO2 surface [deposited on a SiOx/Si wafer by atomic layer deposition (ALD)] by a manufacturable, digital chemical vapor deposition (DCVD) technique. DCVD of Ru was carried out at 280-320 °C using an alternate delivery of Bis (2,2,6,6-tetramethyl-3,5-heptanedionato)(1,5-cyclooctadiene)Ru (dissolved in tetrahydrofuran) and oxygen. The as-deposited Ru films were polycrystalline, dense, and conducting (resistivity ˜20.6 μΩ cm). However, Rutherford backscattering spectroscopy, x-ray photoelectron spectroscopy, and high-resolution electron microscopy results indicate the presence of an amorphous RuOx at the Ru grain boundaries and at the DCVD-Ru/ALD-HfO2 interface. The estimated work function of DCVD-Ru on ALD-HfO2 was ˜5.1 eV. Moreover, the equivalent oxide thickness, hysteresis in capacitance-voltage, and leakage current density at -2 V of the HfO2/SiOx dielectric, after forming gas (95% N2+5% H2) annealing at 450 °C for 30 min, were 1.4 nm, 20 mV, and 7.4×10-7 A cm-2, respectively.

Development of a ruthenium/phosphite catalyst system for domino hydroformylation-reduction of olefins with carbon dioxide.

PubMed

Liu, Qiang; Wu, Lipeng; Fleischer, Ivana; Selent, Detlef; Franke, Robert; Jackstell, Ralf; Beller, Matthias

2014-06-02

An efficient domino ruthenium-catalyzed reverse water-gas-shift (RWGS)-hydroformylation-reduction reaction of olefins to alcohols is reported. Key to success is the use of specific bulky phosphite ligands and triruthenium dodecacarbonyl as the catalyst. Compared to the known ruthenium/chloride system, the new catalyst allows for a more efficient hydrohydroxymethylation of terminal and internal olefins with carbon dioxide at lower temperature. Unwanted hydrogenation of the substrate is prevented. Preliminary mechanism investigations uncovered the homogeneous nature of the active catalyst and the influence of the ligand and additive in individual steps of the reaction sequence. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Investigation of physicochemical and tribological properties of transparent oxide semiconducting thin films based on Ti-V oxides

NASA Astrophysics Data System (ADS)

Mazur, M.; Sieradzka, K.; Kaczmarek, D.; Domaradzki, J.; Wojcieszak, D.; Domanowski, P.

2013-08-01

In this paper investigations of structural and optical properties of nanocrystalline Ti-V oxide thin films are described. The films were deposited onto Corning 7059 glass using a modified reactive magnetron sputtering method. Structural investigations of prepared Ti-V oxides with vanadium addition of 19 at. % revealed amorphous structure, while incorporation of 21 and 23 at. % of vanadium resulted in V2O5 formation with crystallites sizes of 12.7 and 32.4 nm, respectively. All prepared thin films belong to transparent oxide semiconductors due to their high transmission level of ca. 60-75 % in the visible light range, and resistivity in the range of 3.3·102-1.4·105 Ωcm. Additionally, wettability and hardness tests were performed in order to evaluate the usefulness of the films for functional coatings.

Efficient Second-Harmonic Generation in Nanocrystalline Silicon Nanoparticles.

PubMed

Makarov, Sergey V; Petrov, Mihail I; Zywietz, Urs; Milichko, Valentin; Zuev, Dmitry; Lopanitsyna, Natalia; Kuksin, Alexey; Mukhin, Ivan; Zograf, George; Ubyivovk, Evgeniy; Smirnova, Daria A; Starikov, Sergey; Chichkov, Boris N; Kivshar, Yuri S

2017-05-10

Recent trends to employ high-index dielectric particles in nanophotonics are motivated by their reduced dissipative losses and large resonant enhancement of nonlinear effects at the nanoscale. Because silicon is a centrosymmetric material, the studies of nonlinear optical properties of silicon nanoparticles have been targeting primarily the third-harmonic generation effects. Here we demonstrate, both experimentally and theoretically, that resonantly excited nanocrystalline silicon nanoparticles fabricated by an optimized laser printing technique can exhibit strong second-harmonic generation (SHG) effects. We attribute an unexpectedly high yield of the nonlinear conversion to a nanocrystalline structure of nanoparticles supporting the Mie resonances. The demonstrated efficient SHG at green light from a single silicon nanoparticle is 2 orders of magnitude higher than that from unstructured silicon films. This efficiency is significantly higher than that of many plasmonic nanostructures and small silicon nanoparticles in the visible range, and it can be useful for a design of nonlinear nanoantennas and silicon-based integrated light sources.

In Situ FTIR and NMR Spectroscopic Investigations on Ruthenium-Based Catalysts for Alkene Hydroformylation.

PubMed

Kubis, Christoph; Profir, Irina; Fleischer, Ivana; Baumann, Wolfgang; Selent, Detlef; Fischer, Christine; Spannenberg, Anke; Ludwig, Ralf; Hess, Dieter; Franke, Robert; Börner, Armin

2016-02-18

Homogeneous ruthenium complexes modified by imidazole-substituted monophosphines as catalysts for various highly efficient hydroformylation reactions were characterized by in situ IR spectroscopy under reaction conditions and NMR spectroscopy. A proper protocol for the preformation reaction from [Ru3 (CO)12] is decisive to prevent the formation of inactive ligand-modified polynuclear complexes. During catalysis, ligand-modified mononuclear ruthenium(0) carbonyls were detected as resting states. Changes in the ligand structure have a crucial impact on the coordination behavior of the ligand and consequently on the catalytic performance. The substitution of CO by a nitrogen atom of the imidazolyl moiety in the ligand is not a general feature, but it takes place when structural prerequisites of the ligand are fulfilled. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Influence of Weak External Magnetic Field on Amorphous and Nanocrystalline Fe-based Alloys

NASA Astrophysics Data System (ADS)

Degmová, J.; Sitek, J.

2010-07-01

Nanoperm, Hitperm and Finamet amorphous and nanocrystalline alloys were measured by Mössbauer spectrometry in a weak external magnetic field of 0.5 T. It was shown that the most sensitive parameters of Mössbauer spectra are the intensities of the 2nd and the 5th lines. Rather small changes were observed also in the case of internal magnetic field values. The spectrum of nanocrystalline Nanoperm showed the increase in A23 parameter (ratio of line intensities) from 2.4 to 3.7 and decrease of internal magnetic field from 20 to 19 T for amorphous subspectrum under the influence of magnetic field. Spectrum of nanocrystalline Finemet shown decrease in A23 parameter from 3.5 to 2.6 almost without a change in the internal magnetic field value. In the case of amorphous Nanoperm and Finemet samples, the changes are almost negligible. Hitperm alloy showed the highest sensitivity to the weak magnetic field, when the A23 parameter increased from 0.4 to 2.5 in the external magnetic fields. The A23 parameter of crystalline subspectrum increased from 2.7 to 3.8 and the value of internal magnetic field corresponding to amorphous subspectrum increased from 22 to 24 T. The behavior of nanocrystalline alloys under weak external magnetic field was analyzed within the three-level relaxation model of magnetic dynamics in an assembly of single-domain particles.

Remediation of arsenic and lead with nanocrystalline zinc sulfide.

PubMed

Piquette, Alan; Cannon, Cody; Apblett, Allen W

2012-07-27

Nanocrystalline (1.7 ± 0.3 nm) zinc sulfide with a specific surface area up to 360 m(2) g(-1) was prepared from the thermal decomposition of a single-source precursor, zinc ethylxanthate. Zinc ethylxanthate decomposes to cubic zinc sulfide upon exposure to temperatures greater than or equal to 125 °C. The resulting zinc sulfide was tested as a water impurity extractant. The target impurities used in this study were As(5+), As(3+), and Pb(2+). The reaction of the nanocrystalline ZnS with Pb(2+) proceeds as a replacement reaction where solid PbS is formed and Zn(2+) is released into the aqueous system. Removal of lead to a level of less than two parts per billion is achievable. The results of a detailed kinetics experiment between the ZnS and Pb(2+) are included in this study. Unlike the instance of lead, both As(5+) and As(3+) adsorb on the surface of the ZnS extractant as opposed to an ion-exchange process. An uptake capacity of > 25 mg g(-1) for the removal of As(5+) is possible. The uptake of As(3+) appears to proceed by a slower process than that of the As(5+) with a capacity of nearly 20 mg g(-1). The nanocrystalline zinc sulfide was extremely successful for the removal of arsenic and lead from simulated oil sand tailing pond water.

Solid state amorphization of nanocrystalline nickel by cryogenic laser shock peening

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

Ye, Chang, E-mail: cye@uakron.edu; Ren, Zhencheng; Zhao, Jingyi

2015-10-07

In this study, complete solid state amorphization in nanocrystalline nickel has been achieved through cryogenic laser shock peening (CLSP). High resolution transmission electron microscopy has revealed the complete amorphous structure of the sample after CLSP processing. A molecular dynamic model has been used to investigate material behavior during the shock loading and the effects of nanoscale grain boundaries on the amorphization process. It has been found that the initial nanoscale grain boundaries increase the initial Gibbs free energy before plastic deformation and also serve as dislocation emission sources during plastic deformation to contribute to defect density increase, leading to themore » amorphization of pure nanocrystalline nickel.« less

Structure and mechanical properties of foils made of nanocrystalline beryllium

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

Zhigalina, O. M., E-mail: zhigal@ns.crys.ras.ru; Semenov, A. A.; Zabrodin, A. V.

2016-07-15

The phase composition and structural features of (45–90)-μm-thick foils obtained from nanocrystalline beryllium during multistep thermomechanical treatment have been established using electron microscopy, electron diffraction, electron backscattering diffraction, and energy-dispersive analysis. This treatment is shown to lead to the formation of a structure with micrometer- and submicrometer-sized grains. The minimum average size of beryllium grains is 352 nm. The inclusions of beryllium oxide (BeO) of different modifications with tetragonal (sp. gr. P4{sub 2}/mnm) and hexagonal (sp. gr. P6{sub 3}/mmc) lattices are partly ground during deformation to a size smaller than 100 nm and are located along beryllium grain boundaries inmore » their volume, significantly hindering migration during treatment. The revealed structural features of foils with submicrometer-sized crystallites provide the thermal stability of their structural state. Beryllium with this structure is a promising material for X-ray instrument engineering and for the production of ultrathin (less than 10 μm) vacuum-dense foils with very high physicomechanical characteristics.« less

Grain boundary character distribution in nanocrystalline metals produced by different processing routes

DOE PAGES

Bober, David B.; Kumar, Mukal; Rupert, Timothy J.; ...

2015-12-28

Nanocrystalline materials are defined by their fine grain size, but details of the grain boundary character distribution should also be important. Grain boundary character distributions are reported for ball-milled, sputter-deposited, and electrodeposited Ni and Ni-based alloys, all with average grain sizes of ~20 nm, to study the influence of processing route. The two deposited materials had nearly identical grain boundary character distributions, both marked by a Σ3 length percentage of 23 to 25 pct. In contrast, the ball-milled material had only 3 pct Σ3-type grain boundaries and a large fraction of low-angle boundaries (16 pct), with the remainder being predominantlymore » random high angle (73 pct). Furthermore, these grain boundary character measurements are connected to the physical events that control their respective processing routes. Consequences for material properties are also discussed with a focus on nanocrystalline corrosion. As a whole, the results presented here show that grain boundary character distribution, which has often been overlooked in nanocrystalline metals, can vary significantly and influence material properties in profound ways.« less

Effects of Bi Addition on the Microstructure and Mechanical Properties of Nanocrystalline Ag Coatings.

PubMed

Wang, Yuxin; Cheng, Guang; Tay, See Leng; Guo, Yunxia; Sun, Xin; Gao, Wei

2017-08-10

In this study we investigated the effects of Bi addition on the microstructure and mechanical properties of an electrodeposited nanocrystalline Ag coating. Microstructural features were investigated with transmission electron microscopy (TEM). The results indicate that the addition of Bi introduced nanometer-scale Ag-Bi solid solution particles and more internal defects to the initial Ag microstructures. The anisotropic elastic-plastic properties of the Ag nanocrystalline coating with and without Bi addition were examined with nanoindentation experiments in conjunction with the recently-developed inverse method. The results indicate that the as-deposited nanocrystalline Ag coating contained high mechanical anisotropy. With the addition of 1 atomic percent (at%) Bi, the anisotropy within Ag-Bi coating was very small, and yield strength of the nanocrystalline Ag-Bi alloy in both longitudinal and transverse directions were improved by over 100% compared to that of Ag. On the other hand, the strain-hardening exponent of Ag-Bi was reduced to 0.055 from the original 0.16 of the Ag coating. Furthermore, the addition of Bi only slightly increased the electrical resistivity of the Ag-Bi coating in comparison to Ag. Results of our study indicate that Bi addition is a promising method for improving the mechanical and physical performances of Ag coating for electrical contacts.

Platinum Nickel Nanowires as Methanol Oxidation Electrocatalysts

DOE PAGES

Alia, Shaun M.; Pylypenko, Svitlana; Neyerlin, Kenneth C.; ...

2015-08-27

We investigated platinum(Pt) nickel (Ni) nanowires (PtNiNWs) as methanol oxidation reaction (MOR) catalysts in rotating disk electrode (RDE) half-cells under acidic conditions. Pt-ruthenium (Ru) nanoparticles have long been the state of the art MOR catalyst for direct methanol fuel cells (DMFCs) where Ru provides oxophilic sites, lowering the potential for carbon monoxide oxidation and the MOR onset. Ru, however, is a precious metal that has long term durability concerns. Ni/Ni oxide species offer a potential to replace Ru in MOR electrocatalysis. PtNiNWs were investigated for MOR and oxygen annealing was investigated as a route to improve catalyst performance (mass activitymore » 65% greater) and stability to potential cycling. Our results presented show that PtNiNWs offer significant promise in the area, but also result in Ni ion leaching that is a concern requiring further evaluation in fuel cells.« less

Electrogenerated chemiluminescence of tris(2,2'-bipyridine)ruthenium(II) using N-(3-aminopropyl)diethanolamine as coreactant.

PubMed

Kitte, Shimeles Addisu; Wang, Chao; Li, Suping; Zholudov, Yuriy; Qi, Liming; Li, Jianping; Xu, Guobao

2016-10-01

Coreactant plays a critical role for the application of electrochemiluminescence (ECL). Herein, N-(3-aminopropyl)diethanolamine (APDEA) has been explored as a potential coreactant for enhancing tris(2,2'-bipyridyl)ruthenium(II) ECL. It is much more effective than tripropylamine at gold and platinum electrodes although it has one primary amine group besides a tertiary amine group. The presence of primary amine group and hydroxyl groups in APDEA promotes the oxidation rates of amine and thus remarkably increases ECL intensity. The ECL intensities of the Ru(bpy)3 (2+)/APDEA system are approximately 10 and 36 times stronger than that of Ru(bpy)3 (2+)/tripropylamine system and about 1.6 and 1.14 times stronger than that of Ru(bpy)3 (2+)/N-butyldiethanolamine system at Au and Pt electrodes, respectively. The ECL intensity of the Ru(bpy)3 (2+)/APDEA system is 2.42 times stronger than that of Ru(bpy)3 (2+)/N-butyldiethanolamine at glassy carbon electrodes.

Performance comparison of tin oxide anodes to commercially available dimensionally stable anodes.

PubMed

Watts, Richard J; Finn, Dennis D; Wyeth, Megan S; Teel, Amy L

2008-06-01

Dimensionally stable anodes (DSAs) demonstrate potential for the electrochemical treatment of industrial waste streams and disinfection of effluent. Oxidation by laboratory-prepared tin oxide DSAs was compared with that of commercially available ruthenium oxide, iridium oxide, and mixed metal oxide DSAs, using hexanol as a probe molecule. The performance of the four anodes was similar in two-chamber reactors, in which the anode cell was separated from the cathode cell by a Nafion membrane, which allows transmission of current between the chambers, but not passage of chemical constituents. The anodes were then evaluated in single-cell reactors, which are more representative of potential treatment and disinfection applications. However, in the single-cell reactors, the tin oxide anodes were significantly more effective at oxidation and generated higher quality cyclic voltammograms than the other DSAs. These results suggest that tin oxide anodes have greater potential than the three commercially available DSAs tested for industrial waste stream treatment and effluent disinfection.

Comparative study on corrosion resistance and in vitro biocompatibility of bulk nanocrystalline and microcrystalline biomedical 304 stainless steel.

PubMed

Nie, F L; Wang, S G; Wang, Y B; Wei, S C; Zheng, Y F

2011-07-01

SUS 304 stainless steels have been widely used in orthodontics and implants such as archwires, brackets, and screws. The purpose of present study was to investigate the biocompatibility of both the commercial microcrystalline biomedical 304 stainless steel (microcrystalline 304ss) and novel-fabricated nanocrystalline 304 stainless steel (nanocrystalline 304ss). Bulk nanocrystalline 304ss sheets had been successfully prepared by microcrystalline 304ss plates using severe rolling technique. The electrochemical corrosion and ion release behavior immersion in artificial saliva were measured to evaluate the property of biocorrosion in oral environment. The cell lines of murine and human cell lines from oral and endothelial environment were co-cultured with extracts to evaluate the cytotoxicity and provide referential evidence in vivo. The polarization resistance trials indicated that nanocrystalline 304ss is more corrosion resistant than the microcrystalline 304ss in oral-like environment with higher corrosion potential, and the amount of toxic ions released into solution after immersion is lower than that of the microcrystalline 304ss and the daily dietary intake level. The cytotoxicity results also elucidated that nanocrystalline 304ss is biologically compatible in vitro, even better than that of microcrystalline 304ss. Based on the much higher mechanical and physical performances, nanocrystalline 304ss with enhanced biocorrosion property, well-behaved in vitro cytocompatibility can be a promising alternative in orthodontics and fixation fields in oral cavity. Copyright © 2011 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Solution-processed nanocrystalline PbS on paper substrate with pencil traced electrodes as visible photodetector

NASA Astrophysics Data System (ADS)

Vankhade, Dhaval; Chaudhuri, Tapas K.

2018-04-01

Paper-based PbS photodetector sensitive in the visible spectrum is reported. Nanocrystalline PbS-on-paper devices are fabricated by a spin coating method on white paper (300 GSM) from a methanolic precursor solution. Photodetector cells of gap 0.2 cm and length 0.5 cm are prepared by drawing contacts by monolithic cretacolor 8B pencil. X-ray diffractometer confirmed the deposition of nanocrystalline PbS films with 14 nm crystallites. The SEM illustrated the uniform coating of nanocrystalline PbS thin films on cellulose fibres of papers having an average thickness of fibres are 10 µm. The linear J-V characteristics in dark and under illumination of light using graphite trace on nanocrystalline PbS-on-paper shows good ohmic contact. The resistivity of pencil trace is 30 Ω.cm. Spectral response measurements of photodetector reveal the excellent sensitivity from 400 to 700 nm with a peak at 550 nm. The best responsivity anddetectivity are 0.7 A/W and 1.4 × 1012 Jones respectively. These paper-based low-cost photodetectors devices have fast photoresponse and recovery without baseline deviation.

Thermal transport in nanocrystalline Si and SiGe by ab initio based Monte Carlo simulation.

PubMed

Yang, Lina; Minnich, Austin J

2017-03-14

Nanocrystalline thermoelectric materials based on Si have long been of interest because Si is earth-abundant, inexpensive, and non-toxic. However, a poor understanding of phonon grain boundary scattering and its effect on thermal conductivity has impeded efforts to improve the thermoelectric figure of merit. Here, we report an ab-initio based computational study of thermal transport in nanocrystalline Si-based materials using a variance-reduced Monte Carlo method with the full phonon dispersion and intrinsic lifetimes from first-principles as input. By fitting the transmission profile of grain boundaries, we obtain excellent agreement with experimental thermal conductivity of nanocrystalline Si [Wang et al. Nano Letters 11, 2206 (2011)]. Based on these calculations, we examine phonon transport in nanocrystalline SiGe alloys with ab-initio electron-phonon scattering rates. Our calculations show that low energy phonons still transport substantial amounts of heat in these materials, despite scattering by electron-phonon interactions, due to the high transmission of phonons at grain boundaries, and thus improvements in ZT are still possible by disrupting these modes. This work demonstrates the important insights into phonon transport that can be obtained using ab-initio based Monte Carlo simulations in complex nanostructured materials.

Thermal transport in nanocrystalline Si and SiGe by ab initio based Monte Carlo simulation

PubMed Central

Yang, Lina; Minnich, Austin J.

2017-01-01

Nanocrystalline thermoelectric materials based on Si have long been of interest because Si is earth-abundant, inexpensive, and non-toxic. However, a poor understanding of phonon grain boundary scattering and its effect on thermal conductivity has impeded efforts to improve the thermoelectric figure of merit. Here, we report an ab-initio based computational study of thermal transport in nanocrystalline Si-based materials using a variance-reduced Monte Carlo method with the full phonon dispersion and intrinsic lifetimes from first-principles as input. By fitting the transmission profile of grain boundaries, we obtain excellent agreement with experimental thermal conductivity of nanocrystalline Si [Wang et al. Nano Letters 11, 2206 (2011)]. Based on these calculations, we examine phonon transport in nanocrystalline SiGe alloys with ab-initio electron-phonon scattering rates. Our calculations show that low energy phonons still transport substantial amounts of heat in these materials, despite scattering by electron-phonon interactions, due to the high transmission of phonons at grain boundaries, and thus improvements in ZT are still possible by disrupting these modes. This work demonstrates the important insights into phonon transport that can be obtained using ab-initio based Monte Carlo simulations in complex nanostructured materials. PMID:28290484

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.

Nanocrystalline SnO2 formation using energetic ion beam.

PubMed

Mohanty, T; Batra, Y; Tripathi, A; Kanjilal, D

2007-06-01

Nanocrystalline tin oxide (SnO2) thin films grown by RF magnetron sputtering technique were characterized by UV-Visible absorption spectroscopy and Photoluminescence spectroscopy. From atomic force microscopic (AFM) and Glancing angle X-ray diffraction (GAXRD) measurements, the radius of grains was found to be approximately 6+/-2 nm. The thin films were bombarded with 250 keV Xe2+ ion beam to observe the stability of nanophases against radiation. For ion bombarded films, optical absorption band edge is shifted towards red region. Atomic force microscopy studies show that the radius of the grains was increased to approximately 8 +/- 1 nm and the grains were nearly uniform in size. The size of the grains has been reduced after ion bombardment in the case of films grown on Si. During this process, defects such as vacancies, voids were generated in the films as well as in the substrates. Ion bombardment induces local temperature increase of thin films causing melting of films. Ion beam induced defects enhances the diffusion of atoms leading to uniformity in size of grains. The role of matrix on ion beam induced grain growth is discussed.

Development of a direct patterning method for functional oxide thin films using ultraviolet irradiation and hybrid-cluster gels and its application to thin-film transistor fabrication

NASA Astrophysics Data System (ADS)

Yoshimoto, Yuuki; Li, Jinwang; Shimoda, Tatsuya

2018-04-01

A gel state exists in the solution-solid conversion process. We found that solidification can be promoted by irradiating the gel with ultraviolet (UV) light. In this study, a patterning method without using a vacuum system or employing photoresist materials has been proposed wherein solidification was applied to a gel by UV irradiation. Indium oxide gel, indium gallium oxide gel, lanthanum zirconium oxide gel, and lanthanum ruthenium oxide gels were successfully patterned by using our technique. Moreover, an oxide thin-film transistor was fabricated by our novel patterning method and was successfully operated.

High temperature behavior of B2-based ruthenium aluminide systems

NASA Astrophysics Data System (ADS)

Cao, Fang

Ru-modified NiAl-based bond coats have the potential to improve the durability of Superalloy-Thermal Barrier Coating systems (TBCs) for advanced gas turbine engines. A fundamental understanding of the high temperature mechanical behavior across the Ni-Al-Ru B2 phase field can provide direction for the development of these new bond coats for TBCs. The purpose of this study has been to describe the fundamental processes of creep deformation in single phase B2 Ru-Al-Ni ternary alloys which would form the basis for the bond coats. To accomplish this, five ternary alloys with compositions located within the B2 field across the NiAl-RuAl phase region were fabricated and investigated. Special emphasis was placed on characterizing creep deformation and describing the operative creep mechanisms in these alloys. At room temperature, brittle failure was observed in the Ni-rich alloys in compression, while improved strength and ductility were displayed in two Ru-rich ternary alloys at temperatures up to 700°C. Exceptional creep strength was observed in these alloys, as compared to other high melting temperature B2 intermetallics. A continuous increase of the melting temperature and creep resistance with the increasing of the Ru/Ni ratio in these alloys was observed. Post-creep dislocation analyses identified the presence of <100> and <110> edge dislocations in the Ni-rich alloys, while uniformly distributed jogged <100> screw dislocations predominated in the Ru-rich ternary alloys. A transition of the creep mechanism from viscous glide controlled to jogged screw motion in these Ru-Al-Ni ternary B2 alloys with increasing Ru/Ni ratio is demonstrated by the characteristics of the creep deformation process, stress change creep tests, post-creep dislocation analyses, and numerical modeling. Additionally, the knowledge of the cyclic oxidation behavior of ruthenium aluminide-based alloy is essential, as many high-temperature applications for which this intermetallic might be

Properties of nanocrystalline Si layers embedded in structure of solar cell

NASA Astrophysics Data System (ADS)

Jurečka, Stanislav; Imamura, Kentaro; Matsumoto, Taketoshi; Kobayashi, Hikaru

2017-12-01

Suppression of spectral reflectance from the surface of solar cell is necessary for achieving a high energy conversion efficiency. We developed a simple method for forming nanocrystalline layers with ultralow reflectance in a broad range of wavelengths. The method is based on metal assisted etching of the silicon surface. In this work, we prepared Si solar cell structures with embedded nanocrystalline layers. The microstructure of embedded layer depends on the etching conditions. We examined the microstructure of the etched layers by a transmission electron microscope and analysed the experimental images by statistical and Fourier methods. The obtained results provide information on the applied treatment operations and can be used to optimize the solar cell forming procedure.

Solvothermal synthesis of nanocrystalline TiO 2 in toluene with surfactant

NASA Astrophysics Data System (ADS)

Kim, Chung-Sik; Moon, Byung Kee; Park, Jong-Ho; Choi, Byung-Chun; Seo, Hyo-Jin

2003-10-01

Synthesis of narrow-dispersed nanocrystalline TiO 2 was investigated by surfactant-aided solvothermal synthetic method in toluene solutions. Titanium isopropoxide (TIP) was used as precursor, which was decomposed at high temperature in the surfactant-dissolved solution. After the solution was thermally treated at 250°C for 20 h in an autoclave, low-dispersed TiO 2 nanocrystalline particles with average size of <6 nm were synthesized. When sufficient amount of TIP or surfactant was added in the solution, long dumbbell-shaped nanorods were formed, which may be due to the oriented growth of particles along [0 0 1] axis. Characterization of products was investigated by X-ray diffraction and transmission electron microscopy.

Optical and electrical properties of mechanochemically synthesized nanocrystalline delafossite CuAlO2.

PubMed

Prakash, T; Prasad, K Padma; Ramasamy, S; Murty, B S

2008-08-01

Nanocrystalline p-type semiconductor copper aluminum oxide (CuAlO2) has been synthesized by mechanical alloying using freshly prepared Cu2O and alpha-AlO2O3 nanocrystals in toluene medium. A study on structural property performed with different alloying and post annealing durations, by X-ray diffraction (XRD) reveals the formation of single phase with average crystallite size approximately 45 nm. Optical absorbance onset at 364.5 nm confirms its wide band gap nature (E(g) = 3.4 eV) and the fluorescence emission behaviour (390 nm) confirms its direct band type transition. The activation energy for electrical conduction has been calculated by Arrhenius plots using impedance measurement. Both grain and grain boundary conductivity takes place with almost equal activation energies of approximately 0.45 eV. The paper discusses synthesis, structural, optical and electrical properties of delafossite CuAlO2 in detail.

Optical, dielectric and morphological studies of sol-gel derived nanocrystalline TiO2 films.

PubMed

Vishwas, M; Sharma, Sudhir Kumar; Narasimha Rao, K; Mohan, S; Gowda, K V Arjuna; Chakradhar, R P S

2009-10-15

Nanocrystalline TiO(2) films have been synthesized on glass and silicon substrates by sol-gel technique. The films have been characterized with optical reflectance/transmittance in the wavelength range 300-1000 nm and the optical constants (n, k) were estimated by using envelope technique as well as spectroscopic ellipsometry. Morphological studies have been carried out using atomic force microscope (AFM). Metal-Oxide-Silicon (MOS) capacitor was fabricated using conducting coating on TiO(2) film deposited on silicon. The C-V measurements show that the film annealed at 300 degrees C has a dielectric constant of 19.80. The high percentage of transmittance, low surface roughness and high dielectric constant suggests that it can be used as an efficient anti-reflection coating on silicon and other optical coating applications and also as a MOS capacitor.

Method for producing electricity using a platinum-ruthenium-palladium catalyst in a fuel cell

DOEpatents

Gorer, Alexander

2004-01-27

A method for producing electricity using a fuel cell that utilizes a ternary alloy composition as a fuel cell catalyst, the ternary alloy composition containing platinum, ruthenium and palladium. The alloy shows increased activity as compared to well-known catalysts.

Heterostructured nanohybrid of zinc oxide-montmorillonite clay.

PubMed

Hur, Su Gil; Kim, Tae Woo; Hwang, Seong-Ju; Hwang, Sung-Ho; Yang, Jae Hun; Choy, Jin-Ho

2006-02-02

We have synthesized heterostructured zinc oxide-aluminosilicate nanohybrids through a hydrothermal reaction between the colloidal suspension of exfoliated montmorillonite nanosheets and the sol solution of zinc acetate. According to X-ray diffraction, N2 adsorption-desorption isotherm, and field emission-scanning electron microscopic analyses, it was found that the intercalation of zinc oxide nanoparticles expands the basal spacing of the host montmorillonite clay, and the crystallites of the nanohybrids are assembled to form a house-of-cards structure. From UV-vis spectroscopic investigation, it becomes certain that calcined nanohybrid contains two kinds of the zinc oxide species in the interlayer space of host lattice and in mesopores formed by the house-of-cards type stacking of the crystallites. Zn K-edge X-ray absorption near-edge structure/extended X-ray absorption fine structure analyses clearly demonstrate that guest species in the nanohybrids exist as nanocrystalline zinc oxides with wurzite-type structure.

Shape-dependence of the thermal and photochemical reactions of methanol on nanocrystalline anatase TiO2

NASA Astrophysics Data System (ADS)

Bennett, David A.; Cargnello, Matteo; Diroll, Benjamin T.; Murray, Christopher B.; Vohs, John M.

2016-12-01

Structure-activity relationships and the influence of particle size and shape on the partial- and photo-oxidation of methanol on nanocrystalline anatase TiO2 were investigated using temperature-programmed desorption. The study employed two distinct nanoparticle morphologies: truncated bipyramids exposing primarily {101} facets, and flatter platelets exposing primarily {001} surfaces, whose nominal sizes ranged from 10 to 25 nm. The platelets were found to be more active for thermally-driven reactions, such as coupling of methoxide groups to produce dimethyl ether, and deoxygenation to produce methane. A dependence of the reactivity of {001} facets for the coupling of methoxide groups to produce dimethyl ether on facet size was also observed. In contrast to the thermally-driven reactions, the bipyramidal nanoparticles were observed to be more active for a range of photochemical reactions, including oxidation and coupling to produce methyl formate, and photo-decomposition of surface methoxide species. This study also shows how well-defined nanocrystals can be used to help bridge the materials gap between studies of single crystal model catalysts and their high surface area industrial analogs.

Temperature dependence of the radiation tolerance of nanocrystalline pyrochlores A 2Ti 2O 7 (A = Gd, Ho and Lu)

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

Wen, J.; Sun, C.; Dholabhai, P. P.

A potentially enhanced radiation resistance of nanocrystalline materials, as a consequence of the high density of interfaces and surfaces, has attracted much attention both to understand the fundamental role of these defect sinks and to develop them for high-radiation environments. Here, irradiation response of nanocrystalline A 2Ti 2O 7 (A = Gd, Ho and Lu) pyrochlore powders with grain sizes of 20–30 nm was investigated by 1-MeV Kr 2+ ion bombardment. In situ transmission electron microscopy (TEM) revealed that the critical amorphization fluence for each nanocrystalline compound at room temperature was greater than that for their coarse-grained counterparts, indicating anmore » enhanced amorphization resistance. The effect of temperature on the irradiation response of one of these compounds, nanocrystalline Lu 2Ti 2O 7, was further examined by performing ion irradiation at an elevated temperature range of 480–600 K. The critical amorphization temperature (T c) was found to be noticeably higher in nanocrystalline Lu 2Ti 2O 7 (610 K) than its coarse-grained counterpart (480 K), revealing that nanocrystalline Lu 2Ti 2O 7 is less resistant to amorphization compared to its coarse-grained phase under high temperatures. We interpret these results with the aid of atomistic simulations. Molecular statics calculations find that cation antisite defects are less energetically costly to form near surfaces than in the bulk, suggesting that the nanocrystalline form of these materials is generally less susceptible to amorphization than coarse-grained counterparts at low temperatures where defect kinetics are negligible. In contrast, at high temperatures, the annealing efficiency of antisite defects by cation interstitials is significantly reduced due to the sink properties of the surfaces in the nanocrystalline pyrochlore, which contributes to the observed higher amorphization temperature in the nano-grained phase than in coarse-grained counterpart. Altogether, these

Temperature dependence of the radiation tolerance of nanocrystalline pyrochlores A 2Ti 2O 7 (A = Gd, Ho and Lu)

DOE PAGES

Wen, J.; Sun, C.; Dholabhai, P. P.; ...

2016-03-21

A potentially enhanced radiation resistance of nanocrystalline materials, as a consequence of the high density of interfaces and surfaces, has attracted much attention both to understand the fundamental role of these defect sinks and to develop them for high-radiation environments. Here, irradiation response of nanocrystalline A 2Ti 2O 7 (A = Gd, Ho and Lu) pyrochlore powders with grain sizes of 20–30 nm was investigated by 1-MeV Kr 2+ ion bombardment. In situ transmission electron microscopy (TEM) revealed that the critical amorphization fluence for each nanocrystalline compound at room temperature was greater than that for their coarse-grained counterparts, indicating anmore » enhanced amorphization resistance. The effect of temperature on the irradiation response of one of these compounds, nanocrystalline Lu 2Ti 2O 7, was further examined by performing ion irradiation at an elevated temperature range of 480–600 K. The critical amorphization temperature (T c) was found to be noticeably higher in nanocrystalline Lu 2Ti 2O 7 (610 K) than its coarse-grained counterpart (480 K), revealing that nanocrystalline Lu 2Ti 2O 7 is less resistant to amorphization compared to its coarse-grained phase under high temperatures. We interpret these results with the aid of atomistic simulations. Molecular statics calculations find that cation antisite defects are less energetically costly to form near surfaces than in the bulk, suggesting that the nanocrystalline form of these materials is generally less susceptible to amorphization than coarse-grained counterparts at low temperatures where defect kinetics are negligible. In contrast, at high temperatures, the annealing efficiency of antisite defects by cation interstitials is significantly reduced due to the sink properties of the surfaces in the nanocrystalline pyrochlore, which contributes to the observed higher amorphization temperature in the nano-grained phase than in coarse-grained counterpart. Altogether, these

3D surface topography study of the biofunctionalized nanocrystalline Ti-6Zr-4Nb/Ca-P

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

Jakubowicz, J., E-mail: jaroslaw.jakubowicz@put.poznan.pl; Adamek, G.; Jurczyk, M.U.

2012-08-15

In this work surface of the sintered Ti-6Zr-4Nb nanocrystalline alloy was electrochemically biofunctionalized. The porous surface was produced by anodic oxidation in 1 M H{sub 3}PO{sub 4} + 2%HF electrolyte at 10 V for 30 min. Next the calcium-phosphate (Ca-P) layer was deposited, onto the formed porous surface, using cathodic potential - 5 V kept for 60 min in 0.042 M Ca(NO{sub 3}){sub 2} + 0.025 M (NH{sub 4}){sub 2}HPO{sub 4} + 0.1 M HCl electrolyte. The deposited Ca-P layer anchored in the pores. The biofunctionalized surface was studied by XRD, SEM and EDS. In vitro tests culture of normalmore » human osteoblast (NHOst) cells showed very good cells proliferation, colonization and multilayering. Using optical profiler, roughness and hybrid 3D surface topography parameters were estimated. Correlation between surface composition, morphology, roughness and biocompatibility results was done. It has been shown by us that surface with appropriate chemical composition and topography, after combined electrochemical anodic and cathodic surface treatment, supports osteoblast adhesion and proliferation. 3D topography measurements using optical profiler play a key role in the biomaterials surface analysis. - Highlights: Black-Right-Pointing-Pointer Nanocrystalline Ti-6Zr-4Nb/Ca-P material was produced for hard tissue implant applications. Black-Right-Pointing-Pointer Calcium-phosphate results in surface biofunctionalization. Black-Right-Pointing-Pointer The biofunctionalized surface shows good in-vitro behavior.« less

Visible light-driven water oxidation promoted by host-guest interaction between photosensitizer and catalyst with a high quantum efficiency.

PubMed

Li, Hua; Li, Fei; Zhang, Biaobiao; Zhou, Xu; Yu, Fengshou; Sun, Licheng

2015-04-08

A highly active supramolecular system for visible light-driven water oxidation was developed with cyclodextrin-modified ruthenium complex as the photosensitizer, phenyl-modified ruthenium complexes as the catalysts, and sodium persulfate as the sacrificial electron acceptor. The catalysts were found to form 1:1 host-guest adducts with the photosensitizer. Stopped-flow measurement revealed the host-guest interaction is essential to facilitate the electron transfer from catalyst to sensitizer. As a result, a remarkable quantum efficiency of 84% was determined under visible light irradiation in neutral aqueous phosphate buffer. This value is nearly 1 order of magnitude higher than that of noninteraction system, indicating that the noncovalent incorporation of sensitizer and catalyst is an appealing approach for efficient conversion of solar energy into fuels.

Ruthenium(II)-catalysed remote C-H alkylations as a versatile platform to meta-decorated arenes

NASA Astrophysics Data System (ADS)

Li, Jie; Korvorapun, Korkit; de Sarkar, Suman; Rogge, Torben; Burns, David J.; Warratz, Svenja; Ackermann, Lutz

2017-06-01

The full control of positional selectivity is of prime importance in C-H activation technology. Chelation assistance served as the stimulus for the development of a plethora of ortho-selective arene functionalizations. In sharp contrast, meta-selective C-H functionalizations continue to be scarce, with all ruthenium-catalysed transformations currently requiring difficult to remove or modify nitrogen-containing heterocycles. Herein, we describe a unifying concept to access a wealth of meta-decorated arenes by a unique arene ligand effect in proximity-induced ruthenium(II) C-H activation catalysis. The transformative nature of our strategy is mirrored by providing a step-economical entry to a range of meta-substituted arenes, including ketones, acids, amines and phenols--key structural motifs in crop protection, material sciences, medicinal chemistry and pharmaceutical industries.

Effects of Bi Addition on the Microstructure and Mechanical Properties of Nanocrystalline Ag Coatings

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

Wang, Yuxin; Cheng, Guang; Tay, See Leng

Here in this study we investigated the effects of Bi addition on the microstructure and mechanical properties of an electrodeposited nanocrystalline Ag coating. Microstructural features were investigated with transmission electron microscopy (TEM). The results indicate that the addition of Bi introduced nanometer-scale Ag-Bi solid solution particles and more internal defects to the initial Ag microstructures. The anisotropic elastic-plastic properties of the Ag nanocrystalline coating with and without Bi addition were examined with nanoindentation experiments in conjunction with the recently-developed inverse method. The results indicate that the as-deposited nanocrystalline Ag coating contained high mechanical anisotropy. With the addition of 1 atomicmore » percent (at%) Bi, the anisotropy within Ag-Bi coating was very small, and yield strength of the nanocrystalline Ag-Bi alloy in both longitudinal and transverse directions were improved by over 100% compared to that of Ag. On the other hand, the strain-hardening exponent of Ag-Bi was reduced to 0.055 from the original 0.16 of the Ag coating. Furthermore, the addition of Bi only slightly increased the electrical resistivity of the Ag-Bi coating in comparison to Ag. Lastly, results of our study indicate that Bi addition is a promising method for improving the mechanical and physical performances of Ag coating for electrical contacts.« less

Effects of Bi Addition on the Microstructure and Mechanical Properties of Nanocrystalline Ag Coatings

DOE PAGES

Wang, Yuxin; Cheng, Guang; Tay, See Leng; ...

2017-08-10

Here in this study we investigated the effects of Bi addition on the microstructure and mechanical properties of an electrodeposited nanocrystalline Ag coating. Microstructural features were investigated with transmission electron microscopy (TEM). The results indicate that the addition of Bi introduced nanometer-scale Ag-Bi solid solution particles and more internal defects to the initial Ag microstructures. The anisotropic elastic-plastic properties of the Ag nanocrystalline coating with and without Bi addition were examined with nanoindentation experiments in conjunction with the recently-developed inverse method. The results indicate that the as-deposited nanocrystalline Ag coating contained high mechanical anisotropy. With the addition of 1 atomicmore » percent (at%) Bi, the anisotropy within Ag-Bi coating was very small, and yield strength of the nanocrystalline Ag-Bi alloy in both longitudinal and transverse directions were improved by over 100% compared to that of Ag. On the other hand, the strain-hardening exponent of Ag-Bi was reduced to 0.055 from the original 0.16 of the Ag coating. Furthermore, the addition of Bi only slightly increased the electrical resistivity of the Ag-Bi coating in comparison to Ag. Lastly, results of our study indicate that Bi addition is a promising method for improving the mechanical and physical performances of Ag coating for electrical contacts.« less

Catalytic oxidation of waste materials

NASA Technical Reports Server (NTRS)

Jagow, R. B.

1977-01-01

Aqueous stream of human waste is mixed with soluble ruthenium salts and is introduced into reactor at temperature where ruthenium black catalyst forms on internal surfaces of reactor. This provides catalytically active surface to convert oxidizable wastes into breakdown products such as water and carbon dioxide.

Effect of rapid thermal annealing on nanocrystalline TiO2 thin films synthesized by swift heavy ion irradiation

NASA Astrophysics Data System (ADS)

Thakurdesai, Madhavi; Kanjilal, D.; Bhattacharyya, Varsha

2012-08-01

Irradiation by swift heavy ions (SHI) is unique tool to synthesize nanocrystalline thin films. We have reported transformation of 100 nm thick amorphous films into nanocrystalline film due to irradiation by 100 MeV Ag ion beam. Oblate shaped nanoparticles having anatase phase of TiO2 were formed on the surface of the irradiated films. In the present investigation, these films are annealed at 350 °C for 2 min in oxygen atmosphere by Rapid Thermal Annealing (RTA) method. During RTA processing, the temperature rises abruptly and this thermal instability is expected to alter surface morphology, structural and optical properties of nanocrystalline TiO2 thin films. Thus in the present work, effect of RTA on SHI induced nanocrystalline thin films of TiO2 is studied. The effect of RTA processing on the shape and size of TiO2 nanoparticles is studied by Atomic Force Microscopy (AFM) and Scanning Electron Microscopy (SEM). Glancing Angle X-ray Diffraction (GAXRD) studies are carried to investigate structural changes induced by RTA processing. Optical characterization is carried out by UV-vis spectroscopy and photoluminescence (PL) spectroscopy. The changes observed in structural and optical properties of nanocrystalline TiO2 thin films after RTA processing are attributed to the annihilation of SHI induced defects.

Influence of coating on nanocrystalline magnetic properties during high temperature thermal ageing

NASA Astrophysics Data System (ADS)

Lekdim, Atef; Morel, Laurent; Raulet, Marie-Ange

2017-05-01

Since their birth or mergence the late 1980s, the nanocrystalline ultrasoft magnetic materials are taking a great importance in power electronic systems conception. One of the main advantages that make them more attractive nowadays is their ability to be packaged since the reduction of the magnetostrictive constant to almost zero. In aircraft applications, due to the high component compactness and to their location (for example near the jet engine), the operating temperature increases and may reach easily 200 °C and more. Consequently, the magnetic thermal ageing may occur but is, unfortunately, weakly studied. This paper focuses on the influence of the coating (packaging type) on the magnetic nanocrystalline performances during a thermal ageing. This study is based on monitoring the magnetic characteristics of two types of nanocrystalline cores (naked and coated) during a thermal activated ageing (100, 150 and 200 °C). Based on a dedicated monitoring protocol, a large magnetic characterization has been done and analyzed. Elsewhere, X-Ray Diffraction and magnetostriction measurements were carried out to support the study of the anisotropy energies evolution with ageing. This latter is discussed in this paper to explain and give hypothesis about the ageing phenomena.

Synthesis characterization and luminescence studies of gamma irradiated nanocrystalline yttrium oxide.

PubMed

Shivaramu, N J; Lakshminarasappa, B N; Nagabhushana, K R; Singh, Fouran

2016-02-05

Nanocrystalline Y2O3 is synthesized by solution combustion technique using urea and glycine as fuels. X-ray diffraction (XRD) pattern of as prepared sample shows amorphous nature while annealed samples show cubic nature. The average crystallite size is calculated using Scherrer's formula and is found to be in the range 14-30 nm for samples synthesized using urea and 15-20 nm for samples synthesized using glycine respectively. Field emission scanning electron microscopy (FE-SEM) image of 1173 K annealed Y2O3 samples show well separated spherical shape particles and the average particle size is found to be in the range 28-35 nm. Fourier transformed infrared (FTIR) and Raman spectroscopy reveals a stretching of Y-O bond. Electron spin resonance (ESR) shows V(-) center, O2(-) and Y(2+) defects. A broad photoluminescence (PL) emission with peak at ~386nm is observed when the sample is excited with 252 nm. Thermoluminescence (TL) properties of γ-irradiated Y2O3 nanopowder are studied at a heating rate of 5 K s(-1). The samples prepared by using urea show a prominent and well resolved peak at ~383 K and a weak one at ~570 K. It is also found that TL glow peak intensity (I(m1)) at ~383 K increases with increase in γ-dose up to ~6.0 kGy and then decreases with increase in dose. However, glycine used Y2O3 shows a prominent TL glow with peaks at 396 K and 590 K. Among the fuels, urea used Y2O3 shows simple and well resolved TL glows. This might be due to fuel and hence particle size effect. The kinetic parameters are calculated by Chen's glow curve peak shape method and results are discussed in detail. Copyright © 2015. Published by Elsevier B.V.

Synthesis characterization and luminescence studies of gamma irradiated nanocrystalline yttrium oxide

NASA Astrophysics Data System (ADS)

Shivaramu, N. J.; Lakshminarasappa, B. N.; Nagabhushana, K. R.; Singh, Fouran

2016-02-01

Nanocrystalline Y2O3 is synthesized by solution combustion technique using urea and glycine as fuels. X-ray diffraction (XRD) pattern of as prepared sample shows amorphous nature while annealed samples show cubic nature. The average crystallite size is calculated using Scherrer's formula and is found to be in the range 14-30 nm for samples synthesized using urea and 15-20 nm for samples synthesized using glycine respectively. Field emission scanning electron microscopy (FE-SEM) image of 1173 K annealed Y2O3 samples show well separated spherical shape particles and the average particle size is found to be in the range 28-35 nm. Fourier transformed infrared (FTIR) and Raman spectroscopy reveals a stretching of Y-O bond. Electron spin resonance (ESR) shows V- center, O2- and Y2 + defects. A broad photoluminescence (PL) emission with peak at 386 nm is observed when the sample is excited with 252 nm. Thermoluminescence (TL) properties of γ-irradiated Y2O3 nanopowder are studied at a heating rate of 5 K s- 1. The samples prepared by using urea show a prominent and well resolved peak at 383 K and a weak one at 570 K. It is also found that TL glow peak intensity (Im1) at 383 K increases with increase in γ-dose up to 6.0 kGy and then decreases with increase in dose. However, glycine used Y2O3 shows a prominent TL glow with peaks at 396 K and 590 K. Among the fuels, urea used Y2O3 shows simple and well resolved TL glows. This might be due to fuel and hence particle size effect. The kinetic parameters are calculated by Chen's glow curve peak shape method and results are discussed in detail.

Structural characterization, electrical conductivity and open circuit voltage studies of the nanocrystalline La10Si6O27 electrolyte material for SOFCs

NASA Astrophysics Data System (ADS)

Jena, Paramananda; Jayasubramaniyan, S.; Patro, P. K.; Lenka, R. K.; Sinha, Amit; Muralidharan, P.; Srinadhu, E. S.; Satyanarayana, N.

2018-02-01

Nanocrystalline La10Si6O27 apatite-type sample was synthesized by the co-precipitation method. Thermal behavior, phase, structure, morphology and elemental composition of La, O and Si of the synthesized La10Si6O27 sample were investigated through TG/DTA, XRD, FTIR, Raman spectroscopy and SEM-EDX measurements respectively. Formation of phase purity of the nanocrystalline La10Si6O27 sample was confirmed by analysing the measured X-ray powder diffraction (XRD) pattern using Rietveld refinement and the calculated average crystallite size of the La10Si6O27 sample was found to be 33 nm. The electrical conductivity of the sintered La10Si6O27 pellet was investigated as a function of temperature ranging from 200 to 800 °C under air and it was found to be 1.92 × 10-3 S cm-1 at 800 °C. The chemical stability of La10Si6O27 powder under oxidizing and reducing atmospheres was confirmed from the analysis of the measured XRD pattern and Raman spectral results. Open circuit potential of a button cell, made up of the La10Si6O27 sample, was tested up to 800 °C with both oxygen and hydrogen at opposite sides of the cell and was found to 1 V. Hence, the results demonstrate that La10Si6O27 could be a promising solid electrolyte material for the solid oxide fuel cell (SOFC) applications.

Study on the corrosion properties of nanocrystalline nickel electrodepositied by reverse pulse current

NASA Astrophysics Data System (ADS)

Cheng, Wen; Ge, Wen; Yang, Qian; Qu, Xinxin

2013-07-01

Nanocrystalline nickel coatings were produced by the method of reverse pulse electrodepositing on the surface of steel sheets. The crystallite size of nanocrystalline nickel coatings was determined by X-ray diffraction (XRD). The effect of saccharin concentration on the crystallite size of the coatings was studied. The average crystallite sizes were diminished as a result of increasing saccharin concentration. CHI660C electrochemical workstation was used to determine the Tafel polarization curves and electrochemical impedance spectroscopy (EIS) of the coatings. The value of corrosion potential, natural corrosion current density, polarizaiton resistance and impedance was calculated, the results suggested that smaller grain size led to higher polarization resistance. EIS gave the charge transfer resistance Rct and pore resistance Rpo variation trend from beginning to 30 min. Scanning electron microscopy (SEM) examination showed the surface morphology of the nickel coatings after the neutral salt spray (NSS) test or bathing in 10% HCl. The images indicated that the corrosion behavior of nanocrystalline nickel coatings was pitting corrosion, the mechanism was also discussed.

New twinning route in face-centered cubic nanocrystalline metals.

PubMed

Wang, Lihua; Guan, Pengfei; Teng, Jiao; Liu, Pan; Chen, Dengke; Xie, Weiyu; Kong, Deli; Zhang, Shengbai; Zhu, Ting; Zhang, Ze; Ma, Evan; Chen, Mingwei; Han, Xiaodong

2017-12-15

Twin nucleation in a face-centered cubic crystal is believed to be accomplished through the formation of twinning partial dislocations on consecutive atomic planes. Twinning should thus be highly unfavorable in face-centered cubic metals with high twin-fault energy barriers, such as Al, Ni, and Pt, but instead is often observed. Here, we report an in situ atomic-scale observation of twin nucleation in nanocrystalline Pt. Unlike the classical twinning route, deformation twinning initiated through the formation of two stacking faults separated by a single atomic layer, and proceeded with the emission of a partial dislocation in between these two stacking faults. Through this route, a three-layer twin was nucleated without a mandatory layer-by-layer twinning process. This route is facilitated by grain boundaries, abundant in nanocrystalline metals, that promote the nucleation of separated but closely spaced partial dislocations, thus enabling an effective bypassing of the high twin-fault energy barrier.

Ferroelectric Polarization in Nanocrystalline Hydroxyapatite Thin Films on Silicon

PubMed Central

Lang, S. B.; Tofail, S. A. M.; Kholkin, A. L.; Wojtaś, M.; Gregor, M.; Gandhi, A. A.; Wang, Y.; Bauer, S.; Krause, M.; Plecenik, A.

2013-01-01

Hydroxyapatite nanocrystals in natural form are a major component of bone- a known piezoelectric material. Synthetic hydroxyapatite is widely used in bone grafts and prosthetic pyroelectric coatings as it binds strongly with natural bone. Nanocrystalline synthetic hydroxyapatite films have recently been found to exhibit strong piezoelectricity and pyroelectricity. While a spontaneous polarization in hydroxyapatite has been predicted since 2005, the reversibility of this polarization (i.e. ferroelectricity) requires experimental evidence. Here we use piezoresponse force microscopy to demonstrate that nanocrystalline hydroxyapatite indeed exhibits ferroelectricity: a reversal of polarization under an electrical field. This finding will strengthen investigations on the role of electrical polarization in biomineralization and bone-density related diseases. As hydroxyapatite is one of the most common biocompatible materials, our findings will also stimulate systematic exploration of lead and rare-metal free ferroelectric devices for potential applications in areas as diverse as in vivo and ex vivo energy harvesting, biosensing and electronics. PMID:23884324

Ferroelectric Polarization in Nanocrystalline Hydroxyapatite Thin Films on Silicon

NASA Astrophysics Data System (ADS)

Lang, S. B.; Tofail, S. A. M.; Kholkin, A. L.; Wojtaś, M.; Gregor, M.; Gandhi, A. A.; Wang, Y.; Bauer, S.; Krause, M.; Plecenik, A.

2013-07-01

Hydroxyapatite nanocrystals in natural form are a major component of bone- a known piezoelectric material. Synthetic hydroxyapatite is widely used in bone grafts and prosthetic pyroelectric coatings as it binds strongly with natural bone. Nanocrystalline synthetic hydroxyapatite films have recently been found to exhibit strong piezoelectricity and pyroelectricity. While a spontaneous polarization in hydroxyapatite has been predicted since 2005, the reversibility of this polarization (i.e. ferroelectricity) requires experimental evidence. Here we use piezoresponse force microscopy to demonstrate that nanocrystalline hydroxyapatite indeed exhibits ferroelectricity: a reversal of polarization under an electrical field. This finding will strengthen investigations on the role of electrical polarization in biomineralization and bone-density related diseases. As hydroxyapatite is one of the most common biocompatible materials, our findings will also stimulate systematic exploration of lead and rare-metal free ferroelectric devices for potential applications in areas as diverse as in vivo and ex vivo energy harvesting, biosensing and electronics.

Ferroelectric polarization in nanocrystalline hydroxyapatite thin films on silicon.

PubMed

Lang, S B; Tofail, S A M; Kholkin, A L; Wojtaś, M; Gregor, M; Gandhi, A A; Wang, Y; Bauer, S; Krause, M; Plecenik, A

2013-01-01

Hydroxyapatite nanocrystals in natural form are a major component of bone--a known piezoelectric material. Synthetic hydroxyapatite is widely used in bone grafts and prosthetic pyroelectric coatings as it binds strongly with natural bone. Nanocrystalline synthetic hydroxyapatite films have recently been found to exhibit strong piezoelectricity and pyroelectricity. While a spontaneous polarization in hydroxyapatite has been predicted since 2005, the reversibility of this polarization (i.e. ferroelectricity) requires experimental evidence. Here we use piezoresponse force microscopy to demonstrate that nanocrystalline hydroxyapatite indeed exhibits ferroelectricity: a reversal of polarization under an electrical field. This finding will strengthen investigations on the role of electrical polarization in biomineralization and bone-density related diseases. As hydroxyapatite is one of the most common biocompatible materials, our findings will also stimulate systematic exploration of lead and rare-metal free ferroelectric devices for potential applications in areas as diverse as in vivo and ex vivo energy harvesting, biosensing and electronics.

Visualizing decoupling in nanocrystalline alloys: A FORC-temperature analysis

NASA Astrophysics Data System (ADS)

Rivas, M.; Martínez-García, J. C.; Gorria, P.

2016-02-01

Devitrifying ferromagnetic amorphous precursors in the adequate conditions may give rise to disordered assemblies of densely packed nanocrystals with extraordinary magnetic softness well explained by the exchange coupling among multiple crystallites. Whether the magnetic exchange interaction is produced by direct contact or mediated by the intergranular amorphous matrix has a strong influence on the behaviour of the system above room temperature. Multi-phase amorphous-nanocrystalline systems dramatically harden when approaching the amorphous Curie temperature (TC) due to the hard grains decoupling. The study of the thermally induced decoupling of nanosized crystallites embedded in an amorphous matrix has been performed in this work by the first-order reversal curves (FORCs) analysis. We selected a Fe-rich amorphous alloy with TC = 330 K, in order to follow the evolution of the FORC diagrams obtained below and above such temperature in samples with different percentages of nanocrystalline phase. The existence of up to four regions exhibiting unlike magnetic behaviours is unambiguously determined from the temperature evolution of the FORC.

Development of biomimetic catalytic oxidation methods and non-salt methods using transition metal-based acid and base ambiphilic catalysts

PubMed Central

MURAHASHI, Shun-Ichi

2011-01-01

This review focuses on the development of ruthenium and flavin catalysts for environmentally benign oxidation reactions based on mimicking the functions of cytochrome P-450 and flavoenzymes, and low valent transition-metal catalysts that replace conventional acids and bases. Several new concepts and new types of catalytic reactions based on these concepts are described. PMID:21558760

Cyclometalated ruthenium(II) complexes with a bis-carbene CCC-pincer ligand.

PubMed

Zhang, You-Ming; Shao, Jiang-Yang; Yao, Chang-Jiang; Zhong, Yu-Wu

2012-08-21

The first series of cyclometalated ruthenium complexes with a CCC-pincer bis-carbene ligand have been obtained as bench-stable compounds. Single-crystal X-ray analysis of one of these complexes with 4'-di-p-anisylamino-2,2':6',2''-terpyridine is presented. The Ru(II/III) redox potentials and MLCT absorptions of these complexes can be varied by attaching an electron-donating or -withdrawing group on the noncyclometalating ligand.

Evidence that abnormal grain growth precedes fatigue crack initiation in nanocrystalline Ni-Fe

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

Furnish, Timothy A.; Bufford, Daniel C.; Ren, Fang

Prior studies on the high-cycle fatigue behavior of nanocrystalline metals have shown that fatigue fracture is associated with abnormal grain growth (AGG). However, those previous studies have been unable to determine if AGG precedes fatigue crack initiation, or vice-versa. The present study shows that AGG indeed occurs prior to crack formation in nanocrystalline Ni-Fe by using a recently developed synchrotron X-ray diffraction modality that has been adapted for in-situ analysis. The technique allows fatigue tests to be interrupted at the initial signs of the AGG process, and subsequent microscopy reveals the precursor damage state preceding crack initiation.

Superparamagnetic nanocrystalline ZnFe2O4 with a very high Curie temperature.

PubMed

Deka, Sasanka; Joy, P A

2008-08-01

Studies on the magnetic properties of nanocrystalline ZnFe2O4 synthesized by an autocombustion method are reported. Superparamagnetic behavior is observed for the nanocrystalline materials with particle sizes of 8 nm and 17 nm, with superparamagnetic blocking temperatures of 65 K and 75 K, respectively. Magnetic hysteresis with very large coercivities of 533 Oe and 325 Oe, respectively, are observed at 12 K. Studies on the temperature variation of the magnetization above room temperature indicate that the Curie temperature is as high as approximately 800 K when compared to the paramagnetic nature of bulk zinc ferrite at room temperature.

Evidence that abnormal grain growth precedes fatigue crack initiation in nanocrystalline Ni-Fe

DOE PAGES

Furnish, Timothy A.; Bufford, Daniel C.; Ren, Fang; ...

2018-09-06

Prior studies on the high-cycle fatigue behavior of nanocrystalline metals have shown that fatigue fracture is associated with abnormal grain growth (AGG). However, those previous studies have been unable to determine if AGG precedes fatigue crack initiation, or vice-versa. The present study shows that AGG indeed occurs prior to crack formation in nanocrystalline Ni-Fe by using a recently developed synchrotron X-ray diffraction modality that has been adapted for in-situ analysis. The technique allows fatigue tests to be interrupted at the initial signs of the AGG process, and subsequent microscopy reveals the precursor damage state preceding crack initiation.

Chemical Mechanical Polishing of Ruthenium, Cobalt, and Black Diamond Films

NASA Astrophysics Data System (ADS)

Peethala, Brown Cornelius

Ta/TaN bilayer serves as the diffusion barrier as well as the adhesion promoter between Cu and the dielectric in 32 nm technology devices. A key concern of future technology devices (<32 nm) for Cu interconnects is the extendibility of TaN/Ta/Cu-seed to sustain the diffusion barrier performance without forming voids and meeting the requirements of low resistivity. These are very challenging requirements for the Ta/TaN bilayer at a thickness of < 5 nm. Hence, ruthenium (Ru) and cobalt (Co), among these, are being considered for replacing Ta/TaN as barrier materials for Cu interconnects in future technology devices. Both are very attractive for reasons such as the capability of direct electroplating of Cu, lower resistivity and for a single layer (vs. a bilayer of Ta/TaN) to act as a barrier. During patterning, they need to be planarized using conventional chemical mechanical polishing (CMP) to achieve a planar surface. However, CMP of these new barrier materials requires novel slurry compositions that provide adequate selectivity towards Cu and dielectric films, and minimize galvanic corrosion. Apart from the application as a barrier, Ru also has been proposed as a lower electrode material in metal-insulator-metal capacitors where high (> 50 nm/min) Ru removal rates (RRs) are required and as a stop layer in magnetic recording head fabrication where low (< 1 nm/min) Ru RRs are desired. A Ru removal rate of ˜60 nm/min was achieved with a colloidal silica-based slurry at pH 9 using potassium periodate (KIO4) as the oxidizer. At this pH, toxic RuO4 does not form eliminating a major challenge in Ru CMP. This removal rate was obtained by increasing the solubility of KIO4 by adding potassium hydroxide (KOH). It was also determined that increased the ionic strength is not responsible for the observed increase in Ru removal rate. Benzotirazole (BTA) and ascorbic acid were added to the slurry to reduce the open circuit potential (Eoc) difference between Cu and Ru to ˜20 m

DETOX{sup SM} catalyzed wet oxidation as a highly suitable pretreatment for vitrification

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

Rogers, T.W.; Dhooge, P.M.; Goldblatt, S.D.

1995-11-01

A catalyzed wet oxidation process has been developed which uses ferric iron in an acidic water solution to oxidize organic compounds in the presence of platinum ion and/or ruthenium ion catalysts. The process is capable of oxidizing a wide range of organic compounds to carbon dioxide and water with great efficiency. The process has been tested in the bench-scale with many different types of organics. Conceptual engineering for application of the process to treatment of liquid and solid organic waste materials has been followed by engineering design for a demonstration unit. Fabrication of the unit and demonstration on hazardous andmore » mixed wastes at two Department of Energy sites is planned in 1995 through 1997.« less

Nanocrystallinity effects on osteoblast and osteoclast response to silicon substituted hydroxyapatite.

PubMed

Casarrubios, Laura; Matesanz, María Concepción; Sánchez-Salcedo, Sandra; Arcos, Daniel; Vallet-Regí, María; Portolés, María Teresa

2016-11-15

Silicon substituted hydroxyapatites (SiHA) are highly crystalline bioceramics treated at high temperatures (about 1200°C) which have been approved for clinical use with spinal, orthopedic, periodontal, oral and craniomaxillofacial applications. The preparation of SiHA with lower temperature methods (about 700°C) provides nanocrystalline SiHA (nano-SiHA) with enhanced bioreactivity due to higher surface area and smaller crystal size. The aim of this study has been to know the nanocrystallinity effects on the response of both osteoblasts and osteoclasts (the two main cell types involved in bone remodelling) to silicon substituted hydroxyapatite. Saos-2 osteoblasts and osteoclast-like cells (differentiated from RAW-264.7 macrophages) have been cultured on the surface of nano-SiHA and SiHA disks and different cell parameters have been evaluated: cell adhesion, proliferation, viability, intracellular content of reactive oxygen species, cell cycle phases, apoptosis, cell morphology, osteoclast-like cell differentiation and resorptive activity. This comparative in vitro study evidences that nanocrystallinity of SiHA affects the cell/biomaterial interface inducing bone cell apoptosis by loss of cell anchorage (anoikis), delaying osteoclast-like cell differentiation and decreasing the resorptive activity of this cell type. These results suggest the potential use of nano-SiHA biomaterial for preventing bone resorption in treatment of osteoporotic bone. Copyright © 2016 Elsevier Inc. All rights reserved.

Wear behavior of Cu-Zn alloy by ultrasonic nanocrystalline surface modification.

PubMed

Cho, In Shik; Amanov, Auezhan; Ahn, Deok Gi; Shin, Keesam; Lee, Chang Soon; Pyoun, Young-Shik; Park, In-Gyu

2011-07-01

The ultrasonic nanocrystalline surface modification (UNSM) was applied to disk specimens made of Cu-Zn alloy in order to investigate the UNSM effects under five various conditions on wear of deformation twinning. In this paper, ball-on-disk test was conducted, and the results of UNSM-treated specimens showed that surface layer dislocation density and multi-directional twins were abruptly increased, and the grain size was altered into nano scale. UNSM delivers force onto the workpiece surface 20,000 times per second with 1,000 to 4,000 contact counts per square millimeter. The UNSM technology creates nanocrystalline and deformation twinning on the workpiece surface. One of the main concepts of this study is that defined phenomena of the UNSM technology, and the results revealed that nanocrystalline and deformation twinning depth might be controlled by means of impact energy of UNSM technology. EBSD and TEM analyses showed that deformation layer was increased up to 268 microm, and initial twin density was 0.001 x 10(6) cm(-2) and increased up to 0.343 x 10(6) cm(-2). Wear volume loss was also decreased from 703 x 10(3) mm3 to 387 x 10(3) mm3. Wear behavior according to deformation depth was observed under three different combinations. This is related to deformation depth which was created by UNSM technology.

Thermal conductivity of self-ion irradiated nanocrystalline zirconium thin films

DOE PAGES

Pulavarthy, Raghu; Wang, Baoming; Hattar, Khalid; ...

2017-07-15

Thermomechanical stability and high thermal conductivity are important for nuclear cladding material performance and reliability, which degrade over time under irradiation. The literature suggests nanocrystalline materials as radiation tolerant, but little or no evidence is present from thermal transport perspective. In this study, we irradiated 10 nm grain size zirconium thin films with 800 keV Zr + beam from a 6 MV HVE Tandem accelerator to achieve various doses of 3 × 10 10 to 3.26 × 10 14 ions/cm 2, corresponding to displacement per atom (dpa) of 2.1 × 10 –4 to 2.28. Transmission electron microscopy showed significant grainmore » growth, texture evolution and oxidation in addition to the creation of displacement defects due to the irradiation. The specimens were co-fabricated with micro-heaters to establish thermal gradients that were mapped using infrared thermometry. An energy balance approach was used to estimate the thermal conductivity of the specimens, as function of irradiation dosage. As a result, up to 32% reduction of thermal conductivity was measured for the sample exposed to a dose of 2.1 dpa (3 × 10 14 ions/cm 2).« less

Solubility of Nanocrystalline Cerium Dioxide: Experimental Data and Thermodynamic Modeling

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

Plakhova, Tatiana V.; Romanchuk, Anna Yu.; Yakunin, Sergey N.

For this study, ultrafine 5 nm ceria isotropic nanoparticles were prepared using the rapid chemical precipitation approach from cerium(III) nitrate and ammonium hydroxide aqueous solutions. The as-prepared nanoparticles were shown to contain predominantly Ce(IV) species. The solubility of nanocrystalline CeO 2 at several pH values was determined using ICP-MS and radioactive tracer methods. Phase composition of the ceria samples remained unchanged upon partial dissolution, while the shape of the particles changed dramatically, yielding nanorods under neutral pH conditions. According to X-ray absorption spectroscopy investigation of the supernatant, Ce(III) was the main cerium species in solution at pH < 4. Basedmore » on the results obtained, a reductive dissolution model was used for data interpretation. According to this model, the solubility product for ceria nanoparticles was determined to be log K sp = -59.3 ± 0.3 in 0.01 M NaClO 4. Taken together, our results show that the pH dependence of ceria anti- and pro-oxidant activity can be related to the dissolution of CeO 2 in aqueous media.« less

Solubility of Nanocrystalline Cerium Dioxide: Experimental Data and Thermodynamic Modeling

DOE PAGES

Plakhova, Tatiana V.; Romanchuk, Anna Yu.; Yakunin, Sergey N.; ...

2016-09-12

For this study, ultrafine 5 nm ceria isotropic nanoparticles were prepared using the rapid chemical precipitation approach from cerium(III) nitrate and ammonium hydroxide aqueous solutions. The as-prepared nanoparticles were shown to contain predominantly Ce(IV) species. The solubility of nanocrystalline CeO 2 at several pH values was determined using ICP-MS and radioactive tracer methods. Phase composition of the ceria samples remained unchanged upon partial dissolution, while the shape of the particles changed dramatically, yielding nanorods under neutral pH conditions. According to X-ray absorption spectroscopy investigation of the supernatant, Ce(III) was the main cerium species in solution at pH < 4. Basedmore » on the results obtained, a reductive dissolution model was used for data interpretation. According to this model, the solubility product for ceria nanoparticles was determined to be log K sp = -59.3 ± 0.3 in 0.01 M NaClO 4. Taken together, our results show that the pH dependence of ceria anti- and pro-oxidant activity can be related to the dissolution of CeO 2 in aqueous media.« less

Thermal conductivity of self-ion irradiated nanocrystalline zirconium thin films

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

Pulavarthy, Raghu; Wang, Baoming; Hattar, Khalid

Thermomechanical stability and high thermal conductivity are important for nuclear cladding material performance and reliability, which degrade over time under irradiation. The literature suggests nanocrystalline materials as radiation tolerant, but little or no evidence is present from thermal transport perspective. In this study, we irradiated 10 nm grain size zirconium thin films with 800 keV Zr + beam from a 6 MV HVE Tandem accelerator to achieve various doses of 3 × 10 10 to 3.26 × 10 14 ions/cm 2, corresponding to displacement per atom (dpa) of 2.1 × 10 –4 to 2.28. Transmission electron microscopy showed significant grainmore » growth, texture evolution and oxidation in addition to the creation of displacement defects due to the irradiation. The specimens were co-fabricated with micro-heaters to establish thermal gradients that were mapped using infrared thermometry. An energy balance approach was used to estimate the thermal conductivity of the specimens, as function of irradiation dosage. As a result, up to 32% reduction of thermal conductivity was measured for the sample exposed to a dose of 2.1 dpa (3 × 10 14 ions/cm 2).« less

Oxidative precipitation of ruthenium oxide for supercapacitors: Enhanced capacitive performances by adding cetyltrimethylammonium bromide

NASA Astrophysics Data System (ADS)

Chen, I.-Li; Wei, Yu-Chen; Chen, Tsan-Yao; Hu, Chi-Chang; Lin, Tsang-Lang

2014-12-01

Thermally stable and porous RuO2·xH2O with superior rate-retention capability is prepared by the H2O2-oxidative precipitation method modified with the cetyltrimethylammonium bromide (CTAB) template. The specific capacitance and rate-retention of RuO2·xH2O are considerably enhanced by the CTAB modification and annealing at 200 °C because of extremely localized crystallization and pore opening of slightly sintered RuO2·xH2O nanoparticles trapped with CTAB. This unique structure, confirmed by the X-ray absorption spectroscopic (XAS), Raman spectroscopic, and transmission electron microscopic (TEM) analyses, favors the utilization of RuO2·xH2O nanocrystals and increases the electrolyte accessibility in comparing with RuO2·xH2O without CTAB modification. The preferential orientation growth along the {101} facet of RuO2 nanocrystals in some local regions is acquired by the CTAB modification and annealing in air at temperatures ≥350 °C. Such preferential orientation growth of RuO2 crystallites is attributable to the oxidation of trapped surfactants during the thermal annealing process, which adsorb on the high surface energy planes of RuO2.

A promising new thermoelectric material - Ruthenium silicide

NASA Technical Reports Server (NTRS)

Vining, Cronin B.; Mccormack, Joseph A.; Zoltan, Andrew; Zoltan, Leslie D.

1991-01-01

Experimental and theoretical efforts directed toward increasing thermoelectric figure of merit values by a factor of 2 or 3 have been encouraging in several respects. An accurate and detailed theoretical model developed for n-type silicon-germanium (SiGe) indicates that ZT values several times higher than currently available are expected under certain conditions. These new, high ZT materials are expected to be significantly different from SiGe, but not unreasonably so. Several promising candidate materials have been identified which may meet the conditions required by theory. One such candidate, ruthenium silicide, currently under development at JPL, has been estimated to have the potential to exhibit figure of merit values 4 times higher than conventional SiGe materials. Recent results are summarized.

Intrinsic ferromagnetism in nanocrystalline Mn-doped ZnO depending on Mn concentration.

PubMed

Subramanian, Munisamy; Tanemura, Masaki; Hihara, Takehiko; Soga, Tetsuo; Jimbo, Takashi

2011-04-01

The physical properties of Zn(1-x)Mn(x)O nanoparticles synthesized by thermal decomposition are extensively investigated by X-ray diffraction (XRD), Transmission Electron Microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Raman light scattering and Hysteresis measurements. XRD and XPS spectra reveal the absence of secondary phase in nanocrystalline ZnO doped with 5% or less Mn; and, later confirms that the valance state of Mn to be 2+ for all the samples. Raman spectra exhibit a peak at 660 cm(-1) which we attribute to the intrinsic lattice defects of ZnO with increasing Mn concentration. Overall, our results demonstrate that ferromagnetic properties can be realized while Mn-doped ZnO obtained in the nanocrystalline form.

Analysis of a nanocrystalline polymer dispersion of ebselen using solid-state NMR, Raman microscopy, and powder X-ray diffraction.

PubMed

Vogt, Frederick G; Williams, Glenn R

2012-07-01

Nanocrystalline drug-polymer dispersions are of significant interest in pharmaceutical delivery. The purpose of this work is to demonstrate the applicability of methods based on two-dimensional (2D) and multinuclear solid-state NMR (SSNMR) to a novel nanocrystalline pharmaceutical dispersion of ebselen with polyvinylpyrrolidone-vinyl acetate (PVP-VA), after initial characterization with other techniques. A nanocrystalline dispersion of ebselen with PVP-VA was prepared and characterized by powder X-ray diffraction (PXRD), confocal Raman microscopy and mapping, and differential scanning calorimetry (DSC), and then subjected to detailed 1D and 2D SSNMR analysis involving ¹H, ¹³C, and ⁷⁷Se isotopes and ¹H spin diffusion. PXRD was used to show that dispersion contains nanocrystalline ebselen in the 35-60 nm size range. Confocal Raman microscopy and spectral mapping were able to detect regions where short-range interactions may occur between ebselen and PVP-VA. Spin diffusion effects were analyzed using 2D SSNMR experiments and are able to directly detect interactions between ebselen and the surrounding PVP-VA. The methods used here, particularly the 2D SSNMR methods based on spin diffusion, provided detailed structural information about a nanocrystalline polymer dispersion of ebselen, and should be useful in other studies of these types of materials.

Ruthenium nanoparticles decorated curl-like porous carbons for high performance supercapacitors

NASA Astrophysics Data System (ADS)

Lou, Bih-Show; Veerakumar, Pitchaimani; Chen, Shen-Ming; Veeramani, Vediyappan; Madhu, Rajesh; Liu, Shang-Bin

2016-01-01

The synthesis of highly dispersed and stable ruthenium nanoparticles (RuNPs; ca. 2-3 nm) on porous activated carbons derived from Moringa Oleifera fruit shells (MOC) is reported and were exploited for supercapacitor applications. The Ru/MOC composites so fabricated using the biowaste carbon source and ruthenium acetylacetonate as the co-feeding metal precursors were activated at elevated temperatures (600-900 oC) in the presence of ZnCl2 as the pore generating and chemical activating agent. The as-prepared MOC carbonized at 900 oC was found to possess a high specific surface area (2522 m2 g-1) and co-existing micro- and mesoporosities. Upon incorporating RuNPs, the Ru/MOC nanocomposites loaded with modest amount of metallic Ru (1.0-1.5 wt%) exhibit remarkable electrochemical and capacitive properties, achiving a maximum capacitance of 291 F g-1 at a current density of 1 A g-1 in 1.0 M H2SO4 electrolyte. These highly stable and durable Ru/MOC electrodes, which can be facily fabricated by the eco-friendly and cost-effective route, should have great potentials for practical applications in energy storage, biosensing, and catalysis.

Manipulating the Rate-Limiting Step in Water Oxidation Catalysis by Ruthenium Bipyridine–Dicarboxylate Complexes

DOE PAGES

Shaffer, David W.; Xie, Yan; Szalda, David J.; ...

2016-11-01

In order to gain a deeper mechanistic understanding of water oxidation by [(bda)Ru(L) 2] catalysts (bdaH 2 = [2,2'-bipyridine]-6,6'-dicarboxylic acid; L = pyridine-type ligand), a series of modified catalysts with one and two trifluoromethyl groups in the 4 position of the bda 2– ligand was synthesized and studied using stopped-flow kinetics. The additional $-$CF 3 groups increased the oxidation potentials for the catalysts and enhanced the rate of electrocatalytic water oxidation at low pH. Stopped-flow measurements of cerium(IV)-driven water oxidation at pH 1 revealed two distinct kinetic regimes depending on catalyst concentration. At relatively high catalyst concentration (ca. ≥10 –4more » M), the rate-determining step (RDS) was a proton-coupled oxidation of the catalyst by cerium(IV) with direct kinetic isotope effects (KIE > 1). At low catalyst concentration (ca. ≤10 –6 M), the RDS was a bimolecular step with k H/k D ≈ 0.8. The results support a catalytic mechanism involving coupling of two catalyst molecules. The rate constants for both RDSs were determined for all six catalysts studied. The presence of $-$CF 3 groups had inverse effects on the two steps, with the oxidation step being fastest for the unsubstituted complexes and the bimolecular step being faster for the most electron-deficient complexes. Finally, though the axial ligands studied here did not significantly affect the oxidation potentials of the catalysts, the nature of the ligand was found to be important not only in the bimolecular step but also in facilitating electron transfer from the metal center to the sacrificial oxidant.« less