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Sample records for rutile a-tio2 experimental

  1. Quantitative analysis of nanometer anatase-rutile mixtures via experimentation and theoretical calculation.

    PubMed

    Guo, Li; Zhou, Zhiqiang; Jia, Peiyun; Ye, Feng

    2012-12-01

    In this paper, we developed a method based on X-ray diffractometry for determining the weight ratio of nanometer anatase to rutile or their relative amounts in TiO2 polymorphs, and corresponding formulas for such determination were put forward. The very key constant K in these formulas has been specially evaluated by experimentalizing nanometer polymorphs of titanium dioxide. Furthermore, a theoretical value of K was obtained through detailed theoretical calculation based on X-ray powder diffraction theory. The K value concluded from experimentation coincides well with that yielded from theoretical calculation, thus the validity and reliability of the experimental K value has been further confirmed. This coincidence may also suggest the applicability of X-ray powder diffraction theory to nanometer crystals. With this method, the relative amounts of nanometer anatase and rutile in their mixtures or the weight ratio of nanometer anatase to rutile in any a mixture can be easily determined only upon a XRD test.

  2. Crystals size and surface chemistry dependent phase diagram for nanocrystals of rutile and anatase: Experimental studies and computer modeling

    NASA Astrophysics Data System (ADS)

    Xu, H.; Barnard, A. S.

    2008-12-01

    It is well known that rutile is the thermodynamically stable phase of TiO2 under ambient conditions at the macroscale, and that anatase is the thermodynamically stable phase at the nanoscale. Both anatase and rutile have superior performance in a range of advanced photochemical applications. It is important for our understanding of the stability of nanostructures in different chemical and physical environments, because both rutile and anatase nanocrystals are used in different chemical and engineering environments. Using a size-, shape- and temperature-dependent thermodynamic model we have generated the first phase diagram for anatase and rutile nanocrystals by incorporating more experimentally relevant parameters (both the equilibrium shape and surface chemistry). Results from hydrothermal synthesis and DFT-based computer modeling show acidic environment favors rutile formation. The acidic solution also favors OH2-terminated surfaces of both anatase and rutile. The boundary between rutile an danatase ranges from ~ 10 nm to ~ 50 nm, depending on temperature and surface composition. The calculated phase map indicates that the equilibrium boundary between anatase and rutile nano-crystals is surface charge chemistry dependent, which relates to both their formation and post-synthesis environments.

  3. Adsorption of L-aspartate to rutile (α-TiO 2): Experimental and theoretical surface complexation studies

    NASA Astrophysics Data System (ADS)

    Jonsson, Caroline M.; Jonsson, Christopher L.; Estrada, Charlene; Sverjensky, Dimitri A.; Cleaves, H. James, II; Hazen, Robert M.

    2010-04-01

    Interactions between aqueous amino acids and mineral surfaces influence many geochemical processes from biomineralization to the origin of life. However, the specific reactions involved and the attachment mechanisms are mostly unknown. We have studied the adsorption of L-aspartate on the surface of rutile (α-TiO 2, pH PPZC = 5.4) in NaCl(aq) over a wide range of pH, ligand-to-solid ratio and ionic strength, using potentiometric titrations and batch adsorption experiments. The adsorption is favored below pH 6 with a maximum of 1.2 μmol of adsorbed aspartate per m 2 of rutile at pH 4 in our experiments. The adsorption decreases at higher pH because the negatively charged aspartate molecule is repelled by the negatively charged rutile surface above pH PPZC. At pH values of 3-5, aspartate adsorption increases with decreasing ionic strength. The adsorption of aspartate on rutile is very similar to that previously published for glutamate ( Jonsson et al., 2009). An extended triple-layer model was used to provide a quantitative thermodynamic characterization of the aspartate adsorption data. Two reaction stoichiometries identical in reaction stoichiometry to those for glutamate were needed. At low surface coverages, aspartate, like glutamate, may form a bridging-bidentate surface species binding through both carboxyl groups, i.e. "lying down" on the rutile surface. At high surface coverages, the reaction stoichiometry for aspartate was interpreted differently compared to glutamate: it likely involves an outer-sphere or hydrogen bonded aspartate surface species, as opposed to a partly inner-sphere complex for glutamate. Both the proposed aspartate species are qualitatively consistent with previously published ATR-FTIR spectroscopic results for aspartate on amorphous titanium dioxide. The surface complexation model for aspartate was tested against experimental data for the potentiometric titration of aspartate in the presence of rutile. In addition, the model correctly

  4. Experimental investigation and application of the equilibrium rutile + orthopyroxene = quartz + ilmenite

    USGS Publications Warehouse

    Hayob, J.L.; Bohlen, S.R.; Essene, E.J.

    1993-01-01

    Equilibria in the Sirf (Silica-Ilmenite-Rutile-Ferrosilite) system: {Mathematical expression} have been calibrated in the range 800-1100?? C and 12-26 kbar using a piston-cylinder apparatus to assess the potential of the equilibria for geobarometry in granulite facies assemblages that lack garnet. Thermodynamic calculations indicate that the two end-member equilibria involving quartz + geikielite = rutile + enstatite, and quartz + ilmenite = rutile + ferrosilite, are metastable. We therefore reversed equilibria over the compositional range Fs40-70, using Ag80Pd20 capsules with {Mathematical expression} buffered at or near iron-wu??stite. Ilmenite compositions coexisting with orthopyroxene are {Mathematical expression} of 0.06 to 0.15 and {Mathematical expression} of 0.00 to 0.01, corresponding to KD values of 13.3, 10.2, 9.0 and 8.0 (??0.5) at 800, 900, 1000 and 1100?? C, respectively, where KD=(XMg/XFe)Opx/(XMg/XFe)Ilm. Pressures have been calculated using equilibria in the Sirf system for granulites from the Grenville Province of Ontario and for granulite facies xenoliths from central Mexico. Pressures are consistent with other well-calibrated geobarometers for orthopyroxeneilmenite pairs from two Mexican samples in which oxide textures appear to represent equilibrium. Geologically unreasonable pressures are obtained, however, where oxide textures are complex. Application of data from this study on the equilibrium distribution of iron and magnesium between ilmenite and orthopyroxene suggests that some ilmenite in deep crustal xenoliths is not equilibrated with coexisting pyroxene, while assemblages from exposed granulite terranes have reequilibrated during retrogression. The Sirf equilibria are sensitive to small changes in composition and may be used for determination of activity/composition (a/X) relations of orthopyroxene if an ilmenite model is specified. A symmetric regular solution model has been used for orthopyroxene in conjunction with activity models

  5. The provenance of rutile.

    USGS Publications Warehouse

    Force, E.R.

    1980-01-01

    Most coarse detrital rutile is derived from high-grade metamorphic rocks. Contrary to a conventional assumption, independent rutile grains are particularly rare in igneous rocks except alkalic rocks. The use of rutile in the zircon-tourmaline-rutile index of mineralogic maturity is only partially valid, owing to its restricted provenance. -Author

  6. Crystallization Behavior and Growing Process of Rutile Crystals in Ti-Bearing Blast Furnace Slag

    NASA Astrophysics Data System (ADS)

    Zhang, Wu; Zhang, Li; Li, Yuhai; Li, Xin

    2016-09-01

    The aim of the present work is to elucidate crystallization and growing process of rutile crystals in Ti-bearing blast furnace slag. The samples were taken from the liquid slag and quenched at once at elevated temperatures in order to analyze phase transaction of titanium and grain size of rutile crystals. Crystallization and growing kinetics of rutile crystals under elevated temperature conditions were calculated, and the crystallization process of rutile crystals under isothermal conditions was expressed by Avrami equation. The effects of experimental parameters, such as experimental temperatures, SiO2 addition, cooling rate, crystal seed addition and oxygen flow, were investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM), the optimal conditions for rutile crystals to grow up were obtained. Distribution and movement state of rutile crystals in the slag were analyzed.

  7. The determination and optimization of (rutile) pigment particle size distributions

    NASA Technical Reports Server (NTRS)

    Richards, L. W.

    1972-01-01

    A light scattering particle size test which can be used with materials having a broad particle size distribution is described. This test is useful for pigments. The relation between the particle size distribution of a rutile pigment and its optical performance in a gray tint test at low pigment concentration is calculated and compared with experimental data.

  8. Surface character and membranolytic activity of rutile and anatase: two titanium dioxide polymorphs.

    PubMed Central

    Nolan, R P; Langer, A M; Weisman, I; Herson, G B

    1987-01-01

    Biological studies of two titanium dioxide polymorphs, rutile and anatase, have produced conflicting results. Generally, the in vivo and in vitro methods used to evaluate pneumoconiotic dusts have shown the polymorphs to be inert, but occasionally both minerals have been reported to produce effects consistent with biologically active minerals. Many of these reports failed to specify which polymorph was used experimentally. While this limited the value of the data, the problem was further compounded by the variation in the surface properties of each polymorph depending on whether the specimen was a naturally occurring mineral or was made synthetically. Five naturally occurring and 11 synthetically produced titanium dioxide specimens were studied. The physical characterisation of each specimen entailed the determination of the polymorph type(s) by continuous scan x ray diffraction and the size distribution by transmission electron microscopy. The ability of each specimen to lyse erythrocytes was determined and compared with quartz. Only two, both synthetic rutiles, were found to be active. The hydrogen bonding ability of the surfaces of these rutiles were compared with inert rutile and quartz. The binding properties of the active rutile have been found to be consistent with those properties associated with biologically active quartz. The surface properties of rutile are the determinants of its activity. Because natural and synthetic rutiles possess different surface properties, they display different activities. Images PMID:3676122

  9. Application of rutile thermometry to eclogites

    NASA Astrophysics Data System (ADS)

    Zack, T.; Luvizotto, G. L.

    2005-12-01

    To evaluate how well the rutile thermometer (Zr content in rutile coexisting with zircon and quartz; Zack et al. 2004; CMP 148, 471-488) can be applied to eclogites, we measured 8 samples that cover the whole temperature range of naturally-occurring eclogites (400-900oC). SIMS is the method of choice for such a study as the low concentrations expected at only 400oC can be measured with very high precision (better than 5 percent on a 10 ppm level). We calibrated the Heidelberg SIMS by using relatively homogeneous rutiles that span a range of Zr contents (100, 260 and 770 ppm; determined by high-accuracy isotope dilution MC-ICP-MS). The calibration of the Heidelberg SIMS facility through these three rutiles as well as titanites, MPI-DING glasses and NIST-SRM 610 glass show no matrix effect for Zr determination outside 15 percent (2 sigma), thus SIMS analysis of Zr in rutile is straightforward. For all samples except one calculated temperatures agree with independently determined thermometry. However, even more encouraging is the fact that temperatures calculated from 5-10 rutiles within one sample agrees better than 20oC, hence enforcing the claim that rutile thermometry is a powerful tool for relative temperature determinations, as examplified for two UHP provinces (WGR and Erzgebirge).

  10. High-voltage atmospheric breakdown across intervening rutile dielectrics.

    SciTech Connect

    Williamson, Kenneth Martin; Simpson, Sean; Coats, Rebecca Sue; Jorgenson, Roy Eberhardt; Hjalmarson, Harold Paul; Pasik, Michael Francis

    2013-09-01

    This report documents work conducted in FY13 on electrical discharge experiments performed to develop predictive computational models of the fundamental processes of surface breakdown in the vicinity of high-permittivity material interfaces. Further, experiments were conducted to determine if free carrier electrons could be excited into the conduction band thus lowering the effective breakdown voltage when UV photons (4.66 eV) from a high energy pulsed laser were incident on the rutile sample. This report documents the numerical approach, the experimental setup, and summarizes the data and simulations. Lastly, it describes the path forward and challenges that must be overcome in order to improve future experiments for characterizing the breakdown behavior for rutile.

  11. LA-MC-ICPMS Pb Pb dating of rutile from slowly cooled granulites: Confirmation of the high closure temperature for Pb diffusion in rutile

    NASA Astrophysics Data System (ADS)

    Vry, Julie K.; Baker, Joel A.

    2006-04-01

    Rapid Pb-Pb dating of natural rutile crystals by laser ablation multiple-collector inductively coupled plasma mass spectrometry (LA-MC-ICPMS) is investigated as a tool for constraining geological temperature-time histories. LA-MC-ICPMS was used to analyse Pb isotopes in rutile from granulite-facies rocks from the Reynolds Range, Northern Territory, Australia. The resultant ages were compared with previous U-Pb zircon and monazite age determinations and new mica (muscovite, phlogopite, and biotite) Rb-Sr ages from the same metamorphic terrane. Rutile crystals ranging in size from 3.5 to 0.05 mm with ⩽20 ppm Pb were ablated with a 300-25 μm diameter laser beam. Crystals larger than 0.5 mm yielded sufficiently precise 206Pb/ 204Pb and 207Pb/ 204Pb ratios to correct for the presence of common Pb, and individual rutile crystals often exhibited sufficient Pb isotopic heterogeneity to allow isochron calculations to be performed on replicate analyses of a single crystal. The mean of 12 isochron ages is 1544 ± 8 Ma (2 SD), with isochron ages for single crystals having uncertainties as low as ±1.3 Myr (2 SD). The 207Pb- 206Pb ages calculated without correction for common Pb are typically <0.5% higher than the common-Pb-corrected isochron ages reflecting the very minor amounts of common Pb present in the rutile. The LA-MC-ICPMS method described samples only the outer 0.1-0.2 mm of the rutile crystals, resulting in a grain size-independent apparent closure temperature ( Tc) for Pb diffusion in rutile that is less than the Tc of monazite ⩽0.1 mm in diameter, but significantly higher than the Rb-Sr system in muscovite (550 °C), phlogopite (435 °C) and biotite (400 °C). Even small rutile crystals are extremely resistant to isotopic resetting. For the established slow cooling rate of ca. 3 °C/Myr, the Tc for Pb diffusion in the analysed rutile is ca. 630 °C. This is in excellent agreement with recent experimental results that indicate that rutile has a higher Tc than

  12. Study on the catalytic activity of vanadium doped TiO2: Anatase-to-rutile phase transition

    NASA Astrophysics Data System (ADS)

    Zhang, Huiming; Bian, He; Zhang, Shiguo

    2016-01-01

    The catalytic activity of vanadium doped TiO2 in the ethylbenzene oxidative dehydrogenation with CO2 was studied experimentally and theoretically. The experimental results showed that the reduction of ethylbenzene conversion and the styrene selectivity was caused by the transition of anatase to rutile phase. Theoretical results showed that the transition of the anatase to rutile phase was mainly caused by vanadium ions and oxygen vacancies.

  13. Zircon-rutile-ilmenite froth flotation process

    SciTech Connect

    Schmidt, R.; Denham, D.L. Jr.

    1992-04-21

    This patent describes a method for separating a mixture of minerals comprising at least zircon, ilmenite and rutile. It comprises adding an acid solution to the mixture to acidify to a pH of between about 2.0 and 6.0; adding starch to the mixture to depress the ilmenite and the rutile; adding a source of fluoride ions to the mixture to provide a negative surface charge on the zircon surface to activate the zircon; adding an amine cationic collector to the mixture to float the activated zircon; subjecting the mixture containing the added acid solution, the fluoride ions, the starch and the cationic collector, to froth flotation; and withdrawing a float product comprising the zircon and a sink product comprising the ilmenite and rutile.

  14. Self-assembly of multilevel branched rutile-type TiO2 structures via oriented lateral and twin attachment

    PubMed Central

    Jordan, Vanja; Javornik, Uroš; Plavec, Janez; Podgornik, Aleš; Rečnik, Aleksander

    2016-01-01

    Recent breakthrough of novel hierarchic materials, orchestrated through oriented attachment of crystal subunits, opened questions on what is the mechanism of their self-assembly. Using rutile-type TiO2, synthesized by hydrothermal reaction of Ti(IV)-butoxide in highly acidic aqueous medium, we uncovered the key processes controlling this nonclassical crystallization process. Formation of complex branched mesocrystals of rutile is accomplished by oriented assembly of precipitated fibers along the two low-energy planes, i.e. {110} and {101}, resulting in lateral attachment and twinning. Phase analysis of amorphous material enclosed in pockets between imperfectly assembled rutile fibers clearly shows harmonic ordering resembling that of the adjacent rutile structure. To our understanding this may be the first experimental evidence indicating the presence of electromagnetic force-fields that convey critical structural information through which oriented attachment of nanocrystals is made possible. PMID:27063110

  15. Self-assembly of multilevel branched rutile-type TiO2 structures via oriented lateral and twin attachment

    NASA Astrophysics Data System (ADS)

    Jordan, Vanja; Javornik, Uroš; Plavec, Janez; Podgornik, Aleš; Rečnik, Aleksander

    2016-04-01

    Recent breakthrough of novel hierarchic materials, orchestrated through oriented attachment of crystal subunits, opened questions on what is the mechanism of their self-assembly. Using rutile-type TiO2, synthesized by hydrothermal reaction of Ti(IV)-butoxide in highly acidic aqueous medium, we uncovered the key processes controlling this nonclassical crystallization process. Formation of complex branched mesocrystals of rutile is accomplished by oriented assembly of precipitated fibers along the two low-energy planes, i.e. {110} and {101}, resulting in lateral attachment and twinning. Phase analysis of amorphous material enclosed in pockets between imperfectly assembled rutile fibers clearly shows harmonic ordering resembling that of the adjacent rutile structure. To our understanding this may be the first experimental evidence indicating the presence of electromagnetic force-fields that convey critical structural information through which oriented attachment of nanocrystals is made possible.

  16. Element-specific Kikuchi patterns of Rutile.

    PubMed

    Vos, M; Winkelmann, A; Nolze, G

    2015-09-01

    The kinetic energy of keV electrons backscattered from a rutile (TiO2) surface depends measurably on the mass of the scattering atom. This makes it possible to determine separately the angular distribution of electrons backscattered elastically from either Ti or O. Diffraction effects of these backscattered electrons inside the rutile crystal lead to the formation of Kikuchi patterns. The element-resolved Kikuchi patterns of Ti and O differ characteristically, but each can be described fairly well in terms of the dynamical theory of diffraction. Qualitatively, much of the differences can be understood by considering the relative arrangement of the Ti and O atoms with respect to planes defined by the crystal lattice.

  17. Implications of near-rim compositional zoning in rutile for geothermometry, geospeedometry, and trace element equilibration

    NASA Astrophysics Data System (ADS)

    Kohn, Matthew J.; Penniston-Dorland, Sarah C.; Ferreira, Jean C. S.

    2016-10-01

    In principle, compositional profiling of the near-rim region of minerals can provide insight into cooling rates, but presumes that loss or gain of material from the crystal rim is not kinetically restricted. Trace element depth profiles collected for Zr, Hf, Ta, Nb, and U in amphibolite-facies rutile grains of the Catalina Schist, southern California, show significant variability within a single rock: Profiles of the same element among different grains can have significantly different slopes, grains with indistinguishable Zr profiles show vastly different Nb profiles, and grains with indistinguishable Nb profiles show different Zr profiles. Textural and kinetic idiosyncrasies within the matrix apparently affect the ability of specific crystals to accept or release trace elements, and impugn the common assumption that mineral surfaces maintain equilibrium at amphibolite-facies conditions. A new model that limits the flux of Zr from rutile grains helps explain commonly observed compositional profiles, and implies that inversion of compositional profiles assuming equilibrium among grain surfaces will invariably overestimate cooling rates. Few grains may record the low closure temperatures that experimentally determined diffusivities imply. Rather, higher temperatures will be retained, depending on the proximity of reactants and products in the matrix. Silicon diffusion does not control Zr reequilibration in rutile, and relative diffusion coefficients ( D's) of trace elements in rutile are D Zr ~ D Hf ~ 10 D Nb ~ 20 D Ta ~ 40 D U.

  18. Preparation of photoactive nitrogen-doped rutile

    NASA Astrophysics Data System (ADS)

    Dolat, D.; Moszyński, D.; Guskos, N.; Ohtani, B.; Morawski, A. W.

    2013-02-01

    An easy way of preparing highly N-doped rutile photocatalysts (N-TiO2/R) in tubular furnace in a constant ammonia (NH3) flow at 800-1000 °C temperature range is presented. New materials were compared to TiO2 samples prepared at the same temperatures in air atmosphere as well as to the starting material. Complete transformation of amorphous and anatase phases to rutile was confirmed by XRD method. Successful incorporation of relatively high amounts of nitrogen (up to 17% at.), in form of either TiO2(N), TiOxNy or TiN, on photocatalysts' surface and in their lattice was confirmed using XPS and XRD analysis. Also presence of Ti3+ was revealed by EPR studies. In contrast to pristine TiO2, the UV-vis/DR absorption spectra of N-modified photocatalysts extended significantly into the visible light region. Whereas nitrogen concentration as well as visible light absorption were found to increase with increasing modification temperature, photocatalytic activity was, on the contrary decreasing. This may be due to the very high nitrogen concentration, obtained at higher modification temperature, as well as the presence of small amount of conductive TiN phase on the N-TiO2/1000 °C photocatalyst surface. The artificial solar light activity of new photocatalysts after thermal treatment in NH3 increased in comparison to starting material, due to nitrogen modification and presence of Ti3+ ions. Activity under UV(-vis) light, though, decreased after modification procedure, probably due to smaller surface areas of new photocatalysts and complete anatase to rutile transformation.

  19. Compositional Variability of Rutile in Hydrothermal Ore Deposits

    NASA Astrophysics Data System (ADS)

    Clark, J. R.; Williams-Jones, A. E.

    2009-05-01

    Rutile is a relatively common accessory phase in many geological environments, and although it is almost always composed dominantly of TiO2, it is also associated with a wide range of minor and trace element substitutions. The most prominent minor elements that occur in rutile are Fe, Cr, V, Nb and Ta. Like Ti, the latter two elements are essentially immobile in most non-magmatic metallic ore deposits, and their concentrations in rutile are largely influenced by precursor mineral compositions. Iron, Cr and V concentrations vary considerably in rutile hosted by ore deposits, and reflect combinations of precursor mineral composition and the bulk chemistry of the local mineralized or altered rock environment. However, in hydrothermal alteration zones, rutile compositions are clearly anomalous compared to those in unaltered host rocks, and have distinctive elemental associations and substitutions in different types of ore deposits. We have evaluated the mineral chemistry of rutile in >40 ore deposits worldwide. In general, rutile in volcanogenic massive sulfide deposits contains Sn (and locally W, Sb and/or Cu). Rutile from mesothermal and related gold deposits invariably contains W, and in some of the larger and more important deposits, also contains Sb and/or V. Tungsten-bearing detrital rutile grains from the Witwatersrand suggest that paleoplacer mineralization may have had a mesothermal/orogenic gold source. In some magmatic-hydrothermal Pd-Ni-Cu deposits, rutile contains Ni and Cu. Rutile associated with granite-related Sn deposits has strongly elevated concentrations of Sn and W, and granite-pegmatite W-Sn deposits contain rutile with these elements plus Nb and Ta. The Olympic Dam deposit hosts rutile that is enriched in W, Sn and Cu. Rutile associated with porphyry and skarn Cu and Cu-Au deposits tends to contain elevated W, Cu (and sometimes V). Although many ore deposits have well-defined and diagnostic rutile compositions, there are some compositional

  20. 40 CFR 721.10230 - Rutile, tin zinc, calcium doped.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... the substance referred to in 40 CFR 721.10231 (PMN P-06-37; CAS No. 389623-07-8) combined. Persons who... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Rutile, tin zinc, calcium doped. 721... Substances § 721.10230 Rutile, tin zinc, calcium doped. (a) Chemical substance and significant new...

  1. 40 CFR 721.10230 - Rutile, tin zinc, calcium doped.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... the substance referred to in 40 CFR 721.10231 (PMN P-06-37; CAS No. 389623-07-8) combined. Persons who... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Rutile, tin zinc, calcium doped. 721... Substances § 721.10230 Rutile, tin zinc, calcium doped. (a) Chemical substance and significant new...

  2. Development of a Laser Ablation ICPMS Rutile Standard

    NASA Astrophysics Data System (ADS)

    Lytle, M. L.; Kohn, M. J.

    2015-12-01

    Rutile is a common accessory mineral in igneous and high-grade metamorphic rocks and igneous, with many applications in geosciences. Rutile geochemistry, especially the high field strength elements (i.e., Nb and Ta), monitors many geological processes including subduction-zone metamorphism, while Zr provides temperature information in buffering assemblages. Rutile can also be used for U-Pb geochronology, but typically low U concentrations can make age dating difficult. Many applications of rutile now rely on laser ablation ICPMS (LA-ICPMS) analysis, a major disadvantage of this technique is the lack of reliable rutile standards. Here, we present laser ablation data of several rutile megacrysts from around the world, illustrating typical geochemical characteristics of potential standards. Whole-grain transects and depth profiles were collected on several rutiles, including Graves Mountain, Kragerø, Madagascar, Mozambique, Quebec, and Diamantina. Most transects, particularly across Graves Mountain and Diamantina, show dramatic zoning in Zr (up to 100 ppm), U (up to 10 ppm), and Nb (up to 1000 ppm). Rutile grains from Mozambique and Kragerø show little variation in concentration in Zr, U, and Nb. However, U concentrations generally range from 1ppm (Graves Mountain) to 45ppm (Kragero). Depth profiles (30-80s analysis; 15-40 μm) showed a combination of slight surface contamination plus minor to significant near-rim zoning. Some samples, such as Mozambique, show minor concentration changes in Zr, Nb, and Ta over the outer 10 μm but are otherwise unzoned, whereas U concentrations decrease for 25 μm then are constant. Kragero shows depth zoning throughout for Zr, Ta, and U but Nb is unzoned. Some rutile megacrysts show promise as standards (e.g. Mozambique and Kragero), but must be prepared to eliminate crystal surfaces. Other megacrysts would have to be subsampled within specific crystals to isolate chemical homogeneous domains.

  3. Hyperparametric effects in a whispering-gallery mode rutile dielectric resonator at liquid helium temperatures

    SciTech Connect

    Nand, Nitin R.; Goryachev, Maxim; Floch, Jean-Michel le; Creedon, Daniel L.; Tobar, Michael E.

    2014-10-07

    We report the first observation of low power drive level sensitivity, hyperparametric amplification, and single-mode hyperparametric oscillations in a dielectric rutile whispering-gallery mode resonator at 4.2 K. The latter gives rise to a comb of sidebands at 19.756 GHz. Whereas, most frequency combs in the literature have been observed in optical systems using an ensemble of equally spaced modes in microresonators or fibers, the present work represents generation of a frequency comb using only a single-mode. The experimental observations are explained by an additional 1/2 degree-of-freedom originating from an intrinsic material nonlinearity at optical frequencies, which affects the microwave properties due to the extremely low loss of rutile. Using a model based on lumped circuits, we demonstrate that the resonance between the photonic and material 1/2 degree-of-freedom, is responsible for the hyperparametric energy transfer in the system.

  4. Surface speciation of yttrium and neodymium sorbed on rutile: Interpretations using the change distribution model.

    SciTech Connect

    Ridley, Mora K.; Hiemstra, T; Machesky, Michael L.; Wesolowski, David J; Van Riemsdijk, Willem H.

    2012-01-01

    The adsorption of Y3+ and Nd3+ onto rutile has been evaluated over a wide range of pH (3 11) and surface loading conditions, as well as at two ionic strengths (0.03 and 0.3 m), and temperatures (25 and 50 C). The experimental results reveal the same adsorption behavior for the two trivalent ions onto the rutile surface, with Nd3+ first adsorbing at slightly lower pH values. The adsorption of both Y3+ and Nd3+ commences at pH values below the pHznpc of rutile. The experimental results were evaluated using a charge distribution (CD) and multisite complexation (MUSIC) model, and Basic Stern layer description of the electric double layer (EDL). The coordination geometry of possible surface complexes were constrained by molecular-level information obtained from X-ray standing wave measurements and molecular dynamic (MD) simulation studies. X-ray standing wave measurements showed an inner-sphere tetradentate complex for Y3+ adsorption onto the (110) rutile surface (Zhang et al., 2004b). TheMDsimulation studies suggest additional bidentate complexes may form. The CD values for all surface species were calculated based on a bond valence interpretation of the surface complexes identified by X-ray and MD. The calculated CD values were corrected for the effect of dipole orientation of interfacial water. At low pH, the tetradentate complex provided excellent fits to the Y3+ and Nd3+ experimental data. The experimental and surface complexation modeling results show a strong pH dependence, and suggest that the tetradentate surface species hydrolyze with increasing pH. Furthermore, with increased surface loading of Y3+ on rutile the tetradentate binding mode was augmented by a hydrolyzed-bidentate Y3+ surface complex. Collectively, the experimental and surface complexation modeling results demonstrate that solution chemistry and surface loading impacts Y3+ surface speciation. The approach taken of incorporating molecular-scale information into surface complexation models (SCMs

  5. Surface speciation of yttrium and neodymium sorbed on rutile: Interpretations using the charge distribution model

    NASA Astrophysics Data System (ADS)

    Ridley, Moira K.; Hiemstra, Tjisse; Machesky, Michael L.; Wesolowski, David J.; van Riemsdijk, Willem H.

    2012-10-01

    The adsorption of Y3+ and Nd3+ onto rutile has been evaluated over a wide range of pH (3-11) and surface loading conditions, as well as at two ionic strengths (0.03 and 0.3 m), and temperatures (25 and 50 °C). The experimental results reveal the same adsorption behavior for the two trivalent ions onto the rutile surface, with Nd3+ first adsorbing at slightly lower pH values. The adsorption of both Y3+ and Nd3+ commences at pH values below the pHznpc of rutile. The experimental results were evaluated using a charge distribution (CD) and multisite complexation (MUSIC) model, and Basic Stern layer description of the electric double layer (EDL). The coordination geometry of possible surface complexes were constrained by molecular-level information obtained from X-ray standing wave measurements and molecular dynamic (MD) simulation studies. X-ray standing wave measurements showed an inner-sphere tetradentate complex for Y3+ adsorption onto the (1 1 0) rutile surface (Zhang et al., 2004b). The MD simulation studies suggest additional bidentate complexes may form. The CD values for all surface species were calculated based on a bond valence interpretation of the surface complexes identified by X-ray and MD. The calculated CD values were corrected for the effect of dipole orientation of interfacial water. At low pH, the tetradentate complex provided excellent fits to the Y3+ and Nd3+ experimental data. The experimental and surface complexation modeling results show a strong pH dependence, and suggest that the tetradentate surface species hydrolyze with increasing pH. Furthermore, with increased surface loading of Y3+ on rutile the tetradentate binding mode was augmented by a hydrolyzed-bidentate Y3+ surface complex. Collectively, the experimental and surface complexation modeling results demonstrate that solution chemistry and surface loading impacts Y3+ surface speciation. The approach taken of incorporating molecular-scale information into surface complexation models

  6. Rutile solubility in NaF-NaCl-KCl-bearing aqueous fluids at 0.5-2.79 GPa and 250-650 °C

    NASA Astrophysics Data System (ADS)

    Tanis, Elizabeth A.; Simon, Adam; Zhang, Youxue; Chow, Paul; Xiao, Yuming; Hanchar, John M.; Tschauner, Oliver; Shen, Guoyin

    2016-03-01

    The complex nature of trace element mobility in subduction zone environments is thought to be primarily controlled by fluid-rock interactions, episodic behavior of fluids released, mineral assemblages, and element partitioning during phase transformations and mineral breakdown throughout the transition from hydrated basalt to blueschist to eclogite. Quantitative data that constrain the partitioning of trace elements between fluid(s) and mineral(s) are required in order to model trace element mobility during prograde and retrograde metamorphic fluid evolution in subduction environments. The stability of rutile has been proposed to control the mobility of HFSE during subduction, accounting for the observed depletion of Nb and Ta in arc magmas. Recent experimental studies demonstrate that the solubility of rutile in aqueous fluids at temperatures >700 °C and pressures <2 GPa increases by several orders of magnitude relative to pure H2O as the concentrations of ligands (e.g., F and Cl) in the fluid increase. Considering that prograde devolatilization in arcs begins at ∼300 °C, there is a need for quantitative constraints on rutile solubility and the partitioning of HFSE between rutile and aqueous fluid over a wider range of temperature and pressure than is currently available. In this study, new experimental data are presented that quantify the solubility of rutile in aqueous fluids from 0.5 to 2.79 GPa and 250 to 650 °C. Rutile solubility was determined by using synchrotron X-ray fluorescence to measure the concentration of Zr in an aqueous fluid saturated with a Zr-bearing rutile crystal within a hydrothermal diamond anvil cell. At the PT conditions of the experiments, published diffusion data indicate that Zr is effectively immobile (log DZr ∼10-25 m2/s at 650 °C and ∼10-30 m2/s at 250 °C) with diffusion length-scales of <0.2 μm in rutile for our run durations (<10 h). Hence, the Zr/Ti ratio of the starting rutile, which was quantified, does not change

  7. The Magnet Cove Rutile Company mine, Hot Spring County, Arkansas

    USGS Publications Warehouse

    Kinney, Douglas M.

    1949-01-01

    The Magnet Cove Rutile Company mine was mapped by the U.S. Geological Survey in November 1944. The pits are on the northern edge of Magnet Cove and have been excavated in the oxidized zone of highly weathered and altered volcanic agglomerate. The agglomerate is composed of altered mafic igneous rocks in a matrix of white to gray clay, a highly altered tuff. The agglomerate appears layered and is composed of tuffaceous clay material below and igneous blocks above. The agglomerate is cut by aplite and lamprophyre dikes. Alkalic syenite dikes crop out on the ridge north of the pits. At the present stage of mine development the rutile seems to be concentrated in a narrow zone beneath the igneous blocks of the agglomerate. Rutile, associated with calcite and pyrite, occurs as disseminated acicular crystals and discontinuous vein-like masses in the altered tuff. Thin veins of rutile locally penetrate the mafic igneous blocks of the agglomerate.

  8. The Reaction Titanite+Kyanite=Anorthite+Rutile and Titanite-Rutile Barometry in Eclogites

    USGS Publications Warehouse

    Manning, C.F.; Bohlen, S.R.

    1991-01-01

    Titanite and rutile are a common mineral pair in eclogites, and many equilibria involving these phases are potentially useful in estimating pressures of metamorphism. We have reversed one such reaction, {Mathematical expression} using a piston-cylinder apparatus. Titanite+kyanite is the high-pressure assemblage and our results locate the equilibrium between 15.5 15.9, 17.7-17.9, 18.8-19.0, and 20.0-20.2 kb at 900, 1000, 1050, and 1100??C, respectively. The experiments require a positive dP/dT of between 20.5 and 23.5 bars/??C for the reaction. We use the reversed equilibrium and two other reactions, {Mathematical expression} and {Mathematical expression} to calculate metamorphic conditions for three eclogite localities. Using these reactions in conjunction with garnet-clinopyroxene Fe2+-Mg exchange equilibria, conditions of metamorphism were 16 kb and 750??C for kyaniteeclogites from Glenelg, Scotland, 21 kb and 625??C for eclogite-facies mica schists from the Tauern Window, Austria, and 46 kb and 850??C for eclogite-facies biotite gneisses from the Kokchetav Massif, USSR. For the Scottish and Austrian eclogites, the pressures derived from the titanite-rutile reactions provide additional constraints on pressures for these localities, leading to precise estimates of metamorphic conditions. In the case of the Soviet Union eclogites, the results show that the silicate-oxide assemblage is consistent with the remarkable occurrence of diamond inclusions in the garnets. The results of this study suggest that titanite and rutile stably coexist in many eclogites and that titanite solid solutions are ideal or nearly so. ?? 1991 Springer-Verlag.

  9. Rutile is holding Nb and Ta in the mantle, negligible Nb and Ta in the core

    NASA Astrophysics Data System (ADS)

    McDonough, W. F.; Rudnick, R. L.

    2008-12-01

    Continental Crust has a significant depletion in Nb and Ta relative to La that has been attributed to convergent margin (arc) magmatism and greater retention of Nb and Ta in the mantle source. This depleted pattern is a consequence of the plotting order of elements, which has been established by the relative partitioning behavior of elements during MORB-OIB genesis. It is our hypothesis that rutile in subducting slabs or delaminated lower continental crust is the important phase causing Nb(Ta)-depletion in the continental crust, as well as lowering its Nb/Ta. Experimental studies reveal a range of Nb/Ta fractionation responses in residual rutile depending on temperature and phase relations(melting vs dehydration). Examples of rutile-bearing, refractory eclogites have been identified that serve as analog materials for residues of the continental crust. These rutiles have radiogenic Hf isotopes (Vervoort, unpubl. data), and thus are not recent precipitates from metasomatic melts, as has been recently suggested. What remains is to understand the total silicate Earth's mass balance. In this regard, it is worth noting that early Archean Barbarton komatiites possess chondritic La/Nb ratios, and Nb/Ta ~15, a value comparable to Allende CV3 chondrite. This observation is not consistent with the storage of Nb (or Ta) in the core and suggests that the silicate Earth controls the planetary budget of Nb and Ta. Constraints on the amount of Nb in the core must be evaluated by multi-element approaches, using ratios of refractory lithophile elements. Chondritic ratios for La/Nb and Nb/Ta are not defined simply as a single value with a restricted range and are not always constant, with examples of both negligible and distinct differences between groups of chondrites. The database for chondrites is still small for Nb and Ta.

  10. Mechanisms of impurity diffusion in rutile

    SciTech Connect

    Peterson, N.L.; Sasaki, J.

    1984-01-01

    Tracer diffusion of /sup 46/Sc, /sup 51/Cr, /sup 54/Mn, /sup 59/Fe, /sup 60/Co, /sup 63/Ni, and /sup 95/Zr, was measured as functions of crystal orientation, temperature, and oxygen partial pressure in rutile single crystals using the radioactive tracer sectioning technique. Compared to cation self-diffusion, divalent impurities (e.g., Co and Ni) diffuse extremely rapidly in TiO/sub 2/ and exhibit a large anisotropy in the diffusion behavior; divalent-impurity diffusion parallel to the c-axis is much larger than it is perpendicular to the c-axis. The diffusion of trivalent impurity ions (Sc and Cr) and tetravalent impurity ions (Zr) is similar to cation self-diffusion, as a function of temperature and of oxygen partial pressure. The divalent impurity ions Co and Ni apparently diffuse as interstitial ions along open channels parallel to the c-axis. The results suggest that Sc, Cr, and Zr ions diffuse by an interstitialcy mechanism involving the simultaneous and cooperative migration of tetravalent interstitial titanium ions and the tracer-impurity ions. Iron ions diffused both as divalent and as trivalent ions. 8 figures.

  11. Thermo-selective TmxTi1-xO2-x/2 nanoparticles: from Tm-doped anatase TiO2 to a rutile/pyrochlore Tm2Ti2O7 mixture. An experimental and theoretical study with a photocatalytic application

    NASA Astrophysics Data System (ADS)

    Navas, Javier; Sánchez-Coronilla, Antonio; Aguilar, Teresa; de Los Santos, Desireé M.; Hernández, Norge C.; Alcántara, Rodrigo; Fernández-Lorenzo, Concha; Martín-Calleja, Joaquín

    2014-10-01

    This is an experimental and theoretical study of thulium doped TiO2 nanoparticles. From an experimental perspective, a method was used to synthesize thulium-doped TiO2 nanoparticles in which Tm3+ replaces Ti4+ in the lattice, which to our knowledge has neither been reported nor studied theoretically so far. Different proportions of anatase and rutile phases were obtained at different annealing temperatures, and XRD and Raman spectroscopy also revealed the presence of a pyrochlore phase (Tm2Ti2O7) at 1173 K. Thus, the structure of the Tm-doped nanoparticles was thermally-controlled. Furthermore, XPS showed the presence of Tm3+ in the samples synthesized, which produces oxygen vacancies to maintain the local neutrality in the lattice. The presence of Tm3+ in the samples led to changes in the UV-Vis absorption spectra, so they showed photoluminescence properties and new states in the band gap, which produce a new lower energy electronic transition than the main TiO2 one. Periodic DFT calculations were performed to understand the experimentally produced structures. The production of oxygen vacancies was analysed and the changes generated in the structure were fully detailed. The DOS and PDOS analyses confirmed the experimental results obtained using UV-Vis spectroscopy, and showed that the new electronic states in the band gap are due to interactions of the f state of Tm and the p state of O. Likewise, the charge study and the ELF analysis indicate that when Tm is introduced into the TiO2 structure, the Ti-O bond around the oxygen vacancy is strengthened. Finally, an example of a photocatalytic application was developed to show the high efficiency of the samples due to the heterojunction in the interfaces of the phases in the samples, which improved the charge separation and the good charge carrier mobility due to the presence of the pyrochlore phase, as was also shown theoretically.This is an experimental and theoretical study of thulium doped TiO2 nanoparticles. From

  12. Hydrogen Impurity Defects in Rutile TiO2

    PubMed Central

    Mo, Li-Bin; Wang, Yu; Bai, Yang; Xiang, Qing-Yun; Li, Qun; Yao, Wen-Qing; Wang, Jia-Ou; Ibrahim, Kurash; Wang, Huan-Hua; Wan, Cai-Hua; Cao, Jiang-Li

    2015-01-01

    Hydrogen-related defects play crucial roles in determining physical properties of their host oxides. In this work, we report our systematic experimental and theoretical (based on density functional theory) studies of the defect states formed in hydrogenated-rutile TiO2 in gaseous H2 and atomic H. In gas-hydrogenated TiO2, the incorporated hydrogen tends to occupy the oxygen vacancy site and negatively charged. The incorporated hydrogen takes the interstitial position in atom-hydrogenated TiO2, forming a weak O-H bond with the closest oxygen ion, and becomes positive. Both states of hydrogen affect the electronic structure of TiO2 mainly through changes of Ti 3d and O 2p states instead of the direct contributions of hydrogen. The resulted electronic structures of the hydrogenated TiO2 are manifested in modifications of the electrical and optical properties that will be useful for the design of new materials capable for green energy economy. PMID:26627134

  13. Hydrogen Impurity Defects in Rutile TiO2

    NASA Astrophysics Data System (ADS)

    Mo, Li-Bin; Wang, Yu; Bai, Yang; Xiang, Qing-Yun; Li, Qun; Yao, Wen-Qing; Wang, Jia-Ou; Ibrahim, Kurash; Wang, Huan-Hua; Wan, Cai-Hua; Cao, Jiang-Li

    2015-12-01

    Hydrogen-related defects play crucial roles in determining physical properties of their host oxides. In this work, we report our systematic experimental and theoretical (based on density functional theory) studies of the defect states formed in hydrogenated-rutile TiO2 in gaseous H2 and atomic H. In gas-hydrogenated TiO2, the incorporated hydrogen tends to occupy the oxygen vacancy site and negatively charged. The incorporated hydrogen takes the interstitial position in atom-hydrogenated TiO2, forming a weak O-H bond with the closest oxygen ion, and becomes positive. Both states of hydrogen affect the electronic structure of TiO2 mainly through changes of Ti 3d and O 2p states instead of the direct contributions of hydrogen. The resulted electronic structures of the hydrogenated TiO2 are manifested in modifications of the electrical and optical properties that will be useful for the design of new materials capable for green energy economy.

  14. Formation and Diffusion of Water Dimers on Rutile TiO2(110)

    NASA Astrophysics Data System (ADS)

    Matthiesen, J.; Hansen, J. Ø.; Wendt, S.; Lira, E.; Schaub, R.; Lægsgaard, E.; Besenbacher, F.; Hammer, B.

    2009-06-01

    From an interplay of time-lapsed high resolution scanning tunneling microscopy and density functional theory calculations we reveal the formation and diffusion of water dimers on hydrated rutile TiO2(110)-(1×1) surfaces, i.e., surfaces containing OHbr groups. At temperatures between ˜150 and ˜210K water monomers diffusing along the Ti troughs were found to form stable water dimers that diffuse faster than the water monomers. An H bond mediated rollover mechanism operating for the water dimers explains the experimental findings.

  15. Niobian rutile in an Apollo 14 KREEP fragment.

    NASA Technical Reports Server (NTRS)

    Hlava, P. F.; Prinz, M.; Keil, K.

    1972-01-01

    Niobian rutile was found in a KREEP lithic fragment of basaltic texture. The niobian rutile contains 85.3% TiO2, 7.1% Nb2O5, 2.65% Cr2O3, 0.70% ZrO2, 0.61% SiO2, 0.82% Al2O3 0.61% FeO, 0.52% CaO, 0.22% V2O3 in addition to minor amounts of MnO, MgO, and CeO2. Rare-earth elements were not detected, in contrast with lunar niobian rutile of Marvin (1971). Coexisting minerals in the KREEP fragment are major amounts of plagioclase and orthopyroxene, and minor amounts of olivine, ilmenite, augite, barian K-feldspar, whitlockite, troilite, Ni-Fe, zirkelite, and chromite.

  16. Microwave-hydrothermal process for the synthesis of rutile

    SciTech Connect

    Baldassari, Sara; Komarneni, Sridhar . E-mail: komarneni@psu.edu; Mariani, Emilia; Villa, Carla

    2005-11-03

    The synthesis of pure rutile titanium dioxide is not an easy achievement, as the crystallization process generally leads to mixtures of two or even three phases; moreover the synthetic processes normally used by industry require harsh reaction conditions. We carried out the synthesis of titanium dioxide from an aqueous titanium tetrachloride solution under microwave irradiation in the reaction time range of 5-120 min. We mostly obtained mixtures of rutile and anatase, but obtained single-phase rutile after a 2-h treatment at 160 deg. C; transmission electron micrographs revealed well-dispersed spherical nanoparticles. We also investigated the effects of dilution and addition of a dispersant (polyvinylpyrrolidone) on phase crystallization and particle shape.

  17. A recipe for the use of rutile in sedimentary provenance analysis

    NASA Astrophysics Data System (ADS)

    Triebold, Silke; von Eynatten, Hilmar; Zack, Thomas

    2012-12-01

    Rutile has received considerable attention in the last decade as a valuable petrogenetic indicator mineral. Based on both new and previously published data, we carve out advantages and pitfalls regarding TiO2-minerals in sedimentary provenance analysis. This results in a recipe for the use of rutile in provenance studies. The main points are: Rutile geochemistry from different grain size fractions does not differ systematically, and hence rutiles should be extracted from the fraction containing the most rutile grains (usually 63-200 μm). Similarly, different magnetic susceptibility of rutile does not systematically imply different trace element composition. Before interpretation of TiO2-mineral data, it is important to determine the polymorph type. Rutile, anatase and brookite appear to differ systematically in trace element composition. As an alternative to Raman spectroscopy, chemical classification according to Nb, Cr, Sn, Fe, V, and Zr concentrations can be applied. For rutile, a new host lithology discrimination scheme based on Cr-Nb systematics is introduced (x = 5 ∗ (Nb [ppm] - 500) - Cr [ppm]), which leads to better classification results than previously published discrimination methods. According to this equation, metamafic rutiles have negative values of x, while metapelitic rutiles have positive values. Evaluation of the growth temperature calculations of metamorphic rutile after different authors shows that the equations given by Tomkins et al. (2007) should be applied to both metamafic and metapelitic rutiles. Although there is a pressure effect on the Zr incorporation in rutile, the pressure range for most rutiles of 5-15 kbar introduces an uncertainty in calculated temperature of no more than ± 35 °C. The distribution of calculated temperatures from detrital rutiles is crucial; only well-defined temperature populations should be used for thermometry interpretation.

  18. Surface Complexation of Neodymium at the Rutile-Water Interface: A Potentiometric and Modeling Study in NaCl Media to 250°C

    SciTech Connect

    Ridley, Mora K.; Machesky, Michael L.; Wesolowski, David J; Palmer, Donald

    2005-01-01

    The adsorption of Nd{sup 3+} onto rutile surfaces was examined by potentiometric titration from 25 to 250 C, in 0.03 and 0.30m NaCl background electrolyte. Experimental results show that Nd{sup 3+} sorbs strongly, even at low temperature, with adsorption commencing below the pHznpc of rutile. In addition, there is a systematic increase in Nd{sup 3+} adsorption with increasing temperature. The experimental results were rationalized and described using surface oxygen proton affinities computed from the MUlti SIte Complexation or MUSIC model, coupled with a Stern-based three-layer description of the oxide/water interface. Moreover, molecular-scale information was incorporated successfully into the surface complexation model, providing a unique geometry for the adsorption of Nd{sup 3+} on rutile. The primary mode of Nd{sup 3+} adsorption was assumed to be the tetradentate configuration found for Y{sup 3+} adsorption on the rutile (110) surface from previously described in situ X-ray standing wave experiments, wherein the sorbing cations bond directly with two adjacent ''terminal'' and two adjacent ''bridging'' surface oxygen atoms. Similarly, the adsorption of Na{sup +} counterions was also assumed to be tetradentate, as supported by MD simulations of Na{sup +} interactions with the rutile (110) surface, and by analogous X-ray standing wave results for Rb{sup +} adsorption on rutile. Fitting parameters for Nd{sup 3+} adsorption included binding constants for the tetradentate adsorption complex and capacitance values for the inner-sphere binding plane. In addition, hydrolysis of the tetradentate adsorption complex was permitted and resulted in significantly improved model fits at higher temperature and pH values. The modeling results indicate that the Stern-based MUSIC surface-complexation model adequately accommodates molecular-scale information to uniquely rationalize and describe multivalent ion adsorption systematically into the hydrothermal regime.

  19. Surface complexation of neodymium at the rutile-water interface: A potentiometric and modeling study in NaCl media to 250°C

    NASA Astrophysics Data System (ADS)

    Ridley, Moira K.; Machesky, Michael L.; Wesolowski, David J.; Palmer, Donald A.

    2005-01-01

    The adsorption of Nd 3+ onto rutile surfaces was examined by potentiometric titration from 25 to 250°C, in 0.03 and 0.30 m NaCl background electrolyte. Experimental results show that Nd 3+ sorbs strongly, even at low temperature, with adsorption commencing below the pH znpc of rutile. In addition, there is a systematic increase in Nd 3+ adsorption with increasing temperature. The experimental results were rationalized and described using surface oxygen proton affinities computed from the MUlti SIte Complexation or MUSIC model, coupled with a Stern-based three-layer description of the oxide/water interface. Moreover, molecular-scale information was incorporated successfully into the surface complexation model, providing a unique geometry for the adsorption of Nd 3+ on rutile. The primary mode of Nd 3+ adsorption was assumed to be the tetradentate configuration found for Y 3+ adsorption on the rutile (110) surface from previously described in situ X-ray standing wave experiments, wherein the sorbing cations bond directly with two adjacent "terminal" and two adjacent "bridging" surface oxygen atoms. Similarly, the adsorption of Na + counterions was also assumed to be tetradentate, as supported by MD simulations of Na + interactions with the rutile (110) surface, and by analogous X-ray standing wave results for Rb + adsorption on rutile. Fitting parameters for Nd 3+ adsorption included binding constants for the tetradentate adsorption complex and capacitance values for the inner-sphere binding plane. In addition, hydrolysis of the tetradentate adsorption complex was permitted and resulted in significantly improved model fits at higher temperature and pH values. The modeling results indicate that the Stern-based MUSIC surface-complexation model adequately accommodates molecular-scale information to uniquely rationalize and describe multivalent ion adsorption systematically into the hydrothermal regime.

  20. Distribution of rutile in metamorphic rocks and implications for placer deposits

    USGS Publications Warehouse

    Goldsmith, R.; Force, E.R.

    1978-01-01

    Pelitic units in the eastern Great Smoky Mountains of the North Carolina Blue Ridge contain rutile grains only in kyanite and higher zones. Adjacent non-pelitic rocks do not contain rutile at kyanite grade but commonly contain sphene. Detrital rutile breaks down at metamorphic grades lower than those at which metamorphic rutile forms. Similarly, pelitic rocks in southeastern Connecticut contain rutile grains above, but not below, the sillimanite isograd. Most non-pelitic rocks there contain rutile only in the hypersthene zone. The slight difference in behavior of rutile in the two terranes is attributed primarily to a slight difference in calcium content of the pelites. In both areas, rutile commonly appears first as inclusions in garnet. Geologic maps showing metamorphic and stratigraphic or compositional information should be useful as prospecting tools for placer deposits. A variety of rocks at granulite facies and pelitic rocks of the upper amphibolite facies contain rutile and these could provide an extensive source for rutile in rutile placer deposits. ?? 1978 Springer-Verlag.

  1. Band Alignment and Controllable Electron Migration between Rutile and Anatase TiO2

    PubMed Central

    Mi, Yang; Weng, Yuxiang

    2015-01-01

    TiO2 is the most promising semiconductor for photocatalytic splitting of water for hydrogen and degradation of pollutants. The highly photocatalytic active form is its mixed phase of two polymorphs anatase and rutile rather than their pristine compositions. Such a synergetic effect is understood by the staggered band alignment favorable to spatial charge separation. However, electron migration in either direction between the two phases has been reported, the reason of which is still unknown. We determined the band alignment by a novel method, i.e., transient infrared absorption-excitation energy scanning spectra, showing their conduction bands being aligned, thus the electron migration direction is controlled by dynamical factors, such as varying the particle size of anatase, putting electron or hole scavengers on either the surface of anatase or rutile phases, or both. A quantitative criterion capable of predicting the migration direction under various conditions including particle size and surface chemical reactions is proposed, the predictions have been verified experimentally in several typical cases. This would give rise to a great potential in designing more effective titania photocatalysts. PMID:26169699

  2. UV-black rutile TiO{sub 2}: An antireflective photocatalytic nanostructure

    SciTech Connect

    Sanz, Ruy Zimbone, Massimo; Buccheri, Maria Antonietta; Scuderi, Viviana; Impellizzeri, Giuliana; Privitera, Vittorio; Romano, Lucia; Scuderi, Mario; Nicotra, Giuseppe; Jensen, Jens

    2015-02-21

    This work presents an experimental study on the specific quantitative contributions of antireflective and effective surface areas on the photocatalytic and antibacterial properties of rutile TiO{sub 2} nanospikes. They are studied when continuously distributed over the whole surface and when integrated into well-defined microstructures. The nanospikes were produced following MeV ion beam irradiation of bulk rutile TiO{sub 2} single crystals and subsequent chemical etching. The ion beam irradiation generated embedded isolated crystalline nanoparticles inside an etchable amorphous TiO{sub 2} layer, and nanospikes fixed to the not etchable TiO{sub 2} bulk substrate. The produced nanospikes are shown to resist towards aggressive chemical environments and act as an efficient UV antireflective surface. The photocatalytic activity experiments were performed under the ISO 10678:2010 protocol. The photonic and quantum efficiency are reported for the studied samples. The combined micro- and nanostructured surface triples the photonic efficiency compared to the initial flat surface. Results also revealed that the antireflective effect, due to the nanostructuring, is the dominating factor compared to the increase of surface area, for the observed photocatalytic response. The obtained results may be taken as a general strategy to design and precisely evaluate photoactive nanostructures.

  3. Density functional theory study of the mechanism of Li diffusion in rutile RuO{sub 2}

    SciTech Connect

    Jung, Jongboo; Cho, Maenghyo; Zhou, Min

    2014-01-15

    First-principle calculations are carried out to study the diffusion of Li ions in rutile structure RuO{sub 2}, a material for positive electrodes in rechargeable Li ion batteries. The calculations focus on migration pathways and energy barriers for diffusion in Li-poor and Li-rich phases using the Nudged Elastic Band Method. Diffusion coefficients estimated based on calculated energy barriers are in good agreement with experimental values reported in the literature. The results confirm the anisotropic nature of diffusion of Li ions in one-dimensional c channels along the [001] crystalline direction of rutile RuO{sub 2} and show that Li diffusion in the Li-poor phase is faster than in the Li-rich phase. The findings of fast Li diffusion and feasible Li insertion at low temperatures in the host rutile RuO{sub 2} suggest this material is a good ionic conductor for Li transport. The finding also suggests possible means for enhancing the performance of RuO{sub 2}-based electrode materials.

  4. Surface structures and thermodynamics of low-index of rutile, brookite and anatase - A comparative DFT study

    NASA Astrophysics Data System (ADS)

    Esch, Tobit R.; Gadaczek, Immanuel; Bredow, Thomas

    2014-01-01

    Titania surfaces have been studied theoretically and experimentally for many decades due to their photocatalytic properties. In this paper we present a theoretical study where we compare the low-index surfaces of rutile, anatase and brookite in terms of their stability and relaxation. The convergence behavior with the number of layers is analyzed with large all-electron basis sets and a hybrid DFT method (PW1PW). With this method a good agreement with recent experimental results for the surface relaxation is achieved. Frequency calculations for all considered surfaces were performed to obtain surface enthalpies and analyze the stability of the 1 × 1 surface-patterns.

  5. Zr-in-rutile thermometry in eclogite and vein from southwestern Tianshan, China

    NASA Astrophysics Data System (ADS)

    Chen, Zhen-Yu; Zhang, Li-Fei; Du, Jin-Xue; Lü, Zeng

    2013-02-01

    Trace element LA-ICPMS analyses of rutile from eclogites and veins from southwestern Tianshan, China, are carried out for testing the validity of Zr-in-rutile thermometry in low-T/UHP eclogites. Mineral inclusions in rutile and time-resolved mass spectrometer data are carefully examined to identify and reject contaminated data. The Zr contents vary between individual grains from the same sample; rutile inclusions in garnet, amphibole, and paragonite have a narrower range of Zr contents than matrix rutiles that always show the highest Zr contents, which reflects the progressive rutile growth in the eclogites. Average Zr concentrations in rutile from all six investigated eclogite samples statistically belong to one well-defined population (34 ± 5 ppm; 33 ± 11 ppm; 26 ± 7 ppm; 36 ± 17 ppm; 22 ± 6 ppm; 40 ± 17 ppm), while average Zr concentration in rutile from the three veins belong to a second well-defined population (55 ± 7 ppm; 66 ± 6 ppm; 55 ± 5 ppm). The peak temperature of eclogite can be estimated as 535-570 °C at a pressure of 2.7 GPa inverted from the discovery of well preserved coesite in an increasing number of rocks from southwestern Tianshan. The mineral assemblage of the veins suggests their retrograde formation in the epidote-amphibolite facies; the growth temperature of vein rutile is 530-540 °C at ˜1.0 GPa. A robust P-T path constructed by Zr-in-rutile thermometry in eclogites and veins indicates that the rocks underwent a rapid uplift involving an early isothermal decompression from eclogite to epidote-amphibolite facies. Zr in rutile from eclogites and veins can serve as a pressure indicator in study area that suggests the pressure has a significant effect to the Zr-in-rutile thermometry.

  6. Mineral inclusions in rutile: A novel recorder of HP-UHP metamorphism

    NASA Astrophysics Data System (ADS)

    Hart, Emma; Storey, Craig; Bruand, Emilie; Schertl, Hans-Peter; Alexander, Bruce D.

    2016-07-01

    The ability to accurately constrain the secular record of high- and ultra-high pressure metamorphism on Earth is potentially hampered as these rocks are metastable and prone to retrogression, particularly during exhumation. Rutile is among the most widespread and best preserved minerals in high- and ultra-high pressure rocks and a hitherto untested approach is to use mineral inclusions within rutile to record such conditions. In this study, rutiles from three different high- and ultrahigh-pressure massifs have been investigated for inclusions. Rutile is shown to contain inclusions of high-pressure minerals such as omphacite, garnet and high silica phengite, as well as diagnostic ultrahigh-pressure minerals, including the first reported occurrence of exceptionally preserved monomineralic coesite in rutile from the Dora-Maira massif. Chemical comparison of inclusion and matrix phases show that inclusions generally represent peak metamorphic assemblages; although rare prograde phases such as titanite, omphacite and corundum have also been identified implying that rutile grows continuously during prograde burial and traps mineralogic evidence of this evolution. Pressure estimates obtained from mineral inclusions, when used in conjunction with Zr-in-rutile thermometry, can provide additional constraints on the metamorphic conditions of the host rock. This study demonstrates that rutile is an excellent repository for high- and ultra-high pressure minerals and that the study of mineral inclusions in rutile may profoundly change the way we investigate and recover evidence of such events in both detrital populations and partially retrogressed samples.

  7. Transformations of PTCDA structures on rutile TiO2 induced by thermal annealing and intermolecular forces.

    PubMed

    Godlewski, Szymon; Prauzner-Bechcicki, Jakub S; Glatzel, Thilo; Meyer, Ernst; Szymoński, Marek

    2015-01-01

    Transformations of molecular structures formed by perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) molecules on a rutile TiO2(110) surface are studied with low-temperature scanning tunnelling microscopy. We demonstrate that metastable molecular assemblies transform into differently ordered structures either due to additional energy provided by thermal annealing or when the influence of intermolecular forces is increased by the enlarged amount of deposited molecules. Proper adjustment of molecular coverage and substrate temperature during deposition allows for fabrication of desired assemblies. Differences between PTCDA/TiO2(110) and PTCDA/TiO2(011) systems obtained through identical experimental procedures are discussed.

  8. 40 CFR 721.10231 - Rutile, tin zinc, sodium-doped.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... referred to in 40 CFR 721.10230 (PMN P-06-36; CAS No. 389623-01-2) combined. Persons who wish to pursue... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Rutile, tin zinc, sodium-doped. 721... Substances § 721.10231 Rutile, tin zinc, sodium-doped. (a) Chemical substance and significant new...

  9. 40 CFR 721.10231 - Rutile, tin zinc, sodium-doped.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... referred to in 40 CFR 721.10230 (PMN P-06-36; CAS No. 389623-01-2) combined. Persons who wish to pursue... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Rutile, tin zinc, sodium-doped. 721... Substances § 721.10231 Rutile, tin zinc, sodium-doped. (a) Chemical substance and significant new...

  10. A simple method to synthesize N-doped rutile titania with enhanced photocatalytic activity in sunlight

    SciTech Connect

    Gandhe, Aditi R.; Fernandes, Julio B. . E-mail: juliofernandes@rediffmail.com

    2005-09-15

    This study demonstrates a simple route for the synthesis of nanocrystalline N doped rutile titania by calcination of acidified TiCl{sub 3} in presence of urea. Urea was used as a source of nitrogen. The N doped rutile titania was yellow in colour and showed excellent photocatalytic activity in sunlight.

  11. Comparison of Dye-Sensitized Rutile- and Anatase-Based TiO2 Solar Cells

    SciTech Connect

    Park, N. G.; van de Lagemaat, J.; Frank, A. J.

    2000-01-01

    The objective of this work is to develop and optimize the new dye-sensitized solar cell technology. In view of the infancy of rutile material development for solar cells, the PV response of the dye-sensitized rutile-based solar cell is remarkably close to that of the anatase-based cell.

  12. Mossbauer and spectral (visible and near-IR) data for Fe(3+)-substituted rutile

    NASA Technical Reports Server (NTRS)

    Lauer, H. V., Jr.; Morris, R. V.; Vempati, R. K.

    1994-01-01

    Titanohematite and rutile containing some Fe(3+) are possible highly oxidized weathering products of ilmenite and titanomagnetities. We report here Moessbauer and reflectivity data (visible and near-IR) for Fe(3+)-substituted rutile as a part of our continuing studies of ferric-substituted minerals that might have bearing on the interpretation of Martian spectral data.

  13. Topotaxial reactions during the genesis of oriented rutile/hematite intergrowths from Mwinilunga (Zambia)

    NASA Astrophysics Data System (ADS)

    Rečnik, Aleksander; Stanković, Nadežda; Daneu, Nina

    2015-02-01

    Oriented rutile/hematite intergrowths from Mwinilunga in Zambia were investigated by electron microscopy methods in order to resolve the complex sequence of topotaxial reactions. The specimens are composed of up to several-centimeter-large euhedral hematite crystals covered by epitaxially grown reticulated rutile networks. Following a top-down analytical approach, the samples were studied from their macroscopic crystallographic features down to subnanometer-scale analysis of phase compositions and occurring interfaces. Already, a simple morphological analysis indicates that rutile and hematite are met near the orientation relationship. However, a more detailed structural analysis of rutile/hematite interfaces using electron diffraction and high-resolution transmission electron microscopy (HRTEM) has shown that the actual relationship between the rutile and hosting hematite is in fact . The intergrowth is dictated by the formation of equilibrium interfaces leading to 12 possible directions of rutile exsolution within a hematite matrix and 144 different incidences between the intergrown rutile crystals. Analyzing the potential rutile-rutile interfaces, these could be classified into four classes: (1) non-crystallographic contacts at 60° and 120°, (2) {101} twins with incidence angles of 114.44° and their complementaries at 65.56°, (3) {301} twins at 54.44° with complementaries at 125.56° and (4) low-angle tilt boundaries at 174.44° and 5.56°. Except for non-crystallographic contacts, all other rutile-rutile interfaces were confirmed in Mwinilunga samples. Using a HRTEM and high-angle annular dark-field scanning TEM methods combined with energy-dispersive X-ray spectroscopy, we identified remnants of ilmenite lamellae in the vicinity of rutile exsolutions, which were an important indication of the high-T formation of the primary ferrian-ilmenite crystals. Another type of exsolution process was observed in rutile crystals, where hematite precipitates

  14. Trace element composition of rutile and Zr-in-rutile thermometry in meta-ophiolitic rocks from the Kazdağ Massif, NW Turkey

    NASA Astrophysics Data System (ADS)

    Şengün, Fırat; Zack, Thomas

    2016-08-01

    In northwest Turkey, ophiolitic meta-gabbros are exposed on the Kazdağ Massif located in the southern part of the Biga Peninsula. Trace element composition of rutile and Zr-in-rutile temperatures were determined for meta-gabbros from the Kazdağ Massif. The Zr content of all rutiles range from 176 to 428 ppm and rutile grains usually have a homogeneous Zr distribution. The rutile grains from studied samples in the Kazdağ Massif are dominated by subchondritic Nb/Ta (11-19) and Zr/Hf ratios (20-33). Nb/Ta and Zr/Hf show positive correlation, which is probably produced by silicate fractionation. The Nb/Ta and Zr/Hf ratios increase with a decrease in Ta and Hf contents. The core of rutile grains are generally characterized by low Nb/Ta ratios of 17-18 whereas the rims exhibit relatively high Nb/Ta ratios of 19-23. Trace element analyses in rutile suggest that these rutile grains were grown from metamorphic fluids. The P-T conditions of meta-gabbros were estimated by both Fe-Mg exchange and Zr-in-rutile thermometers, as well as by the Grt-Hb-Plg-Q geothermobarometer. The temperature range of 639 to 662 °C calculated at 9 kbar using the Zr-in-rutile thermometer is comparable with temperature estimates of the Fe-Mg exchange thermometer, which records amphibolite-facies metamorphism of intermediate P-T conditions. The P-T conditions of meta-ophiolitic rocks suggest that they occur as a different separate higher-pressure tectonic slice in the Kazdağ metamorphic sequence. Amphibolite-facies metamorphism resulted from northward subduction of the İzmir-Ankara branch of the Neo-Tethyan Ocean under the Sakarya Zone. Metamorphism was followed by internal imbrication of the Kazdağ metamorphic sequence resulting from southerly directed compression during the collision.

  15. Extended model of the channel diffusivity in the rutile structure

    NASA Astrophysics Data System (ADS)

    Ruebenbauer, K.; Wdowik, U. D.; Kwater, M.; Kowalik, J. T.

    1996-11-01

    A model describing the diffusivity of a highly diluted and randomly distributed substitutional cationic impurity via the open and almost empty <001> channels in the rutile structure has been developed recently. The above model is based upon the assumption that the insignificant fraction of the impurities resides in the channels. An extended model is developed that allows for a significant fraction of the impurities to stay within channels, and it is used to evaluate emission Mössbauer spectra originating from the diffusing impurities embedded in single-crystalline samples. Final results are shown for the 14.4-keV Mössbauer line in 57Co(Fe). It is shown that spectral line positions depend upon the wave-vector transfer to the system, and that the data are sensitive to the fraction of both parent and daughter impurities residing in the channels.

  16. Plasma sprayed rutile titania-nanosilver antibacterial coatings

    NASA Astrophysics Data System (ADS)

    Gao, Jinjin; Zhao, Chengjian; Zhou, Jingfang; Li, Chunxia; Shao, Yiran; Shi, Chao; Zhu, Yingchun

    2015-11-01

    Rutile titania (TiO2) coatings have superior mechanical properties and excellent stability that make them preferential candidates for various applications. In order to prevent infection arising from bacteria, significant efforts have been focused on antibacterial TiO2 coatings. In the study, titania-nanosilver (TiO2/Ag) coatings with five different kinds of weight percentages of silver nanoparticles (AgNPs) were prepared by plasma spray. The feedstock powders, which had a composition of rutile TiO2 powders containing 1-10,000 ppm AgNPs, were double sintered and deposited on stainless steel substrates with optimized spraying parameters. X-Ray diffraction and scanning electron microscopy were used to analysize the phase composition and surface morphology of TiO2/Ag powders and coatings. Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) were employed to examine the antibacterial activity of the as-prepared coatings by bacterial counting method. The results showed that silver existed homogeneously in the TiO2/Ag coatings and no crystalline changed happened in the TiO2 structure. The reduction ratios on the TiO2/Ag coatings with 10 ppm AgNPs were as high as 94.8% and 95.6% for E. coli and S. aureus, respectively, and the TiO2/Ag coatings with 100-1000 ppm AgNPs exhibited 100% bactericidal activity against E. coli and S. aureus, which indicated the TiO2/Ag coatings with more than 10 ppm AgNPs had strong antibacterial activity. Moreover, the main factors influencing the antibacterial properties of TiO2/Ag coatings were discussed with grain size and the content of silver as well as the microstructure of the coatings.

  17. An oxygen barometer for rutile-ilmenite assemblages: oxidation state of metasomatic agents in the mantle

    NASA Astrophysics Data System (ADS)

    Zhao, Donggao; Essene, Eric J.; Zhang, Youxue

    1999-03-01

    Oxygen fugacity has been calculated for rutile-ilmenite assemblages from the reaction 2Fe 2O 3 (in ilmenite) + 4TiO 2 (rutile) = 4FeTiO 3 (in ilmenite) + O 2. The equation log fO 2=22.59-25925/ T-3.09log T+0.0016535 P+48.836 P/ T-4log aIlmFeTiO 3+2log aIlmFe 2O 3+4log aRutTiO 2, where T is in kelvin and P is in kbar, was derived from available thermodynamic data. The hypothetical end-member rutile-ilmenite reaction is located between the magnetite-hematite and Ni-NiO (NNO) buffers. The rutile-ilmenite oxygen barometer has been applied to ilmenite-bearing assemblages in mantle xenoliths from kimberlites, including the metasomatic MARID (mica-amphibole-rutile-ilmenite-diopside) suite and a MORID (mica-orthopyroxene-rutile-ilmenite-diopside) vein, along with rutile-ilmenite assemblages in eclogites and in Granny Smith diopside megacrysts. The oxygen fugacities of MARID and MORID lie around the NNO buffer and are comparable to those in metasomatized spinel lherzolites. Most MARID and MORID assemblages yield a more oxidizing fO 2 than the EMOD (enstatite-magnesite-olivine-diamond) buffer, such that MARID and MORID fluid or melt would tend to destroy diamond or graphite by oxidation.

  18. Secondary Ionization Mass Spectrometry (SIMS) U-Th-Pb Geochronology of Rutile Under O2+ Bombardment

    NASA Astrophysics Data System (ADS)

    Schmitt, A. K.; Zack, T.

    2012-12-01

    In-situ geochronology of rutile can be applied to a large range of geological problems, from exhumation of lower crust to sedimentary provenance. Recent attempts to improve SIMS U-Pb rutile dating were stifled by crystal orientation dependent instrumental fractionation between Pb and U, leading to considerable uncertainty in the calibration [1], [2]. Here, we demonstrate that injection of oxygen into the sputtered target region (O2 flooding) significantly reduces variation in the depth sputter rate for rutile. O2 flooding also correlates with increased homogeneity of the UO2+/U+ vs. Pb/U relative sensitivity calibration, resulting in higher precision for U-Pb ages. We also successfully tested an O2+ beam for rutile analysis. Natural and synthetic rutiles were found to efficiently dissipate local charges from positive ion bombardment, whereas charging largely prohibits the use of an O2+ primary beam for insulating silicates and phosphates that are common targets for in-situ geochronology. The advantage of the O2+ beam for rutile analysis is an ~10-times more intense beam current at a lateral resolution equivalent to conventionally used O- or O2- beams. The intense O2+ beam is also efficient in removing surficial Pb contamination. This leads to highly radiogenic Pb yields and combined with a 208Pb-based correction minimizes bias in the common Pb correction resulting from unresolved interferences on the conventionally used 204Pb. We compared three well-characterized rutiles where high-precision U-Pb ages are available: R10b (Gjerstad, Norway; 1090 Ma), R19 (Blumberg, Australia; 489.5 Ma), and JIMP-1B (Windmill Hills, Australia; 2625 Ma). O2+ -generated SIMS U-Pb and Pb-Pb age averages are accurate within <1% for Paleozoic to Archean rutile, the best accuracy reached so far for any in-situ rutile dating study. This underscores the potential of SIMS U-Th-Pb rutile geochronology at a precision and accuracy commensurate to zircon over a wide range of ages. Other potential

  19. Hydrothermal synthesis of anatase nanoleaves and size dependence of anatase-rutile transformation upon heating

    NASA Astrophysics Data System (ADS)

    Lisnycha, T. V.; Kirillov, S. A.; Potapenko, A. V.; Terikovska, T. E.; Kosilov, V. V.; Vyshnevskiy, O. A.

    2016-01-01

    Amorphous TiO2 obtained by adding TiCl4 to an alkaline medium crystallizes slowly and upon 3 years ageing transforms to nanosized anatase containing an admixture of brookite. The hydrothermal treatment of this sample in solutions of lithium hydroxide leads to anatase nanoleaves, and the more concentrated LiOH solution, the greater the nanoleaves and the smaller their specific surface area. The thermal treatment of nanoleaves leads to the bulk rutile, and the greater the specific surface area of anatase nanoleaves, the lower the anatase-rutile transition temperature. This is in line with conclusions based on the thermodynamic stability of nanosized anatase over the bulk rutile.

  20. Rutile and topaz in Precambrian gneiss, Jefferson and Clear Creek Counties, Colorado

    USGS Publications Warehouse

    Sheridan, Douglas M.; Taylor, Richard B.; Marsh, Sherman P.

    1968-01-01

    Disseminated rutile and major amounts of topaz have been identified in Precambrian topaz-quartz gneiss northwest of Evergreen, Colo. The rutile occurs in quartz-topaz-sillimanite gneiss that forms a stratigraphic unit which is 11 to 100 feet thick and is identified along strike for more than 7,000 feet. Three composite chip samples taken across this unit contain 2.2 to 4.2 percent of rutile, by weight, in grains averaging from 0.1 to 0.3 millimeter in size. The topaz content, by weight, in the same samples ranges from 23 to 67 percent.

  1. New Robust Reference Materials for In Situ Single Grain Rutile U-Pb Geochronology and Method Refinements for Detrital Rutile Analysis by LA-MC-ICP-MS

    NASA Astrophysics Data System (ADS)

    Parrish, R. R.; Bracciali, L.; Condon, D. J.; Horstwood, M. S.; Najman, Y.

    2012-12-01

    While rutile (TiO2) occurs in the heavy mineral suite of detrital sediments and originates mainly in medium- to high-grade metamorphic and some igneous rocks, there are very few applications of U-Pb dating of rutile to provenance studies; this is due to an overreliance on zircon, low U content of rutile limiting measurement quality by in situ methods, a higher proportion of common Pb relative to zircon, and a lack of widely available good quality reference materials. We have addressed these issues and characterized two ~ 1.8 Ga rutile reference materials by SEM, trace elements, U-Pb ID-TIMS, and intra-grain and inter-grain U-Pb LA-MC-ICP-MS analysis using mixed faraday and multiple ion counting detectors with high sensitivity. We have assessed U-Pb discordance and in situ variations in relative common Pb and age and their bearing on the quality of the reference materials for in situ U-Pb dating. The rutiles (Sugluk-4 and PCA-S207) come from granulite facies belts of the Canadian Shield, namely the northern Cape Smith Belt of Quebec and the Snowbird Tectonic Zone (Sasatchewan). The ID-TIMS data are slightly discordant due to variable common Pb and limited Pb loss; the variation in 6 single grains of Sugluk-4, that we use as the primary reference material, is <1% in 206Pb/238U, and <2% for 207Pb/206Pb (95 % conf.); after common Pb correction these variations are <1%. The measured variations are smaller than in existing reference materials (i.e. R10) in current use. LA-ICP-MC-MS data (n ~ 500 for each) have a reproducibility of 206Pb/238U and 207Pb/206Pb of ~2-4% (at the 2S level), which is only modestly worse than long-term data for multiple zircon standards, this being due to the real variation in measured values arising from limited Pb loss, age variation, and common Pb variability [1]. We have applied our refined method to the provenance of rutile from drainages from British Columbia, Bhutan, and the Brahmaputra River of NE India (predominant rutile ages ~ 50, 15

  2. Impact of anatase and rutile titanium dioxide nanoparticles on uptake carriers and efflux pumps in Caco-2 gut epithelial cells

    NASA Astrophysics Data System (ADS)

    Dorier, M.; Brun, E.; Veronesi, G.; Barreau, F.; Pernet-Gallay, K.; Desvergne, C.; Rabilloud, T.; Carapito, C.; Herlin-Boime, N.; Carrière, M.

    2015-04-01

    TiO2 microparticles are widely used in food products, where they are added as a white food colouring agent. This food additive contains a significant amount of nanoscale particles; still the impact of TiO2 nanoparticles (TiO2-NPs) on gut cells is poorly documented. Our study aimed at evaluating the impact of rutile and anatase TiO2-NPs on the main functions of enterocytes, i.e. nutrient absorption driven by solute-liquid carriers (SLC transporters) and protection against other xenobiotics driven by efflux pumps from the ATP-binding cassette (ABC) family. We show that acute exposure of Caco-2 cells to both anatase (12 nm) and rutile (20 nm) TiO2-NPs induce early upregulation of a battery of efflux pumps and nutrient transporters. In addition they cause overproduction of reactive oxygen species and misbalance redox repair systems, without inducing cell mortality or DNA damage. Taken together, these data suggest that TiO2-NPs may increase the functionality of gut epithelial cells, particularly their property to form a protective barrier against exogenous toxicants and to absorb nutrients.TiO2 microparticles are widely used in food products, where they are added as a white food colouring agent. This food additive contains a significant amount of nanoscale particles; still the impact of TiO2 nanoparticles (TiO2-NPs) on gut cells is poorly documented. Our study aimed at evaluating the impact of rutile and anatase TiO2-NPs on the main functions of enterocytes, i.e. nutrient absorption driven by solute-liquid carriers (SLC transporters) and protection against other xenobiotics driven by efflux pumps from the ATP-binding cassette (ABC) family. We show that acute exposure of Caco-2 cells to both anatase (12 nm) and rutile (20 nm) TiO2-NPs induce early upregulation of a battery of efflux pumps and nutrient transporters. In addition they cause overproduction of reactive oxygen species and misbalance redox repair systems, without inducing cell mortality or DNA damage. Taken

  3. Surface Protonation at the Rutile (110) Interface: Explicit Incorporation of Solvation Structure within the Refined MUSIC Model Framework

    SciTech Connect

    Machesky, Michael L.; Predota, M.; Wesolowski, David J

    2008-11-01

    The detailed solvation structure at the (110) surface of rutile ({alpha}-TiO{sub 2}) in contact with bulk liquid water has been obtained primarily from experimentally verified classical molecular dynamics (CMD) simulations of the ab initio-optimized surface in contact with SPC/E water. The results are used to explicitly quantify H-bonding interactions, which are then used within the refined MUSIC model framework to predict surface oxygen protonation constants. Quantum mechanical molecular dynamics (QMD) simulations in the presence of freely dissociable water molecules produced H-bond distributions around deprotonated surface oxygens very similar to those obtained by CMD with nondissociable SPC/E water, thereby confirming that the less computationally intensive CMD simulations provide accurate H-bond information. Utilizing this H-bond information within the refined MUSIC model, along with manually adjusted Ti-O surface bond lengths that are nonetheless within 0.05 {angstrom} of those obtained from static density functional theory (DFT) calculations and measured in X-ray reflectivity experiments (as well as bulk crystal values), give surface protonation constants that result in a calculated zero net proton charge pH value (pHznpc) at 25 C that agrees quantitatively with the experimentally determined value (5.4 {+-} 0.2) for a specific rutile powder dominated by the (110) crystal face. Moreover, the predicted pH{sub znpc} values agree to within 0.1 pH unit with those measured at all temperatures between 10 and 250 C. A slightly smaller manual adjustment of the DFT-derived Ti-O surface bond lengths was sufficient to bring the predicted pH{sub znpc} value of the rutile (110) surface at 25 C into quantitative agreement with the experimental value (4.8 {+-} 0.3) obtained from a polished and annealed rutile (110) single crystal surface in contact with dilute sodium nitrate solutions using second harmonic generation (SHG) intensity measurements as a function of ionic

  4. Modeling the surface complexation of calcium at the rutile-water interface to 250°C

    NASA Astrophysics Data System (ADS)

    Ridley, Moira K.; Machesky, Michael L.; Wesolowski, David J.; Palmer, Donald A.

    2004-01-01

    The adsorption behavior of metal-(hydr)oxide surfaces can be described and rationalized using a variety of surface complexation models. However, these models do not uniquely describe experimental data unless some additional insight into actual binding mechanisms for a given system is available. This paper presents the results of applying the MUlti SIte Complexation or MUSIC model, coupled with a Stern-based three layer description of the electric double layer, to Ca 2+ adsorption data on rutile surfaces from 25 to 250°C in 0.03 and 0.30 m NaCl background electrolyte. Model results reveal that the tetradentate adsorption configuration found for Sr 2+ adsorbed on the rutile (110) surface in the in situ X-ray standing wave experiments of Fenter et al. (2000) provides a good fit to all Ca 2+ adsorption data. Furthermore, it is also shown that equally good fits result from other plausible adsorption complexes, including various monodentate and bidentate adsorption configurations. These results amply demonstrate the utility of in situ spectroscopic data to constrain surface complexation modeling, and the ability of the MUSIC model approach to accommodate this spectroscopic information. Moreover, this is the first use of any surface complexation model to describe multivalent ion adsorption systematically into the hydrothermal regime.

  5. On the properties of binary rutile MO2 compounds, M = Ir, Ru, Sn, and Ti: A DFT study

    NASA Astrophysics Data System (ADS)

    Novell-Leruth, Gerard; Carchini, Giuliano; López, Núria

    2013-05-01

    We have studied the properties of bulk and different surfaces of rutile oxides, IrO2, RuO2, SnO2, and TiO2, and their binary compounds by means of density functional theory. As mixtures are employed in many applications, we have investigated the solubility, segregation, and overlayer formation of one of these oxides on a second metal from the series, as these aspects are critical for the chemical and electrochemical performances. Our results show that the bulk solubility is possible for several combinations. The electronic structure analysis indicates the activation of Ir states in IrxTi1-xO2 mixtures when compared to the parent IrO2 compound or the reduction in the band gap of TiO2 when Sn impurities are present. Segregation and oxygen-induced segregation of the second metal for the most common surfaces show a great extent of possibilities ranging from strong segregation to antisegregation, which depends on the oxygen ambient. The interaction of guest rutile overlayers on hosts is favourable and a wide range of growth properties (from multilayer formation to tridimensional particles) can be observed. Finally, a careful comparison with experimental information is presented, and for those cases where no data is available, the computed database can be used as a guideline by experimentalists.

  6. Inclusions of Cr- and Cr-Nb-Rutile in pyropes from the Internatsionalnaya kimberlite pipe, Yakutia

    NASA Astrophysics Data System (ADS)

    Rezvukhin, D. I.; Malkovets, V. G.; Sharygin, I. S.; Kuzmin, D. V.; Litasov, K. D.; Gibsher, A. A.; Pokhilenko, N. P.; Sobolev, N. V.

    2016-02-01

    The results of study of rutile inclusions in pyrope from the Internatsionalnaya kimberlite pipe are presented. Rutile is characterized by unusually high contents of impurities (up to 25 wt %). The presence of Cr2O3 (up to 9.75 wt %) and Nb2O5 (up to 15.57 wt %) are most typical. Rutile inclusions often occur in assemblage with Ti-rich oxides: picroilmenite and crichtonite group minerals. The Cr-pyropes with inclusions of rutile, picroilmenite, and crichtonite group minerals were formed in the lithospheric mantle beneath the Mirnyi field during their joint crystallization from melts enriched in Fe, Ti, and other incompatible elements as a result of metasomatic enrichment of the depleted lithospheric mantle.

  7. Formation of rutile fasciculate zone induced by sunlight irradiation at room temperature and its hemocompatibility.

    PubMed

    Zhang, Xuan-Hui; Zheng, Xiang; Cheng, Yuan; Li, Guo-Hua; Chen, Xiao-Ping; Zheng, Jian-Hui

    2013-08-01

    The fasciculate zone of phase pure rutile was fabricated under sunlight irradiation at room temperature, using titanium tetrachloride as a sole precursor. The crystal phase, morphology and microstructure, and optical absorption behavior of the samples were characterized by X-ray Diffraction, High-Resolution Transmission Electron Microscope (HRTEM) and UV-vis Diffuse Reflectance Spectra (DRS), respectively. XRD results show that the crystal phase of the sample is composed of rutile only, and a lattice distortion displays in the crystallite of the sample. HRTEM results show that the morphology of rutile particle is fasciculate zone constituted of nanoparticles with a diameter of 4-7 nm, and these particles grow one by one and step by step. The pattern of the selected area electron diffraction of the sample is Kikuchi type, which can be attributed to the predominant orientation growth of rutile nanoparticles along [001] induced by sunlight irradiation. DRS results show that the absorption threshold of the sample is 415 nm, corresponding to the band gap energy of 2.99 eV, which is lower than the band gap energy of rutile, 3.03 eV. Blood compatibility measurement shows that the sample has no remarkable effect on hemolytic and coagulation activity. The percent hemolysis of red blood cells is less than 5% even treated with a big dosage of the fasciculate rutile and under UV irradiation, and there are no obvious changes of plasma recalcification time after the rutile treatment. Thus, the novel structure of rutile fasciculate has low potential toxicity for blood and is hemocompatibility safe.

  8. 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.

  9. CoReO 4, a new rutile-type derivative with ordering of two cations

    NASA Astrophysics Data System (ADS)

    Baur, Werner H.; Joswig, Werner; Pieper, Gerhard; Kassner, Dethard

    1992-07-01

    CoReO 4 crystallizes in space group Cmmm with a = 6.5156(7)Å, b = 6.7418(8)Å, c = 2.8923(3)Å. It is most likely to be formulated as Co +3Re +5O 4. The bonding topology of the connections of the coordination octahedra around the Co and the Re atoms is identical to the arrangement of the coordination octahedra in the rutile type. Octahedral edge-sharing rutile-type chains of compositions CoO 4 and ReO 4 are present which are connected via corners, resulting in an overall chemical formula of CoReO 4. The space group type of CoReO 4, Cmmm, is a maximal nonisomorphic subgroup of order two of the space group type of rutile, P4 2/mnm; it is translationengleich with its supergroup. The space group type of MgUO 4, Imam, is in turn a maximal nonisomorphic subgroup of order two of space group Cmmm; it is klassengleich with its supergroup. Thus the structure type of CoReO 4 can be seen as an intermediate step in the reduction of the symmetry of the rutile type proper to the distorted rutile-type variant represented by MgUO 4. The crystal structure of CoReO 4 represents a new type derived from the rutile type by ordering of two cations. It is the fourth structure type of this kind.

  10. Novel Nanostructures of Rutile Fabricated by Templating against Yarns of Polystyrene Nanofibrils and Their Catalytic Applications

    PubMed Central

    Lu, Ping; Xia, Younan

    2013-01-01

    This article describes a facile approach to the synthesis of rutile nanostructures in the form of porous fibers or bundles of nanotubes by maneuvering the surface wettability of yarns made of polystyrene nanofibrils. Specifically, hierarchically porous fibers were obtained by hydrolyzing titanium tetraisopropoxide to form TiO2 nanoparticles in the void spaces among hydrophobic nanofibrils in each yarn. After calcination in air at 800 °C, the resultant fibers were comprised of many interconnected rutile nanoparticles whose diameters were in the range of 20–80 nm. After converting the nanofibrils and yarns into hydrophilic surfaces through plasma treatment, however, the TiO2 formed conformal coatings on the surfaces of nanofibrils in each yarn during hydrolysis instead of just filling the void spaces among the nanofibrils. As a result, bundles of rutile nanotubes were obtained after the sample had been calcined in air at 800 °C. The thermodynamically stable rutile nanostructures were then explored as supports for Pt nanoparticles whose catalytic activity was evaluated using the reduction of p-nitrophenol by NaBH4. The Pt supported on porous rutile fibers exhibited a better performance than the Pt on rutile nanotubes in terms of both induction time (tind) and apparent rate constant (kapp). PMID:23763369

  11. Multiple step growth of single crystalline rutile nanorods with the assistance of self-assembled monolayer for dye sensitized solar cells.

    PubMed

    Yang, Mengjin; Neupane, Suman; Wang, Xuewen; He, Jin; Li, Wenzhi; Pala, Nezih

    2013-10-01

    A novel multiple step growth (MSG) process has been developed to synthesize rutile nanorods (NRs) on fluorine-doped tin oxide (FTO) glass with the assistance of a self-assembled monolayer (SAM) aiming to increase the internal surface area of the 1D materials for dye sensitized solar cell (DSSC) applications. The experimental result reveals that the SAM layer can be selectively decomposed at the tip of the nanorod, namely the rutile (001) surface, due to the anisotropic photocatalytic property of the rutile. The remaining SAM layer on the side-wall of the NRs remains intact and serves as water repellent which prevents the radial growth of the NRs during the next step hydrothermal synthesis; therefore, the spacing between the NRs and the porosity of the NR array can be retained after additional growth cycles. On the other hand, introduction of a middle layer formed via TiCl4 solution treatment before the next growth cycle is found to be an effective way to control the diameters of the newly grown NRs. The performance of DSSC made from the rutile NRs grown using the MSG technique has been examined, and it is significantly affected by the internal surfaces of the NRs. Furthermore, the MSG combined with NR etching treatment by acid at low temperature (150 °C) leads to a significant enhancement in the solar cell performance. The gigantic wettability difference of the NRs before and after the SAM treatment as well as the MSG method could be adapted to prepare superhydrophobic and superhydrophilic nanostructured patterns for other applications.

  12. Electrochemical chlorine evolution at rutile oxide (110) surfaces.

    PubMed

    Hansen, Heine A; Man, Isabela C; Studt, Felix; Abild-Pedersen, Frank; Bligaard, Thomas; Rossmeisl, Jan

    2010-01-01

    Based on density functional theory (DFT) calculations we study the electrochemical chlorine evolution reaction on rutile (110) oxide surfaces. First we construct the Pourbaix surface diagram for IrO(2) and RuO(2), and from this we find the chlorine evolution reaction intermediates and identify the lowest overpotential at which all elementary reaction steps in the chlorine evolution reaction are downhill in free energy. This condition is then used as a measure for catalytic activity. Linear scaling relations between the binding energies of the intermediates and the oxygen binding energies at cus-sites are established for MO(2) (M being Ir, Ru, Pt, Ti). The linear relations form the basis for constructing a generalized surface phase diagram where two parameters, the potential and the binding energy of oxygen, are needed to determine the surface composition. We calculate the catalytic activity as function of the oxygen binding energy, giving rise to a Sabatier volcano. By combining the surface phase diagram and the volcano describing the catalytic activity, we find that the reaction mechanism differs depending on catalyst material. The flexibility in reaction path means that the chlorine evolution activity is high for a wide range of oxygen binding energies. We find that the required overpotential for chlorine evolution is lower than the overpotential necessary for oxygen evolution. PMID:20024470

  13. Surface and interstitial transition barriers in rutile (110) surface growth

    NASA Astrophysics Data System (ADS)

    Sanville, E. J.; Vernon, L. J.; Kenny, S. D.; Smith, R.; Moghaddam, Y.; Browne, C.; Mulheran, P.

    2009-12-01

    We present calculated surface and interstitial transition barriers for Ti, O, O2 , TiO, and TiO2 atoms and clusters at the rutile (110) surface. Defect structures involving these small clusters, including adcluster and interstitial binding sites, were calculated by energy minimization using density-functional theory (DFT). Transition energies between these defect sites were calculated using the NEB method. Additionally, a modified SMB-Q charge equilibration empirical potential and a fixed-charge empirical potential were used for a comparison of the transition energy barriers. Barriers of 1.2-3.5 eV were found for all studied small cluster transitions upon the surface except for transitions involving O2 . By contrast, the O2 diffusion barriers along the [001] direction upon the surface are only 0.13 eV. The QEq charge equilibration model gave mixed agreement with the DFT calculations, with the barriers ranging between 0.8 and 5.8 eV.

  14. A systematic evaluation of the Zr-in-rutile thermometer in ultra-high temperature (UHT) rocks

    NASA Astrophysics Data System (ADS)

    Pape, Jonas; Mezger, Klaus; Robyr, Martin

    2016-05-01

    The Zr-in-rutile geothermometer is potentially a widely applicable tool to estimate peak metamorphic temperatures in rocks from diverse geological settings. In order to evaluate its usefulness and reliability to record and preserve high temperatures in granulite facies rocks, rutile from UHT rocks was investigated to assess different mechanisms of Zr (re-)distribution following cooling from high temperature. Granulite facies paragneisses from the lowermost part of the Ivrea Zone, Italy, incorporated as thin sheets into the extensive basaltic body of the Mafic Complex were selected for this study. The results show that Zr-in-rutile thermometry, if properly applied, is well suited to identify and study UHT terranes as it preserves a record of temperatures up to 1190 °C, although the thermometer is susceptible to partial post-peak metamorphic resetting by Zr diffusion. Texturally homogeneous rutile grains preserve Zr concentrations corresponding to temperatures of prograde rutile growth. Diverse rutile textures and relationships between some rutile host grains and included or adjacent Zr-bearing phases bear testimony to varying mechanisms of partial redistribution and resetting of Zr in rutile during cooling and link Zr-in-rutile temperatures to different steps of the metamorphic evolution. Rutile grains that equilibrated their Zr concentrations at temperatures above 1070 °C (i.e. 1.1 wt% Zr) could not retain all Zr in the rutile structure during cooling and exsolved baddeleyite (ZrO2). By subsequent reaction of baddeleyite exsolution lamellae with SiO2, zircon needles formed before the system finally closed at 650-700 °C without significant net loss of Zr from the whole host rutile grain. By reintegration of zircon exsolution needles, peak metamorphic temperatures of up to 1190 °C are derived for the studied rocks, which demonstrates the suitability of this solution thermometer to record UHT conditions and also confirms the extraordinary geological setting of the

  15. Interstitial silicon ions in rutile Ti O2 crystals

    NASA Astrophysics Data System (ADS)

    Golden, E. M.; Giles, N. C.; Yang, Shan; Halliburton, L. E.

    2015-04-01

    Electron paramagnetic resonance (EPR) is used to identify a new and unique photoactive silicon-related point defect in single crystals of rutile Ti O2 . The importance of this defect lies in its assignment to interstitial silicon ions and the unexpected establishment of silicon impurities as a major hole trap in Ti O2 . Principal g values of this new S =1 /2 center are 1.9159, 1.9377, and 1.9668 with principal axes along the [1 ¯10 ],[001 ] , and [110 ] directions, respectively. Hyperfine structure in the EPR spectrum shows the unpaired spin interacting equally with two Ti nuclei and unequally with two Si nuclei. These silicon ions are present in the Ti O2 crystals as unintentional impurities. Principal values for the larger of the two Si hyperfine interactions are 91.4, 95.4, and 316.4 MHz with principal axes also along the [1 ¯10 ],[001 ] , and [110 ] directions. The model for the defect consists of two adjacent Si ions, one at a tetrahedral interstitial site and the other occupying a Ti site. Together, they form a neutral nonparamagnetic [Siint-S iTi] 0 complex. When a crystal is illuminated below 40 K with 442-nm laser light, holes are trapped by these silicon complexes and form paramagnetic [Siint-S iTi] + defects, while electrons are trapped at oxygen vacancies. Thermal anneal results show that the [Siint-S iTi] + EPR signal disappears in two steps, coinciding with the release of electrons from neutral oxygen vacancies and singly ionized oxygen vacancies. These released electrons recombine with the holes trapped at the silicon complexes.

  16. Transformations of PTCDA structures on rutile TiO2 induced by thermal annealing and intermolecular forces

    PubMed Central

    Godlewski, Szymon; Glatzel, Thilo; Meyer, Ernst; Szymoński, Marek

    2015-01-01

    Summary Transformations of molecular structures formed by perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) molecules on a rutile TiO2(110) surface are studied with low-temperature scanning tunnelling microscopy. We demonstrate that metastable molecular assemblies transform into differently ordered structures either due to additional energy provided by thermal annealing or when the influence of intermolecular forces is increased by the enlarged amount of deposited molecules. Proper adjustment of molecular coverage and substrate temperature during deposition allows for fabrication of desired assemblies. Differences between PTCDA/TiO2(110) and PTCDA/TiO2(011) systems obtained through identical experimental procedures are discussed. PMID:26199854

  17. EPR g factors and defect structures for V4+ and Cr5+ in the rutile-type crystals

    NASA Astrophysics Data System (ADS)

    Wang, Minjie; Zhu, Lianxuan

    2016-08-01

    The g-factor formulas for V4+ and Cr5+ ions in the rutile-type crystals are deduced from Jahn-Teller effect and contributions of the charge transfer levels. The tetragonal distortions ΔR = -0.0045, -0.0045 and -0.0067 nm, and Δθ = 0°, -0.001° and 0°, for GeO2:V4+, TiO2:V4+ and TiO2:Cr5+, respectively. The calculations of the g-factors agree well with the experimental values. The contributions of the charge transfer levels to g factors increase with the increasing valence state. It must be taken into account in the precise calculations of g factors for the high valence state d1 ions in crystals.

  18. Single grain detrital rutile U-Pb chronology: a key provenance tracer

    NASA Astrophysics Data System (ADS)

    Bracciali, Laura; Parrish, Randall R.; Najman, Yani; Horstwood, Matthew S. A.; Condon, Daniel J.

    2013-04-01

    Rutile is an accessory mineral commonly found in the heavy mineral suite of detrital rocks due to its stability during the sedimentary processes. This mineral originates mainly in medium- to high-grade metamorphic and some igneous rocks and similarly to zircon and other U-bearing minerals can be dated by the U-Pb method. Nevertheless, there are still very few applications of U-Pb dating of rutile to provenance studies, likely because it usually has a lower U content compared to zircon (which in turn leads to lower radiogenic Pb content limiting measurement quality) and it can contain a relatively large proportion of common (non radiogenic) Pb. In addition, there is a scarcity of widely available good quality natural rutile reference materials that can be used to assess reproducibility and accuracy of the dating technique. We have addressed these issues and characterized two ~ 1.8 Ga rutile reference materials (namely Sugluk-4 and PCA-S207 from granulite facies belts of the Canadian Shield) by SEM, trace elements, U-Pb ID-TIMS, and intra-grain and inter-grain U-Pb LA-MC-ICP-MS analysis. LA-U-Pb data (n ~ 500 for each of the two reference materials, collected using a New Wave Research 193 nm wavelength laser ablation system coupled to a Nu Plasma HR mass spectrometer) have a reproducibility of 206Pb/238U and 207Pb/206Pb of ~2-4% (at the 2? level), which is only modestly worse than long-term data for multiple zircon standards, this being due to the real variation in measured values arising from limited Pb loss, age variation related to cooling, and common Pb variability. The analytical measurement of rutile U-Pb data is rapid, allows high spatial resolution (the laser sampling protocol employs a 50 or 35 μm static spot) and does not include common Pb correction [1]. We have applied our refined method to constrain provenance of rutile from modern drainages from British Columbia and the eastern Himalaya (with rutile ages as young as 75% of all rutile grains in a

  19. Detrital rutile geochemistry and thermometry from the Dabie orogen: Implications for source-sediment links in a UHPM terrane

    NASA Astrophysics Data System (ADS)

    Liu, Lei; Xiao, Yilin; Wörner, G.; Kronz, A.; Simon, K.; Hou, Zhenhui

    2014-08-01

    This study explores the potential of detrital rutile geochemistry and thermometry as a provenance tracer in rocks from the Central Dabie ultrahigh-pressure metamorphic (UHPM) zone in east-central China that formed during Triassic continental collision. Trace element data of 176 detrital rutile grains selected from local river sediments and 91 rutile grains from distinct bedrocks in the Shuanghe and Bixiling areas, obtained by both electron microprobe (EMP) and in situ LA-ICP-MS analyses, suggest that geochemical compositions and thermometry of detrital rutiles are comparable to those from their potential source rocks. After certification of the Cr-Nb discrimination method for the Central Dabie UHPM zone, we show that 29% of the detrital rutiles in the Shuanghe area were derived from metamafic sources whereas in the Bixiling area that it is up to 76%. Furthermore, the proportion of distinct types of detrital rutiles combined with modal abundances of rutile in metapelites and metamafic bedrocks can be used to estimate the proportion of different source lithologies. Based on this method the proportion of mafic source rocks was estimated to ∼10% at Shuanghe and >60% at Bixiling, respectively, which is consistent with the proportions of eclogite (the major rutile-bearing metamafic rock) distribution in the field. Therefore, the investigation of detrital rutiles is a potential way to evaluate the proportion of metamafic rocks and even to prospect for metamafic bodies in UHPM terranes. Zr-in-rutile temperatures were calculated at different pressures and compared with temperatures derived from rock-in rutiles and garnet-clinopyroxene Fe-Mg thermometers. Temperatures calculated for detrital rutiles range from 606 °C to 707 °C and 566 °C to 752 °C in Shuanghe and Bixiling, respectively, at P = 3 GPa with an average temperatures of ca. 630 °C for both areas. These temperature averages and ranges are similar to those calculated for rutiles from surrounding source rocks

  20. Failure analysis of rutile sleeves in MC3080 lightning arrestor connectors.

    SciTech Connect

    Kilgo, Alice C.; Monroe, Saundra L.; Watson, Chad Samuel; Ernest, Terry L.

    2006-02-01

    The purpose of this SAND Report is to document efforts in the extraction and failure analyses of sleeve-style Lightning Arrestor Connectors (LACs). Several MC3080 and MC3079 LACs were recovered from the field and tested as part of the Enhanced Surveillance Campaign. A portion of these LACs failed retesting. Terry Ernest (01733), the LAC Component Engineer, provided eleven MC3080 LACs for evaluation where four of the LACs failed IR/DCW and one failed FRB requirements. The extraction of rutile sleeves from failed LACs was required to determine the source of failure. Rutile sleeves associated with connector function failures were examined for cracks, debris as well as any other anomalies which could have caused the LAC to not function properly. Sleeves that failed FRB or that experienced high FRB exhibited high symmetry, smooth surface, long-flow amicon, and slightly over-sized inside diameter. LACs that failed DCW or IR requirements had rutile sleeves that exhibited breakdown tracks.

  1. Precise size control over ultrafine rutile titania nanocrystallites in hierarchical nanotubular silica/titania hybrids with efficient photocatalytic activity.

    PubMed

    Gu, Yuanqing; Huang, Jianguo

    2013-08-12

    Hierarchical-structured nanotubular silica/titania hybrids incorporated with particle-size-controllable ultrafine rutile titania nanocrystallites were realized by deposition of ultrathin titania sandwiched silica gel films onto each nanofiber of natural cellulose substances (e.g., common commercial filter paper) and subsequent flame burning in air. The rapid flame burning transforms the initially amorphous titania into rutile phase titania, and the silica gel films suppress the crystallite growth of rutile titania, thereby achieving nano-precise size regulation of ultrafine rutile titania nanocrystallites densely embedded in the silica films of the nanotubes. The average diameters of these nanocrystallites are adjustable in a range of approximately 3.3-16.0 nm by a crystallite size increment rate of about 2.4 nm per titania deposition cycle. The silica films transfer the electrons activated by crystalline titania and generate catalytic reactive species at the outer surface. The size-tuned ultrafine rutile titania nanocrystallites distributed in the unique hierarchical networks significantly improve the photocatalytic performance of the rutile phase titania, thereby enabling a highly efficient photocatalytic degradation of the methylene blue dye under ultraviolet light irradiation, which is even superior to the pure anatase-titania-based materials. The facile stepwise size control of the rutile titania crystallites described here opens an effective pathway for the design and preparation of fine-nanostructured rutile phase titania materials to explore potential applications.

  2. Positron annihilation lifetime characterization of oxygen ion irradiated rutile TiO2

    NASA Astrophysics Data System (ADS)

    Luitel, Homnath; Sarkar, A.; Chakrabarti, Mahuya; Chattopadhyay, S.; Asokan, K.; Sanyal, D.

    2016-07-01

    Ferromagnetic ordering at room temperature has been induced in rutile phase of TiO2 polycrystalline sample by O ion irradiation. 96 MeV O ion induced defects in rutile TiO2 sample has been characterized by positron annihilation spectroscopic techniques. Positron annihilation results indicate the formation of cation vacancy (VTi, Ti vacancy) in these irradiated TiO2 samples. Ab initio density functional theoretical calculations indicate that in TiO2 magnetic moment can be induced either by creating Ti or O vacancies.

  3. Key Role of Rutile Structure for Layered Magnetism in Chromium Compounds

    NASA Astrophysics Data System (ADS)

    Kondo, Yasuhiro; Hotta, Takashi

    CrCl2 and CrF2 with the distorted Rutile-type crystal structure are known to exhibit different antiferromagnetic (AF) structures at low temperatures. CrF2 has a simple N_eel structure in common with other uorides, whereas CrCl2 exhibits a characteristic layered AF structure. We provide a simple scenario to understand the emergence of such layered AF structure on the basis of an orbital degenerate double-exchange model on the Rutile-type structure lattice.

  4. Ethanol photo-oxidation on a rutile TiO2(110) single crystal surface.

    PubMed

    Nadeem, A M; Muir, J M R; Connelly, K A; Adamson, B T; Metson, B J; Idriss, H

    2011-05-01

    The reaction of ethanol has been studied on the surface of rutile TiO(2)(110) by Temperature Programmed Desorption (TPD), online mass spectrometry under UV excitation and photoelectron spectroscopy while the adsorption energies of the molecular and dissociative modes of ethanol were computed using the DFT/GGA method. The most stable configuration is the dissociative adsorption in line with experimental results at room temperature. At 0.5 ML coverage the adsorption energy was found equal to 80 kJ mol(-1) for the dissociative mode (ethoxide, CH(3)CH(2)O(a) + H(a)) followed by the molecular mode (67 kJ mol(-1)). The orientation of the ethoxides along the [001] or [110] direction had minor effect on the adsorption energy although affected differently the Ti and O surface atomic positions. TPD after ethanol adsorption at 300 K indicated two main reactions: dehydration to ethylene and dehydrogenation to acetaldehyde. Pre-dosing the surface with ethanol at 300 K followed by exposure to UV resulted in the formation of acetaldehyde and hydrogen. The amount of acetaldehyde could be directly linked to the presence of gas phase O(2) in the vacuum chamber. The order of this photo-catalytic reaction with respect to O(2) was found to be 0.5. Part of acetaldehyde further reacted with O(2) under UV excitation to give surface acetate species. Because the rate of photo-oxidation of acetates (acetic acid) was slower than that of ethoxides (ethanol), the surface ended up by being covered with large amounts of acetates. A reaction mechanism for acetaldehyde, hydrogen and acetate formation under UV excitation is proposed. PMID:21225073

  5. Effect of TiO2 rutile nanorods on the photoelectrodes of dye-sensitized solar cells

    PubMed Central

    2013-01-01

    In order to enhance the electron transport on the photoelectrodes of dye-sensitized solar cells, one-dimensional rutile nanorods were prepared using electrospun TiO2 nanofibers. The grain size of the nanorods increased with increasing temperature. Electrochemical impedance spectroscopy measurements revealed reduced interface resistance of the cells with the one-dimensional rutile nanorods due to the improved electron transport and the enhanced electrolyte penetration. Intensity-modulated photocurrent/photovoltage spectroscopy showed that the one-dimensional rutile nanorods provided the electrons with a moving pathway and suppressed the recombination of photogenerated electrons. However, an excessive quantity of rutile nanorods created an obstacle to the electrons moving in the TiO2 thin film. The photoelectrode with 7 wt.% rutile nanorods optimized the performance of the dye-sensitized solar cells. PMID:23331863

  6. Vickers indentation hardness of stoichiometric and reduced single crystal TiO2 (rutile) from 25 to 800 C

    NASA Technical Reports Server (NTRS)

    Dellacorte, Christopher; Deadmore, Daniel L.

    1993-01-01

    The indentation microhardness of stoichiometric and reduced single crystal rutile (TiO2) from 25 to 800 C is presented in this paper. The results serve two main purposes. One is to assess the effect of rutile's stoichiometry on its hardness. The other is to test recently suggested theory on solid lubrication with sub Stoichiometric rutile in an effort to better understand shear controlled phenomenon. Microhardness was measured using a Vickers diamond indentor on both vacuum and hydrogen reduced single crystal rutile from 25 to 800 C. The results indicate that stoichiometry and temperature have a pronounced effect on rutile's hardness. The measured effects lend support to theory on solid lubrication by enhanced crystallographic slip and suggest that solid lubricant materials may be produced by careful atomic level tailoring (stoichiometry control).

  7. Crystallization and segregation in vitreous rutile films annealed at high temperature

    SciTech Connect

    Omari, M.A.; Sorbello, R.S.; Aita, C.R.

    2005-11-15

    Vitreous titania films with rutile short-range order were sputter deposited on unheated fused silica substrates, sequentially annealed at 973 and 1273 K, and examined by Raman microscopy, scanning electron microscopy, and x-ray diffraction. A segregated microstructure developed after the 1273 K anneal. This microstructure consists of supermicron-size craters dispersed in a matrix of submicron rutile crystals. Ti-O short-range order in the craters is characteristic of a mixture of two high pressure phases, m-TiO{sub 2} (monoclinic P2{sub 1}/c space group) and {alpha}-TiO{sub 2} (tetragonal Pbcn space group). We calculated that a high average compressive stress parallel to the substrate must be accommodated in the films at 1273 K, caused by the difference in the thermal expansion coefficients of titania and fused silica. The formation of the segregated microstructure is modeled by considering two processes at work at 1273 K to lower a film's internal energy: crystallization and nonuniform stress relief. The Gibbs-Thomson relation shows that small m-TiO{sub 2} crystallites are able to form directly from vitreous TiO{sub 2} at 1273 K. However, the preferred mechanism for forming {alpha}-TiO{sub 2} is likely to be by epitaxial growth at crystalline rutile twin boundaries (secondary crystallization). Both phases are denser than crystalline rutile and reduce the average thermal stress in the films.

  8. Effective dose in the manufacturing process of rutile covered welding electrodes.

    PubMed

    Herranz, M; Rozas, S; Pérez, C; Idoeta, R; Núñez-Lagos, R; Legarda, F

    2013-03-01

    Shielded metal arc welding using covered electrodes is the most common welding process. Sometimes the covering contains naturally occurring radioactive materials (NORMs). In Spain the most used electrodes are those covered with rutile mixed with other materials. Rutile contains some detectable natural radionuclides, so it can be considered a NORM. This paper mainly focuses on the use of MCNP (Monte Carlo N-Particle Transport Code) as a predictive tool to obtain doses in a factory which produces this type of electrode and assess the radiological impact in a specific facility after estimating the internal dose.To do this, in the facility, areas of highest radiation and positions of workers were identified, radioactive content of rutile and rutile covered electrodes was measured, and, considering a worst possible scenario, external dose at working points has been calculated using MCNP. This procedure has been validated comparing the results obtained with those from a pressurised ionisation chamber and TLD dosimeters. The internal dose has been calculated using DCAL (dose and risk calculation). The doses range between 8.8 and 394 μSv yr(-1), always lower than the effective dose limit for the public, 1 mSv yr(-1). The highest dose corresponds to the mixing area.

  9. Preparation of atomically flat rutile TiO2(001) surfaces for oxide film growth

    DOE PAGES

    Wang, Yang; Lee, Shinbuhm; Vilmercati, P.; Lee, Ho Nyung; Weitering, Hanno; Snijders, Paul C.

    2016-01-01

    The availability of low-index rutile TiO2 single crystal substrates with atomically flat surfaces is essential for enabling epitaxialgrowth of rutile transition metal oxide films. The high surface energy of the rutile (001) surface often leads to surface faceting, which precludes the sputter and annealing treatment commonly used for the preparation of clean and atomically flat TiO2(110) substrate surfaces. In this work, we reveal that stable and atomically flat rutile TiO2(001) surfaces can be prepared with an atomically ordered reconstructedsurface already during a furnace annealing treatment in air. We tentatively ascribe this result to the decrease in surface energy associated withmore » the surface reconstruction, which removes the driving force for faceting. Despite the narrow temperature window where this morphology can initially be formed, we demonstrate that it persists in homoepitaxialgrowth of TiO2(001) thin films. The stabilization of surface reconstructions that prevent faceting of high-surface-energy crystal faces may offer a promising avenue towards the realization of a wider range of high quality epitaxial transition metal oxide heterostructures.« less

  10. Niobium-Zirconium Systematics of Meteoritic Rutiles: Application to the Chronology of Mesosiderites

    NASA Astrophysics Data System (ADS)

    Haba, M. K.; Lai, Y.-J.; Yamaguchi, A.; Schönbächler, M.

    2016-08-01

    Nb-Zr systematics of rutiles from mesosiderites was obtained using MC-ICPMS. Our data show an initial 92Nb/93Nb ratio of ~10-5 in the mesosiderite formation region and provide chronological constraint on the early evolution of the parent body.

  11. Molecular modeling of fibronectin adsorption on topographically nanostructured rutile (110) surfaces

    NASA Astrophysics Data System (ADS)

    Guo, Chuangqiang; Wu, Chunya; Chen, Mingjun; Zheng, Ting; Chen, Ni; Cummings, Peter T.

    2016-10-01

    To investigate the topographical dependency of protein adsorption, molecular dynamics simulations were employed to describe the adsorption behavior of the tenth type-III module of fibronectin (FN-III10) on nanostructured rutile (110) surfaces. The results indicated that the residence time of adsorbed FN-III10 largely relied on its binding mode (direct or indirect) with the substrate and the region for protein migration on the periphery (protrusion) or in the interior (cavity or groove) of nanostructures. In the direct binding mode, FN-III10 molecules were found to be 'trapped' at the anchoring sites of rutile surface, or even penetrate deep into the interior of nanostructures, regardless of the presented geometrical features. In the indirect binding mode, FN-III10 molecules were indirectly connected to the substrate via a hydrogen-bond network (linking FN-III10 and interfacial hydrations). The facets created by nanostructures, which exerted restraints on protein migration, were suggested to play an important role in the stability of indirect FN-III10-rutile binding. However, a doubly unfavorable situation - indirect FN-III10-rutile connections bridged by a handful of mediating waters and few constraints on movement of protein provided by nanostructures - would result in an early desorption of protein.

  12. Atomically flat reconstructed rutile TiO2(001) surfaces for oxide film growth

    NASA Astrophysics Data System (ADS)

    Wang, Y.; Lee, S.; Vilmercati, P.; Lee, H. N.; Weitering, H. H.; Snijders, P. C.

    2016-02-01

    The availability of low-index rutile TiO2 single crystal substrates with atomically flat surfaces is essential for enabling epitaxial growth of rutile transition metal oxide films. The high surface energy of the rutile (001) surface often leads to surface faceting, which precludes the sputter and annealing treatment commonly used for the preparation of clean and atomically flat TiO2(110) substrate surfaces. In this work, we reveal that stable and atomically flat rutile TiO2(001) surfaces can be prepared with an atomically ordered reconstructed surface already during a furnace annealing treatment in air. We tentatively ascribe this result to the decrease in surface energy associated with the surface reconstruction, which removes the driving force for faceting. Despite the narrow temperature window where this morphology can initially be formed, we demonstrate that it persists in homoepitaxial growth of TiO2(001) thin films. The stabilization of surface reconstructions that prevent faceting of high-surface-energy crystal faces may offer a promising avenue towards the realization of a wider range of high quality epitaxial transition metal oxide heterostructures.

  13. Effective dose in the manufacturing process of rutile covered welding electrodes.

    PubMed

    Herranz, M; Rozas, S; Pérez, C; Idoeta, R; Núñez-Lagos, R; Legarda, F

    2013-03-01

    Shielded metal arc welding using covered electrodes is the most common welding process. Sometimes the covering contains naturally occurring radioactive materials (NORMs). In Spain the most used electrodes are those covered with rutile mixed with other materials. Rutile contains some detectable natural radionuclides, so it can be considered a NORM. This paper mainly focuses on the use of MCNP (Monte Carlo N-Particle Transport Code) as a predictive tool to obtain doses in a factory which produces this type of electrode and assess the radiological impact in a specific facility after estimating the internal dose.To do this, in the facility, areas of highest radiation and positions of workers were identified, radioactive content of rutile and rutile covered electrodes was measured, and, considering a worst possible scenario, external dose at working points has been calculated using MCNP. This procedure has been validated comparing the results obtained with those from a pressurised ionisation chamber and TLD dosimeters. The internal dose has been calculated using DCAL (dose and risk calculation). The doses range between 8.8 and 394 μSv yr(-1), always lower than the effective dose limit for the public, 1 mSv yr(-1). The highest dose corresponds to the mixing area. PMID:23324444

  14. Enhanced Photocatalytic H2 Production in Core-Shell Engineered Rutile TiO2.

    PubMed

    Yang, Yongqiang; Liu, Gang; Irvine, John T S; Cheng, Hui-Ming

    2016-07-01

    A rationally designed crystalline Ti(3+) core/amorphous Ti(4+) shell configuration can reverse the population disparity between holes and electrons reaching the surface of microsized rutile TiO2 photocatalyst, thus significantly enhancing its photocatalytic activity by two orders of magnitude in terms of the hydrogen production rate under the irradiation of UV-vis light. PMID:27159036

  15. Luna 20 - Mineral chemistry of spinel, pleonaste, chromite, ulvospinel, ilmenite and rutile.

    NASA Technical Reports Server (NTRS)

    Haggerty, S. E.

    1973-01-01

    Review of some of the results of a reflection microscopy and electron microprobe study performed on a part of the Luna 20 soil sample designated as the East Coast Consortium aliquot. The study is restricted to analyses of the oxides of Fe, Ti, Mg, Mn, Cr, and Al in this sample. The spinel mineral group, ilmenite and rutile only are discussed.

  16. Visible Light Absorption of N-Doped TiO2 Rutile Using (LR/RT)-TDDFT and Active Space EOMCCSD Calculations

    SciTech Connect

    Govind, Niranjan; Lopata, Kenneth A.; Rousseau, Roger J.; Andersen, Amity; Kowalski, Karol

    2011-11-03

    We have performed detailed ground and excited state calculations of pure and N-doped TiO2 rutile to model and analyze the experimentally observed UV/Vis spectrum. Using our embedding model we have performed both linear-response (LR) and real-time (RT) TDDFT calculations of the excited states of the pure and N-doped systems. We have also studied the lowest excitations using high-level active space equation-of-motion coupled cluster (EOMCC) approaches involving all single and inter-band double excitations. We compare and contrast the nature of the excitations in detail for the pure and doped systems and also provide an analysis of the excited-state density using our RT-TDDFT calculations. Our calculations indicate a lowering of the band gap and verify the role of the N3- states on the observed spectrum of N-doped TiO2 rutile as suggested by experimental findings. Both RT-TDDFT and EOMCC calculations show that the excitations in pure TiO2 are more delocalized compared with the N-doped system.

  17. Individual and binary toxicity of anatase and rutile nanoparticles towards Ceriodaphnia dubia.

    PubMed

    Iswarya, V; Bhuvaneshwari, M; Chandrasekaran, N; Mukherjee, Amitava

    2016-09-01

    Increasing usage of engineered nanoparticles, especially Titanium dioxide (TiO2) in various commercial products has necessitated their toxicity evaluation and risk assessment, especially in the aquatic ecosystem. In the present study, a comprehensive toxicity assessment of anatase and rutile NPs (individual as well as a binary mixture) has been carried out in a freshwater matrix on Ceriodaphnia dubia under different irradiation conditions viz., visible and UV-A. Anatase and rutile NPs produced an LC50 of about 37.04 and 48mg/L, respectively, under visible irradiation. However, lesser LC50 values of about 22.56 (anatase) and 23.76 (rutile) mg/L were noted under UV-A irradiation. A toxic unit (TU) approach was followed to determine the concentrations of binary mixtures of anatase and rutile. The binary mixture resulted in an antagonistic and additive effect under visible and UV-A irradiation, respectively. Among the two different modeling approaches used in the study, Marking-Dawson model was noted to be a more appropriate model than Abbott model for the toxicity evaluation of binary mixtures. The agglomeration of NPs played a significant role in the induction of antagonistic and additive effects by the mixture based on the irradiation applied. TEM and zeta potential analysis confirmed the surface interactions between anatase and rutile NPs in the mixture. Maximum uptake was noticed at 0.25 total TU of the binary mixture under visible irradiation and 1 TU of anatase NPs for UV-A irradiation. Individual NPs showed highest uptake under UV-A than visible irradiation. In contrast, binary mixture showed a difference in the uptake pattern based on the type of irradiation exposed. PMID:27522033

  18. Determination of electron and hole lifetimes of rutile and anatase TiO{sub 2} single crystals

    SciTech Connect

    Yamada, Yasuhiro; Kanemitsu, Yoshihiko

    2012-09-24

    The dynamical behavior of photoexcited states of TiO{sub 2} governs the activities of TiO{sub 2}-based solar cells and photocatalysts. We determined the lifetimes of photoexcited electrons and holes in rutile and anatase TiO{sub 2} single crystals by combining advantages of time-resolved photoluminescence, photoconductance, and transient absorption spectroscopy. Electrons and holes in rutile show exponential decays with the lifetime of a few tens of nanoseconds, while non-exponential decays are observed in anatase, indicating the presence of multiple carrier trapping processes. We revealed the generic features of the carrier recombination processes in rutile and anatase TiO{sub 2}.

  19. Reduced Step Edges on Rutile TiO2(110) as Competing Defects to Oxygen Vacancies on the Terraces and Reactive Sites for Ethanol Dissociation

    NASA Astrophysics Data System (ADS)

    Martinez, U.; Hansen, J. Ø.; Lira, E.; Kristoffersen, H. H.; Huo, P.; Bechstein, R.; Lægsgaard, E.; Besenbacher, F.; Hammer, B.; Wendt, S.

    2012-10-01

    The rutile TiO2(110) surface is the most studied surface of titania and considered as a prototype of transition metal oxide surfaces. Reactions on flat TiO2(110)-(1×1) surfaces are well studied, but the processes occurring on the step edges have barely been considered. Based on scanning tunneling microscopy studies, we here present experimental evidence for the existence of O vacancies along the ⟨11¯1⟩R step edges (OS vac.’s) on rutile TiO2(110). Both the distribution of bridging O vacancies on the terraces and temperature-programed reaction experiments of ethanol-covered TiO2(110) point to the existence of the OS vac.’s. Based on experiments and density functional theory calculations, we show that OS vac.’s are reactive sites for ethanol dissociation via O-H bond scission. Implications of these findings are discussed.

  20. Fine-grained rutile in the Gulf of Maine - diagenetic origin, source rocks, and sedimentary environment of deposition

    USGS Publications Warehouse

    Valentine, P.C.; Commeau, J.A.

    1990-01-01

    The Gulf of Maine, an embayment of the New England margin, is floored by shallow, glacially scoured basins that are partly filled with late Pleistocene and Holocene silt and clay containing 0.7 to 1.0 wt percent TiO2 chiefly in the form of silt-size rutile. Much of the rutile in the Gulf of Maine mud probably formed diagenetically in poorly cemented Carboniferous and Triassic coarse-grained sedimentary rocks of Nova Scotia and New Brunswick after the dissolution of titanium-rich detrital minerals (ilmenite, ilmenomagnetite). The diagenesis of rutile in coarse sedimentary rocks (especially arkose and graywacke) followed by erosion, segregation, and deposition (and including recycling of fine-grained rutile from shales) can serve as a model for predicting and prospecting for unconsolidated deposits of fine-grained TiO2. -from Authors

  1. Charge compensation in trivalent cation doped bulk rutile TiO2

    NASA Astrophysics Data System (ADS)

    Iwaszuk, Anna; Nolan, Michael

    2011-08-01

    Doping of TiO2 is a very active field, with a particularly large effort expended using density functional theory (DFT) to model doped TiO2; this interest has arisen from the potential for doping to be used in tuning the band gap of TiO2 for photocatalytic applications. Doping is also of importance for modifying the reactivity of an oxide. Finally, dopants can also be unintentionally incorporated into an oxide during processing, giving unexpected electronic properties. To unravel properly how doping impacts on the properties of a metal oxide requires a modelling approach that can describe such systems consistently. Unfortunately, DFT, as used in the majority of studies, is not suitable for application here and in many cases cannot even yield a qualitatively consistent description. In this paper we investigate the doping of bulk rutile TiO2 with trivalent cations, Al, Ga and In, using DFT, DFT corrected for on-site Coulomb interactions (DFT + U, with U on oxygen 2p states) and hybrid DFT (the screened exchange HSE06 exchange correlation functional) in an effort to better understand the performance of DFT in describing such fundamental doping scenarios and to analyse the process of charge compensation with these dopants. With all dopants, DFT delocalizes the oxygen hole polaron that results from substitution of Ti with the lower valence cation. DFT also finds an undistorted geometry and does not produce the characteristic polaron state in the band gap. DFT + U and hybrid DFT both localize the polaron, and this is accompanied by a distortion to the structure around the oxygen hole site. DFT + U and HSE06 both give a polaron state in the band gap. The band gap underestimation present in DFT + U means that the offset of the gap state from both the valence and the conduction band cannot be properly described, while the hybrid DFT offsets should be correct. We have investigated dopant charge compensation by formation of oxygen vacancies. Due to the large number of

  2. Charge compensation in trivalent cation doped bulk rutile TiO2.

    PubMed

    Iwaszuk, Anna; Nolan, Michael

    2011-08-24

    Doping of TiO(2) is a very active field, with a particularly large effort expended using density functional theory (DFT) to model doped TiO(2); this interest has arisen from the potential for doping to be used in tuning the band gap of TiO(2) for photocatalytic applications. Doping is also of importance for modifying the reactivity of an oxide. Finally, dopants can also be unintentionally incorporated into an oxide during processing, giving unexpected electronic properties. To unravel properly how doping impacts on the properties of a metal oxide requires a modelling approach that can describe such systems consistently. Unfortunately, DFT, as used in the majority of studies, is not suitable for application here and in many cases cannot even yield a qualitatively consistent description. In this paper we investigate the doping of bulk rutile TiO(2) with trivalent cations, Al, Ga and In, using DFT, DFT corrected for on-site Coulomb interactions (DFT + U, with U on oxygen 2p states) and hybrid DFT (the screened exchange HSE06 exchange correlation functional) in an effort to better understand the performance of DFT in describing such fundamental doping scenarios and to analyse the process of charge compensation with these dopants. With all dopants, DFT delocalizes the oxygen hole polaron that results from substitution of Ti with the lower valence cation. DFT also finds an undistorted geometry and does not produce the characteristic polaron state in the band gap. DFT + U and hybrid DFT both localize the polaron, and this is accompanied by a distortion to the structure around the oxygen hole site. DFT + U and HSE06 both give a polaron state in the band gap. The band gap underestimation present in DFT + U means that the offset of the gap state from both the valence and the conduction band cannot be properly described, while the hybrid DFT offsets should be correct. We have investigated dopant charge compensation by formation of oxygen vacancies. Due to the large number of

  3. Densely-packed ZnTPPs Monolayer on the Rutile TiO2(110)-(1×1) Surface: Adsorption Behavior and Energy Level Alignment

    PubMed Central

    Rangan, Sylvie; Ruggieri, Charles; Bartynski, Robert; Martínez, José Ignacio; Flores, Fernando; Ortega, José

    2016-01-01

    The adsorption of a densely packed Zinc(II) tetraphenylporphyrin monolayer on a rutile TiO2(110)-(1×1) surface has been studied using a combination of experimental and theoretical methods, aimed at analyzing the relation between adsorption behavior and barrier height formation. The adsorption configuration of ZnTPP was determined from scanning tunnel microscopy (STM) imaging, density functional theory (DFT) calculations and STM image simulation. The corresponding energy alignment was experimentally determined from X-ray and UV-photoemission spectroscopies and inverse photoemission spectroscopy. These results were found in good agreement with an appropriately corrected DFT model, pointing to the importance of local bonding and intermolecular interactions in the establishment of barrier heights. PMID:26998188

  4. Modeling the Interaction between Integrin-Binding Peptide (RGD) and Rutile Surface: The Effect of Cation Mediation on Asp Adsorption

    SciTech Connect

    Wu, Chunya; Skelton, Adam; Chen, Mingjun; Vlcek, Lukas; Cummings, Peter T

    2012-01-01

    The binding of a negatively charged residue, aspartic acid (Asp) in tripeptide arginine-glycine-aspartic acid, onto a negatively charged hydroxylated rutile (110) surface in aqueous solution, containing divalent (Mg{sup 2+}, Ca{sup 2+}, or Sr{sup 2+}) or monovalent (Na{sup +}, K{sup +}, or Rb{sup +}) cations, was studied by molecular dynamics (MD) simulations. The results indicate that ionic radii and charges will significantly affect the hydration, adsorption geometry, and distance of cations from the rutile surface, thereby regulating the Asp/rutile binding mode. The adsorption strength of monovalent cations on the rutile surface in the order Na{sup +} > K{sup +} > Rb{sup +} shows a 'reverse' lyotropic trend, while the divalent cations on the same surface exhibit a 'regular' lyotropic behavior with decreasing crystallographic radii (the adsorption strength of divalent cations: Sr{sup 2+} > Ca{sup 2+} > Mg{sup 2+}). The Asp side chain in NaCl, KCl, and RbCl solutions remains stably H-bonded to the surface hydroxyls and the inner-sphere adsorbed compensating monovalent cations act as a bridge between the COO{sup -} group and the rutile, helping to 'trap' the negatively charged Asp side chain on the negatively charged surface. In contrast, the mediating divalent cations actively participate in linking the COO{sup -} group to the rutile surface; thus the Asp side chain can remain stably on the rutile (110) surface, even if it is not involved in any hydrogen bonds with the surface hydroxyls. Inner- and outer-sphere geometries are all possible mediation modes for divalent cations in bridging the peptide to the rutile surface.

  5. Rietveld X-ray diffraction analysis of nanostructured rutile films of titania prepared by pulsed laser deposition

    SciTech Connect

    Murugesan, S.; Kuppusami, P.; Mohandas, E.

    2010-01-15

    Rietveld powder X-ray diffraction analysis of the rutile films of titanium oxide prepared by pulsed laser deposition was carried out. The crystallite size increased with increase of substrate temperature, while the strain showed a reverse trend. The films synthesized at temperature {>=}573 K showed that the crystal structure was almost close to that of bulk rutile structure. The influence of the substrate temperature on the lattice parameters and oxygen coordinates were also studied in the present work.

  6. Picosecond charge transport in rutile at high carrier densities studied by transient terahertz spectroscopy

    NASA Astrophysics Data System (ADS)

    Zajac, V.; Němec, H.; Kužel, P.

    2016-09-01

    We study terahertz photoconductivity of a rutile single crystal between 10 and 300 K under strong photoexcitation by femtosecond pulses at 266 nm. A marked dependence of the carrier mobility on the carrier density is observed leading to highly complex transport phenomena on a picosecond time scale. We develop a general model of carrier photoconductive response in the case of time dependent inhomogeneous distribution of carrier density and mobility. This allows us to assess an important role of both electrons and holes in the response of photoexcited rutile. At low temperatures, the carrier mobility is initially reduced due to the electron-hole scattering and increases by one order of magnitude upon ambipolar diffusion of the carriers into deeper regions of the sample. At room temperature, contributions of transient hot optical phonons and/or of midinfrared polaron excitations with charge-density-dependent dielectric strength emerge in the photoconductivity spectra.

  7. Evaluation of Surface State Mediated Charge Recombination in Anatase and Rutile TiO2

    PubMed Central

    2016-01-01

    In nanostructured thin films, photogenerated charge carriers can access the surface more easily than in dense films and thus react more readily. However, the high surface area of these films has also been associated with enhanced recombination losses via surface states. We herein use transient absorption spectroscopy to compare the ultrafast charge carrier kinetics in dense and nanostructured TiO2 films for its two most widely used polymorphs: anatase and rutile. We find that nanostructuring does not enhance recombination rates on ultrafast time scales, indicating that surface state mediated recombination is not a key loss pathway for either TiO2 polymorph. Rutile shows faster, and less intensity-dependent recombination than anatase, which we assign to its higher doping density. For both polymorphs, we conclude that bulk rather than surface recombination is the primary determinant of charge carrier lifetime. PMID:27564137

  8. Structure of latent tracks in rutile single crystal of titanium dioxide induced by swift heavy ions

    SciTech Connect

    Awazu, Koichi; Wang, Xiaomin; Fujimaki, Makoto; Komatsubara, Tetsuo; Ikeda, Takahiro; Ohki, Yoshimichi

    2006-08-15

    The structurally damaged zone in titanium dioxide rutile single crystal induced by MeV-order heavy ions was observed using high resolution electronic microscopy (HREM). Stressed regions as well as amorphous regions were identified in the damaged areas. Both stressed and amorphous regions were etched with hydrofluoric acid. The thermal spike model was used to calculate the track radii variation versus electron stopping power. When the calculated lattice temperature did not exceed the melting point of rutile titanium dioxide (2130 K), no structural change introduced by ions, such as 90 MeV Cl, was observed by HREM. It was found that the radius of the lattice temperature over the melting point corresponded closely to the radius of the stressed region. It was concluded that both stressed and amorphous regions are the result of quenching by molten titanium dioxide.

  9. Photoconductive detection of hydrogen in ZnO and rutile TiO2

    NASA Astrophysics Data System (ADS)

    Lavrov, E. V.; Mchedlidze, T.; Herklotz, F.

    2016-08-01

    Hydrogen donors in ZnO and rutile TiO2 are probed by means of photoconductivity and IR absorption. It is shown that the O-H bonds giving rise to the local vibrational modes (LVMs) of interstitial hydrogen at 3611 and 3290 cm-1 in the case of ZnO and TiO2, respectively, also occur in the photoconductivity spectra as Fano resonances. The effects of isotope substitution, concentration, sample thickness, influence of other donors present in both oxides are considered. Based on the shape and frequency of these resonances, it is concluded that the apparent ionization energy of interstitial hydrogen in rutile TiO2 is less than 300 meV. By a direct comparison, we also demonstrate that photoconductive detection of LVMs of defects in thin semiconductor films is superior to the standard IR absorption.

  10. Selective scanning tunneling microscope light emission from rutile phase of VO2.

    PubMed

    Sakai, Joe; Kuwahara, Masashi; Hotsuki, Masaki; Katano, Satoshi; Uehara, Yoichi

    2016-09-28

    We observed scanning tunneling microscope light emission (STM-LE) induced by a tunneling current at the gap between an Ag tip and a VO2 thin film, in parallel to scanning tunneling spectroscopy (STS) profiles. The 34 nm thick VO2 film grown on a rutile TiO2 (0 0 1) substrate consisted of both rutile (R)- and monoclinic (M)-structure phases of a few 10 nm-sized domains at room temperature. We found that STM-LE with a certain photon energy of 2.0 eV occurs selectively from R-phase domains of VO2, while no STM-LE was observed from M-phase. The mechanism of STM-LE from R-phase VO2 was determined to be an interband transition process rather than inverse photoemission or inelastic tunneling processes. PMID:27460183

  11. Selective scanning tunneling microscope light emission from rutile phase of VO2

    NASA Astrophysics Data System (ADS)

    Sakai, Joe; Kuwahara, Masashi; Hotsuki, Masaki; Katano, Satoshi; Uehara, Yoichi

    2016-09-01

    We observed scanning tunneling microscope light emission (STM-LE) induced by a tunneling current at the gap between an Ag tip and a VO2 thin film, in parallel to scanning tunneling spectroscopy (STS) profiles. The 34 nm thick VO2 film grown on a rutile TiO2 (0 0 1) substrate consisted of both rutile (R)- and monoclinic (M)-structure phases of a few 10 nm-sized domains at room temperature. We found that STM-LE with a certain photon energy of 2.0 eV occurs selectively from R-phase domains of VO2, while no STM-LE was observed from M-phase. The mechanism of STM-LE from R-phase VO2 was determined to be an interband transition process rather than inverse photoemission or inelastic tunneling processes.

  12. Rutile TiO2 nanowires on anatase TiO2 nanofibers: a branched heterostructured photocatalysts via interface-assisted fabrication approach.

    PubMed

    Wang, Changhua; Zhang, Xintong; Shao, Changlu; Zhang, Yanli; Yang, Jikai; Sun, Panpan; Liu, Xueping; Liu, Hong; Liu, Yichun; Xie, Tengfeng; Wang, Dejun

    2011-11-01

    A water-dichloromethane interface-assisted hydrothermal method was employed to grow rutile TiO(2) nanowires (NWs) on electrospun anatase TiO(2) nanofibers (NFs), using highly reactive TiCl(4) as precursor. The water-dichloromethane interface inhibited the formation of rutile NWs in water phase, but promoted the selective radial growth of densely packed rutile NWs on anatase NFs to form a branched heterojunction. The density and length of rutile NWs could be readily controlled by varying reaction parameters. A formation mechanism for the branched heterojunction was proposed which involved (1) the entrapment of rutile precursor nanoparticles at water-dichloromethane interface, (2) the growth of rutile NWs on anatase NFs via Ostwald ripening through the scavengering of interface-entrapped rutile nanoparticles. The heterojunction formed at anatase NF and rutile NW enhanced the charge separation of both under ultraviolet excitation, as evidenced by photoluminescence and surface photovoltage spectra. The branched TiO(2) heterostructures showed higher photocatalytic activity in degradation of rodamine B dye solution than anatase NFs, and the mixture of anatase NFs, and P25 powders, which was discussed in terms of the synergistic effect of enhanced charge separation by anatase-rutile heterojunction, high activity of rutile NWs, and increased specific area of branched heterostructures.

  13. Synergistic effect between anatase and rutile TiO2 nanoparticles in dye-sensitized solar cells.

    PubMed

    Li, Gonghu; Richter, Christiaan P; Milot, Rebecca L; Cai, Lawrence; Schmuttenmaer, Charles A; Crabtree, Robert H; Brudvig, Gary W; Batista, Victor S

    2009-12-01

    A synergistic effect between anatase and rutile TiO2 is known, in which the addition of rutile can remarkably enhance the photocatalytic activity of anatase in the degradation of organic contaminants. In this study, mixed-phase TiO2 nanocomposites consisting of anatase and rutile nanoparticles (NPs) were prepared for use as photoanodes in dye-sensitized solar cells (DSSCs) and were characterized by using UV-vis spectroscopy, powder X-ray diffraction and scanning electron microscopy. The addition of 10-15% rutile significantly improved light harvesting and the overall solar conversion efficiency of anatase NPs in DSSCs. The underlying mechanism for the synergistic effect in DSSCs is now explored by using time-resolved terahertz spectroscopy. It is clearly demonstrated that photo-excited electrons injected into the rutile NPs can migrate to the conduction band of anatase NPs, enhancing the photocurrent and efficiency. Interfacial electron transfer from rutile to anatase, similar to that in heterogeneous photocatalysis, is proposed to account for the synergistic effect in DSSCs. Our results further suggest that the synergistic effect can be used to explain the beneficial effect of TiCl4 treatment on DSSC efficiency.

  14. Textural relationship and compositions of ilmenite-corundum exsolutions in rutile from kimberlitic kyanite eclogite xenoliths: microstructural evidence using EBSD

    NASA Astrophysics Data System (ADS)

    Sobolev, N. V.; Schertl, H.; Neuser, R. D.; Lavrentiev, Y. G.; Logvinova, A. M.; Usova, L. V.

    2007-12-01

    Rutile is one of the most common accessory minerals in high pressure (HP) and ultrahigh-pressure (UHP) rocks of crustal and mantle origin. Among those rocks eclogites are very abundant in metamorphic belts and as xenoliths in kimberlite pipes. Some of these xenoliths contain coesite or diamond. Eclogite xenolith rutiles contain high abundance of minor elements reaching up to 0.8 wt.% Al2O3, 2.5 wt.% Fe2O3, 1.4 wt.% Nb2O5, 0.45 wt.% ZrO2 and are mostly heterogeneous with widely varying Al, Fe and Mg contents. These heterogeneities are caused by the presence of closely associated sigmoidal oriented lamellae of ilmenite and corundum which have been detected for the first time in rutile from Roberts Victor mine eclogite xenolith (Sobolev, Yefimova, 2000, Intern. Geol. Rev., v. 42, p. 758-767). We report here on the wide occurrence of such lamellae in rutiles both from diamondiferous kyanite eclogites of Udachnaya mine, Siberia and more samples from Roberts Victor mine confirmed by EMPA. Electron backscatter diffraction (EBSD) measurements on two rutile grains from Roberts Victor mine kyanite eclogite confirm the presence of ilmenite plus corundum exsolutions. We found evidence for respective different crystallographic orientations related to the surrounded rutile host which will be demonstrated in detail in the present study.

  15. Domain structures in rutile in ultrahigh-pressure metamorphic rocks from Dabie Mountains, China.

    PubMed

    Meng, D W; Wu, X L; Meng, X; Han, Y J; Li, D X

    2004-01-01

    According to the HRTEM study, the UHP jadeite-quartzite mineral (Rutile, TiO(2)) in Anhui Province, Dabie Mountains, China, has ultrastructures such as 011 two-dimensional commensurable modulated structures or superstructures, [011] twin domain structures, dislocations and crystal deformations. The SAED patterns and HRTEM images indicate the existence of the deformations and stacking faults on the interface of [011] twin crystal of rutile and its two-dimensional commensurate modulated structures with repetition period 0.753 nm (3d(011)) has tetragonal symmetry, cell parameters a = 3a0 = 1.377 nm (a0 = 0.459 nm), c = c0 = 0.3 nm. The modulated structures of rutile were probably caused by the isomorphic replacement of Ti(4+) and position modulation or occupation modulation of oxygen atoms in different degree; the deformation structures reveal that during the process of crystallization and mineralization, this mineral may be affected by the geological environment (such as temperature, pressure and stress), metamorphism and deformation.

  16. The electronic structure and optical response of rutile, anatase and brookite TiO2

    NASA Astrophysics Data System (ADS)

    Landmann, M.; Rauls, E.; Schmidt, W. G.

    2012-05-01

    In this study, we present a combined density functional theory and many-body perturbation theory study on the electronic and optical properties of TiO2 brookite as well as the tetragonal phases rutile and anatase. The electronic structure and linear optical response have been calculated from the Kohn-Sham band structure applying (semi)local as well as nonlocal screened hybrid exchange-correlation density functionals. Single-particle excitations are treated within the GW approximation for independent quasiparticles. For optical response calculations, two-particle excitations have been included by solving the Bethe-Salpeter equation for Coulomb correlated electron-hole pairs. On this methodological basis, gap data and optical spectra for the three major phases of TiO2 are provided. The common characteristics of brookite with the rutile and anatase phases, which have been discussed more comprehensively in the literature, are highlighted. Furthermore, the comparison of the present calculations with measured optical response data of rutile indicate that discrepancies discussed in numerous earlier studies are due to the measurements rather than related to an insufficient theoretical description.

  17. Selective electrochemical reactivity of rutile VO2 towards the suppression of metal-insulator transition

    NASA Astrophysics Data System (ADS)

    Singh, Sujay; Abtew, Tesfaye A.; Horrocks, Gregory; Kilcoyne, Colin; Marley, Peter M.; Stabile, Adam A.; Banerjee, Sarbajit; Zhang, Peihong; Sambandamurthy, G.

    2016-03-01

    We demonstrate through electrolyte gating measurements of a single nanobeam that the rultile phase of VO2 is electrochemically more reactive than the monoclinic phase. Our results show that the complete suppression of the metal-insulator transition and stabilization of the metallic phase is possible when gate voltage is applied in the rutile metallic phase. The results are discussed based on the formation of oxygen vacancies wherein accommodation of a high concentration of vacancies in the rutile phase selectively stabilizes it by disrupting dimerization of adjacent V-V pairs required for a transition to the monoclinic phase. The creation of oxygen vacancies is proposed to proceed through the oxidation of the electrolyte. Raman spectroscopy data suggest surface metallization upon electrolyte gating with an initial coexistence of insulating monoclinic and metallic domains. The selective electrochemical reactivity of the rutile phase and the resulting defect-induced stabilization of this phase across a vastly expanded temperature window suggest a facile defect engineering route to tune electronic phase transitions.

  18. The Effect of Grain Orientation on Secondary Ion Mass Spectrometry (SIMS) Analysis of Rutile

    NASA Astrophysics Data System (ADS)

    Taylor, R.; Clark, C.; Reddy, S. M.

    2011-12-01

    In situ high precision uranium-lead (U-Pb) analysis of rutile by secondary ion mass spectrometry (SIMS) reveals that instrumental bias for isotope ratios and count rates vary due to crystal orientation. Electron backscatter diffraction (EBSD) techniques have been combined with SIMS data to show consistent and systematic crystal orientation effects, whilst confirming that all analyses are on single crystals and that there is random variation from grain to grain. The result of the orientation effect is to produce an extremely large calibration slope, more than an order of magnitude larger than for other minerals, which can result in highly inaccurate and spurious U-Pb ages from rutile if not taken into account. We present a large standard dataset to highlight this effect and show that by collecting good standard data, from grains in multiple orientations, these effects can be negated and accurate U-Pb SIMS data for rutile can be obtained using a standard calibration slope of ln(Pb/U) vs ln(UO2/UO) = 1.12. Examples from the Anantangiri region, Eastern Ghats, India are used to show the magnitude of these effects on the calibration of unknowns. Evidence is presented to show that the cause of these orientation effects is most likely a combination of channelling of primary ions into the crystal and preferential emission of secondary ions along preferred lattice directions.

  19. Microstructure of Co-doped TiO{sub 2}(110) rutile by ion implantation

    SciTech Connect

    Wang, C.M.; Shutthanandan, V.; Thevuthasan, S.; Droubay, T.; Chambers, S.A.

    2005-04-01

    Co-doped rutile TiO{sub 2} was synthesized by injecting Co ions into single crystal rutile TiO{sub 2} using high energy ion implantation. Microstructures of the implanted specimens were studied in detail using high-resolution transmission electron microscopy (HRTEM), energy dispersive x-ray spectroscopy, electron diffraction, and HRTEM image simulations. The spatial distribution and conglomeration behavior of the implanted Co ions, as well as the point defect distributions induced by ion implantation, show strong dependences on implantation conditions. Uniform distribution of Co ions in the rutile TiO{sub 2} lattice was obtained by implanting at 1075 K with a Co ion fluence of 1.25x10{sup 16} Co/cm{sup 2}. Implanting at 875 K leads to the formation of Co metal clusters. The precipitated Co metal clusters and surrounding TiO{sub 2} matrix exhibit the orientation relationships Co<110> parallel TiO{sub 2}[001] and Co{l_brace}111{r_brace} parallel TiO{sub 2}(110). A structural model representing the interface between Co metal clusters and TiO{sub 2} is developed based on HRTEM imaging and image simulations.

  20. Microstructure of Co-doped TiO₂ (110) Rutile by Ion Implantation

    SciTech Connect

    Wang, Chong M.; Shutthanandan, V.; Thevuthasan, Suntharampillai; Droubay, Timothy C.; Chambers, Scott A.

    2005-04-01

    Co-doped rutile TiO₂ was synthesized by injecting Co ions into single crystal rutile TiO₂ using high energy ion implantation. Microstructures of the implanted specimens were studied in detail using high-resolution transmission electron microscopy (HRTEM), energy dispersive x-ray spectroscopy (EDS), electron diffraction, and HRTEM image simulations. The spatial distribution and conglomeration behavior of the implanted Co ions, as well as the point defect distributions induced by ion implantation, show strong dependences on implantation conditions. Uniform distribution of Co ions in the rutile TiO₂ lattice was obtained by implanting at 1075 K with a Co ion fluence of 1.25x10¹⁶ Co/cm². Implanting at 875 K leads to the formation of Co metal clusters. The precipitated Co metal clusters and surrounding TiO₂ matrix exhibit the orientation relationships Co<110>//TiO₂[001] and Co{111}//TiO₂(110). A structural model representing the interface between Co metal clusters and TiO₂ is developed based on HRTEM imaging and image simulations.

  1. Comment on "Structure and dynamics of liquid water on rutile TiO2(110)

    SciTech Connect

    Wesolowski, David J; Sofo, Jorge O.; Bandura, Andrei V.; Zhang, Zhan; Mamontov, Eugene; Predota, M.; Kumar, Nitin; Kubicki, James D.; Kent, Paul R; Vlcek, Lukas; Machesky, Michael L.; Fenter, Paul; Cummings, Peter T; Anovitz, Lawrence {Larry} M; Skelton, A A; Rosenqvist, Jorgen K

    2012-01-01

    Liu and co-workers [Phys. Rev. B 82, 161415 (2010)] discussed the long-standing debate regarding whether H2O molecules on the defect-free (110) surface of rutile ( -TiO2) sorb associatively, or there is dissociation of some or all first-layer water to produce hydroxyl surface sites. They conducted static density functional theory (DFT) and DFT molecular dynamics (DFT-MD) investigations using a range of cell configurations and functionals. We have reproduced their static DFT calculations of the influence of crystal slab thickness on water sorption energies. However, we disagree with several assertions made by these authors: (a) that second-layer water structuring and hydrogen bonding to surface oxygens and adsorbed water molecules are weak ; (b) that translational diffusion of water molecules in direct contact with the surface approaches that of bulk liquid water; and (c) that there is no dissociation of adsorbed water at this surface in contact with liquid water. These assertions directly contradict our publishedwork, which compared synchrotron x-ray crystal truncation rod, second harmonic generation, quasielastic neutron scattering, surface charge titration, and classical MD simulations of rutile (110) single-crystal surfaces and (110)-dominated powders in contact with bulk water, and (110)-dominated rutile nanoparticles with several monolayers of adsorbed water.

  2. Inactivation of Escherichia coli on anatase and rutile nanoparticles using UV and fluorescent light

    SciTech Connect

    Caratto, V.; Aliakbarian, B.; Casazza, A.A.; Setti, L.; Bernini, C.; Perego, P.; Ferretti, M.

    2013-06-01

    Highlights: ► Photocatalytic deactivation of Escherichia coli in presence of TiO{sub 2} nanoparticles ► The presence of catalyst is less important when the radiation is in the UV range ► Rutile has an higher efficiency respect to anatase under visible light. - Abstract: The photocatalytic deactivation of Escherichia coli HB101 by two different structures of TiO{sub 2}, rutile and anatase (used separately and in a 1:1 mixture), was examined. The microorganism was deposited on a filter membrane containing 520 mg/m{sup 2} of TiO{sub 2} and then irradiated by a neon lamp. In order to study the rate of deactivation of the microorganism we studied four different exposure times: 20, 40, 60 and 90 min. The results showed that rutile has an antimicrobial activity higher than anatase, while the mixture had values near to the average between them in every condition. The highest difference in the inactivation capacity of the two structures is observable at shorter times. The effect of the different crystal phases was evaluated by Scanning Electron Microscopy.

  3. Kinetics study on phase transformation from titania polymorph brookite to rutile

    NASA Astrophysics Data System (ADS)

    Huberty, Jason; Xu, Huifang

    2008-03-01

    TiO 2 is a polymorphic material of great scientific interest due to its semiconductor properties and uses in heterogeneous photocatalysis. Understanding the stability of the polymorphs is important for designing TiO 2-based photocatalysts and solar cells. Although the phase transformation of anatase→rutile has been well studied, there is only one published work on brookite→rutile to date. The brookite→rutile transformation has been studied in this work using natural material from the Magnet Cove igneous complex mechanically processed to several micrometers in size. The pure phase brookite is annealed from 800 to 900 °C without detection of the anatase polymorph. The transformation kinetics are described by both the standard first-order model, with an activation energy of Ea=411.91 kJ/mol, and the Johnson-Mehl-Avrami-Kolmogorov (JMAK) model, with an activation energy of Ea=492.13 kJ/mol. The rate parameter of the first-order model for the phase transformation is expressed as k=6.85×10 14 exp(-49,451/ T) s -1 for the first-order model and k=4.19×10 18 exp(-59,189/ T) s -1 using the JMAK model. The obtained activation energy is higher than that of brookite nano-crystals. Our results show that the JMAK model fits the kinetics data better than other models.

  4. Role of hydroxyl groups on the stability and catalytic activity of Au clusters on rutile surface

    SciTech Connect

    Kent, Paul R

    2011-01-01

    Hydroxyls are present as surface terminations of transition metal oxides under ambient conditions and may modify the properties of supported catalysts. We perform first-principles density functional theory calculations to investigate the role of hydroxyls on the catalytic activity of supported gold clusters on TiO{sub 2} (rutile). We find that they have a long-range effect increasing the adhesion of gold clusters on rutile. While hydroxyls make one gold atom more electronegative, a more complex charge-transfer scenario is observed on larger clusters which are important for catalytic applications. This enhances the molecular adsorption and coadsorption energies of CO and O{sub 2}, thereby increasing the catalytic activity of gold clusters for CO oxidation, consistent with reported experiments. Hydroxyls at the interface between gold and rutile surface are most important to this process, even when not directly bound to gold. As such, accurate models of catalytic processes on gold and other catalysts should include the effect of surface hydroxyls.

  5. Theoretical study of the structure and optical properties of carbon-doped rutile and anatase titanium oxides

    NASA Astrophysics Data System (ADS)

    Kamisaka, Hideyuki; Adachi, Takahisa; Yamashita, Koichi

    2005-08-01

    The structure and optical properties of carbon-doped titanium oxides, TiO2, in the rutile and anatase forms have been investigated theoretically from first principles. Two possible doping sites were studied, carbon at an oxygen site (anion doping) and carbon at a titanium site (cation doping). The calculated structures suggest that cation-doped carbon atoms form a carbonate-type structure, whereas anion-doped carbon atoms do not invoke any significant structural change. A density-of-states analysis revealed three in-gap impurity states for anion doping. The optical properties of anion-doped cells qualitatively agree with the experimentally reported visible-light absorbance values. We ascribe part of the absorption to transitions from the valence band to one of the impurity states. These transitions should be able to promote photocatalytic reactions, because electron holes in the valence band are considered to be crucial for this process. Neither in-gap impurity states nor visible-light absorbance were observed in the case of cation doping. The effect of oxygen vacancies was also investigated. Introduction of oxygen vacancies into anion-doped TiO2 populates the impurity states and thus suppresses photocatalysis. The interaction of a doped carbon atom with an oxygen vacancy at a finite spatial separation was also carried out. The possibility of either a carbon-oxygen vacancy pair or higher carbon-oxygen vacancy complex existing is discussed.

  6. Testing the Jacob's ladder of density functionals for electronic structure and magnetism of rutile VO2

    NASA Astrophysics Data System (ADS)

    Xiao, Bing; Sun, Jianwei; Ruzsinszky, Adrienn; Perdew, John P.

    2014-08-01

    We employ semilocal density functionals [local spin-density approximation (LSDA), Perdew-Burke-Ernzerhof (PBE) generalized gradient approximation (GGA), and meta-GGAs)], LSDA plus Hubbard U (LSDA+U) theory, a nonlocal range-separated Heyd-Scuseria-Ernzerhof hybrid functional (HSE06), and the random-phase approximation (RPA) to assess their performances for the ground-state magnetism and electronic structure of a strongly correlated metal, rutile VO2. Using recent quantum Monte Carlo results as the benchmark, all tested semilocal and hybrid functionals as well as the RPA (with PBE inputs) predict the correct magnetic ground states for rutile VO2. The observed paramagnetism could arise from temperature-disordered local spin moments or from the thermal destruction of these moments. All semilocal functionals also give the correct ground-state metallicity for rutile VO2. However, in the ferromagnetic (FM) and antiferromagnetic (AFM) phases, LSDA+U and HSE06 incorrectly predict rutile VO2 to be a Mott-Hubbard insulator. For the computed electronic structures of FM and AFM phases, we find that the Tao-Perdew-Staroverov-Scuseria (TPSS) and revised TPSS (revTPSS) meta-GGAs give strong 2p-3d hybridizations, resulting in a depopulation of the 2p bands of O atoms, in comparison with other tested meta-GGAs. The regularized TPSS (regTPSS) and meta-GGAs made simple, i.e., MGGA_MS0 and MGGA_MS2, which are free of the spurious order-of-limits problem of TPSS and revTPSS, give electronic states close to those of the PBE GGA and LSDA. In comparison to experiment, semilocal functionals predict better equilibrium cell volumes for rutile VO2 in FM and AFM states than in the spin-unpolarized state. For meta-GGAs, a monotonic decrease of the exchange enhancement factor Fx(s,α) with α for small s, as in the MGGA_MS functionals, leads to large (probably too large) local magnetic moments in spin-polarized states.

  7. Derivation of detrital rutile in the Yaoundé region from the Neoproterozoic Pan-African belt in southern Cameroon (Central Africa)

    NASA Astrophysics Data System (ADS)

    Stendal, Henrik; Toteu, Sadrack Félix; Frei, Robert; Penaye, Joseph; Njel, Urbain Olivier; Bassahak, Jean; Nni, Jean; Kankeu, Boniface; Ngako, Vincent; Hell, Joseph Victor

    2006-04-01

    Rutile, as an important component in alluvial or eluvial heavy mineral deposits, is known in southern Cameroon. These deposits are underlain by the Neoproterozoic low- to high-grade Yaoundé Group. Geochemical, thermometric, fluid inclusion and Pb isotopic studies of the rutile from alluvial and eluvial concentrates and from medium-grade micaschist from the nearby Yaoundé region permit the following conclusions: (1) alluvial and eluvial rutile of the Yaoundé region are derived from the degradation of metapelites, metamafic rocks and pegmatites of the nearby Yaoundé Group; (2) rutile in the Yaoundé Group formed during the Pan-African metamorphism, or was inherited as detrital rutile from a ˜900 Ma source. The study also shows that the rutile can be used to trace the history of the Pan-African belt north of the Congo craton.

  8. High-precision UPb ages of metamorphic rutile: application to the cooling history of high-grade terranes

    USGS Publications Warehouse

    Mezger, K.; Hanson, G.N.; Bohlen, S.R.

    1989-01-01

    Metamorphic rutiles occurring in granulite and upper amphibolite facies metapelitic rocks of the Archean Pikwitonei granulite domain (Manitoba) and the Proterozoic Adirondack terrane (New York) give concordant and near concordant UPb ages. The Pb concentrations in rutile range from 2.85 to 168 ppm, U concentrations range from 10.9 to 390 ppm and the measured 206Pb 204Pb ratios range from 182 to 22,100 corresponding to 238U 204Pb ratios of 398-75,100. The proportions of radiogenic 208Pb are very low, ranging from 0.0 to 6.9% of total radiogenic Pb. The habits of the rutile crystals range from stubby to acicular, the physical properties vary from opaque/black to transparent/reddish-brown. Separate batches of black and reddish-brown rutile grains from the same samples have similar U and Pb concentrations, Pb-isotope ratios, and yield the same U Pb ages within analytical uncertainty. No correlation of U concentration and 206Pb 204Pb ratios with morphology or color of the rutiles was observed among the samples analyzed. Most rutiles yield concordant UPb ages which are reproducible within analytical uncertainty, i.e. generally ??2 Ma. The UPb ages for prograde rutile are younger than the time of peak metamorphism given by UPb ages for garnet and zircon, and also younger than UPb ages for sphene and monazite, and 40Ar 39Ar and KAr ages for hornblende but older than 40Ar 39Ar and KAr ages for biotite from the same area. This suggests that the rutile ages reflect cooling below closure temperatures. Within a single hand-specimen, and thus for an identical thermal history, larger rutile grains give older ages than do smaller grains. This suggests that volume diffusion is the most probable mechanism responsible for the ages being younger than the time of peak metamorphism. It also suggests that the dimensions for such diffusion are directly related to the dimensions of the rutile crystal and not to the dimensions of sub-grain domains, as is the case for Ar diffusion in

  9. Adsorption sites of single noble metal atoms on the rutile TiO2 (1 1 0) surface influenced by different surface oxygen vacancies.

    PubMed

    Matsunaga, Katsuyuki; Chang, Teng-Yuan; Ishikawa, Ryo; Dong, Qian; Toyoura, Kazuaki; Nakamura, Atsutomo; Ikuhara, Yuichi; Shibata, Naoya

    2016-05-01

    Atomic adsorption of Au and Pt on the rutile (1 1 0) surface was investigated by atomic-resolution aberration-corrected scanning transmission electron microscopy (STEM) measurements combined with density functional theory calculations. Au single atoms were deposited on the surface in a vacuum condition, and the observed results were compared with Pt single atoms on the same surface prepared by the same experimental manner. It was found that Au single atoms are stably adsorbed only at the bridging oxygen vacancy sites, which is quite different from Pt single atoms exhibiting the most frequently observed adsorption at the basal oxygen vacancy sites. Such a difference in oxygen-vacancy effect between Au and Pt can be explained by electronic structures of the surface vacancies as well as characters of outermost atomic orbitals of Au and Pt.

  10. A study on native defects and magnetic properties in undoped rutile TiO2 using LDA and LDA+UO p+UTi d methods

    NASA Astrophysics Data System (ADS)

    Shi, Li-Bin; Wang, Yong Ping

    2016-05-01

    The native defects and magnetic properties in undoped rutile TiO2 are studied using local density approximation (LDA) and LDA adding Hubbard parameters (U) schemes. The band gap is adjusted to experimental value of 3.0 eV by combination of UTi d=4.2 eV and UO p=4.8 eV. This LDA+U methodology overcomes the band-gap problem and renders the approach more predictive. The formation energies of oxygen vacancy (VO), oxygen interstitial (Oi), titanium vacancy (VTi), titanium interstitial (Tii), oxygen anti-sites (OTi), and titanium anti-sites (TiO) are investigated by the LDA and LDA+U methods. In addition, some ground state configurations can be obtained by optimization of total spin. It is found that native defects can induce spin polarization and produce magnetic moment.

  11. Why is anatase a better photocatalyst than rutile? - Model studies on epitaxial TiO2 films

    PubMed Central

    Luttrell, Tim; Halpegamage, Sandamali; Tao, Junguang; Kramer, Alan; Sutter, Eli; Batzill, Matthias

    2014-01-01

    The prototypical photocatalyst TiO2 exists in different polymorphs, the most common forms are the anatase- and rutile-crystal structures. Generally, anatase is more active than rutile, but no consensus exists to explain this difference. Here we demonstrate that it is the bulk transport of excitons to the surface that contributes to the difference. Utilizing high –quality epitaxial TiO2 films of the two polymorphs we evaluate the photocatalytic activity as a function of TiO2-film thickness. For anatase the activity increases for films up to ~5 nm thick, while rutile films reach their maximum activity for ~2.5 nm films already. This shows that charge carriers excited deeper in the bulk contribute to surface reactions in anatase than in rutile. Furthermore, we measure surface orientation dependent activity on rutile single crystals. The pronounced orientation-dependent activity can also be correlated to anisotropic bulk charge carrier mobility, suggesting general importance of bulk charge diffusion for explaining photocatalytic anisotropies. PMID:24509651

  12. N719- and D149-sensitized 3D hierarchical rutile TiO2 solar cells--a comparative study.

    PubMed

    Lin, Jianjian; Heo, Yoon-Uk; Nattestad, Andrew; Shahabuddin, Mohammed; Yamauchi, Yusuke; Kim, Jung Ho

    2015-03-21

    Poor dye loading on rutile TiO2 is one of the chief reasons for lower solar-to-electric conversion efficiency (η) in dye-sensitized solar cells (DSCs), compared to their anatase based counterparts. Previously, we showed that similar light harvesting for both rutile and anatase was realized by using a metal-free organic indoline dye, D149 [Sci. Rep., 2014, 4, 5769]. This was in contrast to the bulk of previous studies, which employed ruthenium based N719, leading to significant differences in light harvesting. To date, there has been no report directly comparing N719 and D149 for rutile based DSCs. In this work, three-dimensional hierarchical rutile TiO2 architecture (HRTA), consisting of one-dimensional nanorods, was successfully prepared via a facile hydrothermal method, and subsequently optimized as effective photoelectrodes for DSCs. Two dyes, N719 and D149, were used as sensitizers of the HRTA-based DSCs, with maximum η of 5.6% and 5.8% achieved, respectively. The higher η of the D149-sensitized DSC is ascribed to its higher extinction co-efficient, allowing a greater amount of light to be harvested with a thinner TiO2 layer. This study suggests that some of the limitations typically observed for rutile TiO2 based DSCs can be overcome through the use of strongly absorbing metal-free organic sensitizers. Furthermore, it reemphasises the importance of viewing DSCs as whole systems, rather than individual components.

  13. Atomic-scale surface roughness of rutile and implications for organic molecule adsorption.

    PubMed

    Livi, Kenneth J T; Schaffer, Bernhard; Azzolini, David; Seabourne, Che R; Hardcastle, Trevor P; Scott, Andrew J; Hazen, Robert M; Erlebacher, Jonah D; Brydson, Rik; Sverjensky, Dimitri A

    2013-06-11

    Crystal surfaces provide physical interfaces between the geosphere and biosphere. It follows that the arrangement of atoms at the surfaces of crystals profoundly influences biological components at many levels, from cells through biopolymers to single organic molecules. Many studies have focused on the crystal-molecule interface in water using large, flat single crystals. However, little is known about atomic-scale surface structures of the nanometer- to micrometer-sized crystals of simple metal oxides typically used in batch adsorption experiments under conditions relevant to biogeochemistry and the origins of life. Here, we present atomic-resolution microscopy data with unprecedented detail of the circumferences of nanosized rutile (α-TiO2) crystals previously used in studies of the adsorption of protons, cations, and amino acids. The data suggest that one-third of the {110} faces, the largest faces on individual crystals, consist of steps at the atomic scale. The steps have the orientation to provide undercoordinated Ti atoms of the type and abundance for adsorption of amino acids as inferred from previous surface complexation modeling of batch adsorption data. A remarkably uniform pattern of step proportions emerges: the step proportions are independent of surface roughness and reflect their relative surface energies. Consequently, the external morphology of rutile nanometer- to micrometer-sized crystals imaged at the coarse scale of scanning electron microscope images is not an accurate indicator of the atomic smoothness or of the proportions of the steps present. Overall, our data strongly suggest that amino acids attach at these steps on the {110} surfaces of rutile. PMID:23675906

  14. Microstructure and dielectric properties of (Nb + In) co-doped rutile TiO2 ceramics

    NASA Astrophysics Data System (ADS)

    Li, Jinglei; Li, Fei; Zhuang, Yongyong; Jin, Li; Wang, Linghang; Wei, Xiaoyong; Xu, Zhuo; Zhang, Shujun

    2014-08-01

    The (Nb + In) co-doped TiO2 ceramics recently attracted considerable attention due to their colossal dielectric permittivity (CP) (˜100,000) and low dielectric loss (˜0.05). In this research, the 0.5 mol. % In-only, 0.5 mol. % Nb-only, and 0.5-7 mol. % (Nb + In) co-doped TiO2 ceramics were synthesized by standard conventional solid-state reaction method. Microstructure studies showed that all samples were in pure rutile phase. The Nb and In ions were homogeneously distributed in the grain and grain boundary. Impedance spectroscopy and I-V behavior analysis demonstrated that the ceramics may compose of semiconducting grains and insulating grain boundaries. The high conductivity of grain was associated with the reduction of Ti4+ ions to Ti3+ ions, while the migration of oxygen vacancy may account for the conductivity of grain boundary. The effects of annealing treatment and bias filed on electrical properties were investigated for co-doped TiO2 ceramics, where the electric behaviors of samples were found to be susceptible to the annealing treatment and bias field. The internal-barrier-layer-capacitance mechanism was used to explain the CP phenomenon, the effect of annealing treatment and nonlinear I-V behavior for co-doped rutile TiO2 ceramics. Compared with CaCu3Ti4O12 ceramics, the high activation energy of co-doped rutile TiO2 (3.05 eV for grain boundary) was thought to be responsible for the low dielectric loss.

  15. Slow exhumation of UHP terranes: Titanite and rutile ages of the Western Gneiss Region, Norway

    NASA Astrophysics Data System (ADS)

    Kylander-Clark, A. R. C.; Hacker, B. R.; Mattinson, J. M.

    2008-08-01

    U-Pb ages of titanite and rutile were obtained from the central Western Gneiss Region, Norway, to assess the style and timing of exhumation and cooling of the Western Gneiss UHP terrane. Approximately half of the titanite ages are concordant, the majority of which yield a limited age range from 393 to 390 Ma. The other titanite data are discordant, and define discordia arrays with upper intercept ages of either ˜ 938 Ma or ˜ 1.6 Ga, and a lower intercept of ˜ 389 Ma. Concordant rutile analyses range from 385 to 392 Ma. Both titanite and rutile ages young WNW toward the core of the orogen and are ˜ 4 Ma older than 40Ar/ 39Ar muscovite ages, corresponding to a cooling rate of ˜ 90 °C/Ma. A well-defined boundary between concordant and discordant titanite ages, in combination with the WNW-increasing P- T gradient and the similarity between muscovite cooling ages in the east and eclogite ages in the west, suggests that the WGR remained coherent throughout its exhumation history, and was progressively unroofed from east to west. A 390.2 ± 0.8 Ma titanite in the Sørøyane UHP domain indicates that exhumation occurred at a vertical rate of ˜ 7 mm/yr for ˜ 12 Ma. These rates are slower than estimates from smaller UHP terranes, but similar to other large UHP terranes, suggesting that there may be fundamental differences in the mechanisms controlling the evolution of large UHP terranes that undergo protracted subduction and exhumation, and smaller UHP terranes that undergo rapid subduction and exhumation.

  16. Adhesion of sodium dodecyl sulfate surfactant monolayers with TiO2 (rutile and anatase) surfaces

    SciTech Connect

    Darkins, Robert; Sushko, Maria L.; Liu, Jun; Duffy, Dorothy M.

    2013-09-17

    Surfactants are widely used as templates to control the nucleation and growth of nanostructured metal oxides such as titania. To gain insight into the origin of surfactant-titania interactions responsible for polymorph and orientation selection, we simulate the self-assembly of an anionic surfactant monolayer on various low-index titania surfaces and for a range of densities. We characterize the binding in each case and compute the adhesion energies, finding anatase (100) and rutile (110) to be the strongest-binding surfaces. The sodium counterions in the monolayer are found to dominate the adhesion. It is also observed that the assembly is directed predominantly by surface-monolayer electrostatic complementarity.

  17. Thermodynamic Properties of Rutile (TiO2) Within the Phonon Calculations

    NASA Astrophysics Data System (ADS)

    Kangarlou, Haleh; Abdollahi, Arash

    2016-11-01

    Full phonon calculations have been performed to estimate the thermal properties of rutile (titanium dioxide). Calculations have been carried out using the pseudo-potential method within the local density approximation. Thermodynamic properties including the thermal expansion, thermal expansion coefficient, heat capacity and entropy were calculated as a function of temperature in the framework of quasi-harmonic approximation. Also, to compare the results with the results of other approaches, we apply Debye-Slater and Debye-Gruneisen approaches with the same parameters for electronic calculations. It is found that the phonon calculations provide more accurate estimates in comparison with the other two models.

  18. Isotropic photo-decomposition of spherical organic polymers on rutile TiO₂(110) surfaces.

    PubMed

    Ishida, Nobuyuki; Iwasaki, Tamaki; Fujita, Daisuke

    2011-04-15

    We observed the photo-decomposition process of polystyrene latex (PSL) spheres on a rutile TiO₂(110) single crystal surface by using atomic force microscopy. During the decomposition process, both the height and width of the PSL spheres linearly decreased with the irradiation time in a similar way from the beginning, suggesting that the PSL spheres are isotropically decomposed. This indicates that the interface between the PSL spheres and the TiO₂ surface is not a dominant reaction site, as expected from normal photocatalytic reactions.

  19. Isotropic photo-decomposition of spherical organic polymers on rutile TiO₂(110) surfaces.

    PubMed

    Ishida, Nobuyuki; Iwasaki, Tamaki; Fujita, Daisuke

    2011-04-15

    We observed the photo-decomposition process of polystyrene latex (PSL) spheres on a rutile TiO₂(110) single crystal surface by using atomic force microscopy. During the decomposition process, both the height and width of the PSL spheres linearly decreased with the irradiation time in a similar way from the beginning, suggesting that the PSL spheres are isotropically decomposed. This indicates that the interface between the PSL spheres and the TiO₂ surface is not a dominant reaction site, as expected from normal photocatalytic reactions. PMID:21389569

  20. Synthesis and Characterization of Rutile TiO2Nanopowders Doped with Iron Ions

    PubMed Central

    2009-01-01

    Titanium dioxide nanopowders doped with different amounts of Fe ions were prepared by coprecipitation method. Obtained materials were characterized by structural (XRD), morphological (TEM and SEM), optical (UV/vis reflection and photoluminescence, and Raman), and analytical techniques (XPS and ICP-OES). XRD analysis revealed rutile crystalline phase for doped and undoped titanium dioxide obtained in the same manner. Diameter of the particles was 5–7 nm. The presence of iron ions was confirmed by XPS and ICP-OES. Doping process moved absorption threshold of TiO2into visible spectrum range. Photocatalytic activity was also checked. Doped nanopowders showed normal and up-converted photoluminescence. PMID:20596442

  1. Tailoring the crystal structure of TiO{sub 2} thin films from the anatase to rutile phase

    SciTech Connect

    Kotake, Haruka; Jia, Junjun; Nakamura, Shin-ichi; Shigesato, Yuzo; Okajima, Toshihiro

    2015-07-15

    TiO{sub 2} films with various Sn concentrations were deposited on quartz substrates using rf reactive magnetron sputtering. The crystal structure was investigated by using x-ray diffraction, Raman spectroscopy, and transmission electron microscopy, and the chemical states of Ti and Sn were analyzed by x-ray absorption near edge structure (XANES) spectroscopy. Without Sn doping, TiO{sub 2} films change the crystal structure from rutile to anatase as the total gas pressure increases in the sputtering deposition. On the other hand, Sn doping induces the transformation of TiO{sub 2} crystalline structure from anatase to rutile phase, where the XANES spectra implied that Sn substitutes into Ti site of rutile TiO{sub 2}. Atomic force microscope analyses revealed that the Sn-doped TiO{sub 2} films exhibited a flat surface with the roughness of approximately 2 nm.

  2. Ultra-sensitive pressure dependence of bandgap of rutile-GeO{sub 2} revealed by many body perturbation theory

    SciTech Connect

    Samanta, Atanu; Singh, Abhishek K.; Jain, Manish

    2015-08-14

    The reported values of bandgap of rutile GeO{sub 2} calculated by the standard density functional theory within local-density approximation (LDA)/generalized gradient approximation (GGA) show a wide variation (∼2 eV), whose origin remains unresolved. Here, we investigate the reasons for this variation by studying the electronic structure of rutile-GeO{sub 2} using many-body perturbation theory within the GW framework. The bandgap as well as valence bandwidth at Γ-point of rutile phase shows a strong dependence on volume change, which is independent of bandgap underestimation problem of LDA/GGA. This strong dependence originates from a change in hybridization among O-p and Ge-(s and p) orbitals. Furthermore, the parabolic nature of first conduction band along X-Γ-M direction changes towards a linear dispersion with volume expansion.

  3. A shock-induced polymorph of anatase and rutile from the Chesapeake Bay impact structure, Virginia, U.S.A

    USGS Publications Warehouse

    Jackson, J.C.; Horton, J.W.; Chou, I.-Ming; Belkin, H.E.

    2006-01-01

    A shock-induced polymorph (TiO2II) of anatase and rutile has been identified in breccias from the late Eocene Chesapeake Bay impact structure. The breccia samples are from a recent, partially cored test hole in the central uplift at Cape Charles, Virginia. The drill cores from 744 to 823 m depth consist of suevitic crystalline-clast breccia and brecciated cataclastic gneiss in which the TiO2 phases anatase and rutile are common accessory minerals. Electron-microprobe imaging and laser Raman spectroscopy of TiO2 crystals, and powder X-ray diffraction (XRD) of mineral concentrates, confirm that a high-pressure, ??-PbO2 structured polymorph of TiO2 (TiO2II) coexists with anatase and rutile in matrix-hosted crystals and in inclusions within chlorite. Raman spectra of this polymorph include strong bands at wavenumbers (cm-1) 175, 281, 315, 342, 356, 425, 531, 571, and 604; they appear with anatase bands at 397, 515, and 634 cm-1, and rutile bands at 441 and 608 cm-1. XRD patterns reveal 12 lines from the polymorph that do not significantly interfere with those of anatase or rutile, and are consistent with the TiO2II that was first reported to occur naturally as a shock-induced phase in rutile from the Ries crater in Germany. The recognition here of a second natural shock-induced occurrence of TiO2II suggests that its presence in rocks that have not been subjected to ultrahigh-pressure regional metamorphism can be a diagnostic indicator for confirmation of suspected impact structures.

  4. inner-sphere complexation of cations at the rutile-water interface: A concise surface structural interpretation with the CD and MUSIC model

    SciTech Connect

    Ridley, Mora K.; Hiemstra, T; Van Riemsdijk, Willem H.; Machesky, Michael L.

    2009-01-01

    Acid base reactivity and ion-interaction between mineral surfaces and aqueous solutions is most frequently investigated at the macroscopic scale as a function of pH. Experimental data are then rationalized by a variety of surface complexation models. These models are thermodynamically based which in principle does not require a molecular picture. The models are typically calibrated to relatively simple solid-electrolyte solution pairs and may provide poor descriptions of complex multicomponent mineral aqueous solutions, including those found in natural environments. Surface complexation models may be improved by incorporating molecular-scale surface structural information to constrain the modeling efforts. Here, we apply a concise, molecularly-constrained surface complexation model to a diverse suite of surface titration data for rutile and thereby begin to address the complexity of multi-component systems. Primary surface charging curves in NaCl, KCl, and RbCl electrolyte media were fit simultaneously using a charge distribution (CD) and multisite complexation (MUSIC) model [Hiemstra T. and Van Riemsdijk W. H. (1996) A surface structural approach to ion adsorption: the charge distribution (CD) model. J. Colloid Interf. Sci. 179, 488 508], coupled with a Basic Stern layer description of the electric double layer. In addition, data for the specific interaction of Ca2+ and Sr2+ with rutile, in NaCl and RbCl media, were modeled. In recent developments, spectroscopy, quantum calculations, and molecular simulations have shown that electrolyte and divalent cations are principally adsorbed in various inner-sphere configurations on the rutile 110 surface [Zhang Z., Fenter P., Cheng L., Sturchio N. C., Bedzyk M. J., Pr edota M., Bandura A., Kubicki J., Lvov S. N., Cummings P. T., Chialvo A. A., Ridley M. K., Be ne zeth P., Anovitz L., Palmer D. A., Machesky M. L. and Wesolowski D. J. (2004) Ion adsorption at the rutile water interface: linking molecular and macroscopic

  5. Effect of the rutile content on the photovoltaic performance of the dye-sensitized solar cells composed of mixed-phase TiO2 photoelectrodes.

    PubMed

    Yun, Tae Kwan; Park, Sung Soo; Kim, Duckhyun; Shim, Jae-Hyun; Bae, Jae Young; Huh, Seong; Won, Yong Sun

    2012-01-28

    The effect of the rutile content on the photovoltaic performance of dye-sensitized solar cells (DSSCs) composed of mixed-phase TiO(2) photoelectrode has been investigated. The mixed-phase TiO(2) particles with varied amounts of rutile, relative to anatase phase, are synthesized by an in situ method where the concentration of sulfate ion is used as a phase-controlling parameter in the formation of TiO(2) using TiCl(4) hydrolysis. The surface area (S(BET)) varies from 33 (pure rutile) to 165 (pure anatase) m(2) g(-1). Generally, both the current density (J(sc)) and photo-conversion efficiency (η) decrease as the rutile content increases. The incorporation of rod-shaped rutile particles causes low uptake of dye due to the reduced surface area, as well as slow electron transport in less efficiently-stacked structure. However, maximum J(sc) (14.63 mA cm(-2)) and η (8.69%) appear when relatively low rutile content (16%) is employed. The reported synergistic effect by the efficient interparticle electron transport from rutile to anatase seems to overbalance the decrease of surface area when small amount of rutile particles is incorporated. PMID:22124477

  6. One-step synthesis of nano-micro chestnut TiO2 with rutile nanopins on the microanatase octahedron.

    PubMed

    Hosono, Eiji; Fujihara, Shinobu; Imai, Hiroaki; Honma, Itaru; Masaki, Ichihara; Zhou, Haoshen

    2007-11-01

    The solution synthesis of large single crystals of octahedron-like anatase TiO2 is reported, although this novel result is unexpected in the light of reported theoretical calculations. Moreover, systematic control of the crystal growth of rutile nanopins on the microanatase octahedron single crystal results in a nano-micro chestnut-like TiO2 structure. The control of the formation of rutile nanopins on the large single crystals of anatase in the same solution is an interesting and useful technique, based on thermodynamics and surface chemistry.

  7. The electrochemistry of transparent quantum size rutile nanowire thin films prepared by one-step low temperature chemical bath deposition

    NASA Astrophysics Data System (ADS)

    Berger, Thomas; Lana-Villarreal, Teresa; Monllor-Satoca, Damián; Gómez, Roberto

    2007-10-01

    We performed a spectro- and photoelectrochemical study of electrodes consisting of oriented rutile TiO 2 nanowires with a diameter of ˜2 nm prepared directly by chemical bath deposition on conducting glass. A significant increase (around 0.25 eV with respect to bulk rutile) of the band gap energy for the nanowire film is observed and attributed to quantum size effects, pointing to the presence of individual monocrystalline nanowires with no significant electronic communication among them. This allows for the investigation of morphologically well defined electrodes in the two dimensional quantum confinement regime, which are characterized by particularly good photoelectrocatalytic and electrochromic properties.

  8. Time-resolved shock compression of porous rutile: Wave dispersion in porous solids

    SciTech Connect

    Anderson, M.U.; Graham, R.A.; Holman, G.T.

    1993-08-01

    Rutile (TiO{sub 2}) samples at 60% of solid density have been shock-loaded from 0.21 to 6.1 GPa with sample thickness of 4 mm and studied with the PVDF piezoelectric polymer stress-rate gauge. The technique uses a copper capsule to contain the sample which has PVDF gauge packages in direct contact with front and rear surfaces. A precise measure is made of the compressive stress wave velocity through the sample, as well as the input and propagated shock stress. Initial density is known from sample preparation, and the amount of shock-compression is calculated from the measurement of shock velocity and input stress. Shock states and re-shock states are measured. Observed data are consistent with previously published high pressure data. It is observed that rutile has a ``crush strength`` near 6 GPa. Propagated stress-pulse rise times vary from 234 to 916 nsec. Propagated stress-pulse rise times of shock-compressed HMX, 2Al + Fe{sub 2}O{sub 3}, 3Ni + Al, and 5Ti + 3Si are presented.

  9. Time-resolved shock compression of porous rutile: Wave dispersion in porous solids

    SciTech Connect

    Anderson, M.U.; Graham, R.A.; Holman, G.T. )

    1994-07-10

    Rutile (TiO[sub 2]) samples at 60% of solid density have been shock-loaded from 0.21 to 6.1 GPa with sample thickness of 4 mm and studied with the PVDF piezoelectric polymer stress-rate gauge. The technique uses a copper capsule to contain the sample which has PVDF gauge packages in direct contact with the front and rear surfaces. A precise measure is made of the compressive stress wave velocity through the sample, as well as the input and propagated shock stress. The initial density is known from the sample preparation process, and the amount of shock-compression is calculated from the measurement of shock velocity and input stress. Shock states and re-shock states are measured. The observed data are consistent with previously published high pressure data. It is observed that rutile has a crush strength'' near 6 GPa. Propagated stress-pulse rise times vary from 234 to 916 nsec. Propagated stress-pulse rise times of shock-compressed HMX, 2Al+Fe[sub 2]O[sub 3], 3Ni+Al, and 5Ti+3Si are presented. [copyright] 1994 American Institute of Physics

  10. Rutile TiO2 inverse opal with photonic bandgap in the UV-visible range.

    PubMed

    Li, Yu; Piret, François; Léonard, Timothée; Su, Bao-Lian

    2010-08-01

    Highly organized rutile Titania inverse opal-based photonic crystals that exhibit reflective properties in the UV-Visible range have been constructed. A self-assembly method was employed to infiltrate the interstitial space of a highly organized polymeric opal with a titania alkoxide precursor under well controlled conditions. Further hydrolysis and drying steps led to the formation of polystyrene spheres/amorphous TiO(2) opaline nanocomposites which exhibited very interesting optical properties with a photonic bandgap (PBG) in the infrared range. The TiO(2) inverted opal was subsequently obtained by the removal of the template either by chemical dissolution or calcination. The latter method was shown to yield samples of high quality and the influence of the calcination temperature on photonic crystal properties was studied by XRD, FESEM, EDX and Reflectance measurements. The highly organized, dense and thermally stable TiO(2) inverse opal obtained through calcination shows low defect density and a sharp reflection of incident UV-Vis-NIR light at around 380 nm and is then expected to possess a complete photonic bandgap due to the highly refringent dense rutile phase and the controlled and small lattice parameters of the crystal. The crystalline phase, the structural properties and the excellent thermal stability of the material (up to 1000 degrees C) are discussed.

  11. Photocatalytic chemistry of methanol on rutile TiO₂(011)-(2 × 1).

    PubMed

    Wang, Zhiqiang; Hao, Qunqing; Mao, Xinchun; Zhou, Chuanyao; Dai, Dongxu; Yang, Xueming

    2016-04-21

    Photocatalytic chemistry of methanol on the reconstructed rutile TiO2(011)-(2 × 1) surface upon 266 nm and 400 nm light excitation has been investigated quantitatively using the post-irradiation temperature-programmed desorption (TPD) method. Photochemical products such as formaldehyde, methyl formate and water, which result from the recombination of surface bridging hydroxyls through the abstraction of lattice oxygen atoms, have been identified under both 266 nm and 400 nm light irradiation. However, ethylene is detected only under 266 nm light irradiation. Through an analogy experiment, ethylene production is attributed to the photochemistry and the following thermochemistry of formaldehyde. The absence of the ethylene signal under 400 nm light is consistent with the significantly lower conversion at this wavelength compared with 266 nm. The photocatalytic reaction rate of methanol is also wavelength dependent. Possible reasons for the photon energy dependent phenomena have been discussed. This work not only provides a detailed characterization of the photochemistry of methanol on the rutile TiO2(011)-(2 × 1) surface, but also indicates the importance of photon energy in the photochemistry on TiO2 surfaces. PMID:27020321

  12. Formation of swift heavy ion tracks on a rutile TiO2 (001) surface1

    PubMed Central

    Karlušić, Marko; Bernstorff, Sigrid; Siketić, Zdravko; Šantić, Branko; Bogdanović-Radović, Ivančica; Jakšić, Milko; Schleberger, Marika; Buljan, Maja

    2016-01-01

    Nanostructuring of surfaces and two-dimensional materials using swift heavy ions offers some unique possibilities owing to the deposition of a large amount of energy localized within a nanoscale volume surrounding the ion trajectory. To fully exploit this feature, the morphology of nanostructures formed after ion impact has to be known in detail. In the present work the response of a rutile TiO2 (001) surface to grazing-incidence swift heavy ion irradiation is investigated. Surface ion tracks with the well known intermittent inner structure were successfully produced using 23 MeV I ions. Samples irradiated with different ion fluences were investigated using atomic force microscopy and grazing-incidence small-angle X-ray scattering. With these two complementary approaches, a detailed description of the swift heavy ion impact sites, i.e. the ion tracks on the surface, can be obtained even for the case of multiple ion track overlap. In addition to the structural investigation of surface ion tracks, the change in stoichiometry of the rutile TiO2 (001) surface during swift heavy ion irradiation was monitored using in situ time-of-flight elastic recoil detection analysis, and a preferential loss of oxygen was found. PMID:27738417

  13. Unique adsorption behaviors of carboxylic acids at rutile TiO2(110)

    NASA Astrophysics Data System (ADS)

    Yu, Yan-Yan; Gong, Xue-Qing

    2015-11-01

    The coverage-dependent adsorption behavior of acetic acid (CH3COOH) on rutile TiO2(110) was investigated by means of density functional theory (DFT) calculations, corrected by on-site Coulomb corrections and long-range dispersion interactions. The p(2 × 1) and c(2 × 2) domains of dissociatively adsorbed acetic acid under different coverages have been studied in detail regarding their structural and energetic properties. Adsorptions of formic acid (HCOOH) and carbonic acid (H2CO3) were also considered for better understanding the adsorption behaviors of carboxylic acids. Our calculation results show that carboxylic acids prefer to dissociatively adsorb in bridging bidentate configuration, and it induces significant surface relaxation at the adsorption site, which also affects other surface atoms nearby. Interestingly, we have shown that such adsorption-induced relaxations still maintain bond symmetries for surface Ti cations within the p(2 × 1) domain while they are drastically broken within the c(2 × 2) domain, giving rise to unstable Ti cations at the surface. This work not only explains the long-lasting puzzle of the preferable occurrence of p(2 × 1) domain for the adsorbed carboxylic acids at rutile TiO2(110), it also proposes a novel scheme that metal oxide surfaces may follow when they are involved in the processes like surface functionalization and self-assembly.

  14. Nb-doped rutile TiO₂: a potential anode material for Na-ion battery.

    PubMed

    Usui, Hiroyuki; Yoshioka, Sho; Wasada, Kuniaki; Shimizu, Masahiro; Sakaguchi, Hiroki

    2015-04-01

    The electrochemical properties of the rutile-type TiO2 and Nb-doped TiO2 were investigated for the first time as Na-ion battery anodes. Ti(1-x)Nb(x)O2 thick-film electrodes without a binder and a conductive additive were prepared using a sol-gel method followed by a gas-deposition method. The TiO2 electrode showed reversible reactions of Na insertion/extraction accompanied by expansion/contraction of the TiO2 lattice. Among the Ti(1-x)Nb(x)O2 electrodes with x = 0-0.18, the Ti(0.94)Nb(0.06)O2 electrode exhibited the best cycling performance, with a reversible capacity of 160 mA h g(-1) at the 50th cycle. As the Li-ion battery anode, this electrode also attained an excellent rate capability, with a capacity of 120 mA h g(-1) even at the high current density of 16.75 A g(-1) (50C). The improvements in the performances are attributed to a 3 orders of magnitude higher electronic conductivity of Ti(0.94)Nb(0.06)O2 compared to that of TiO2. This offers the possibility of Nb-doped rutile TiO2 as a Na-ion battery anode as well as a Li-ion battery anode.

  15. Structure and Dynamics of CO2 on Rutile TiO2(110)-1×1

    SciTech Connect

    Lin, Xiao; Yoon, Yeohoon; Petrik, Nikolay G.; Li, Zhenjun; Wang, Zhitao; Glezakou, Vassiliki Alexandra; Kay, Bruce D.; Lyubinetsky, Igor; Kimmel, Gregory A.; Rousseau, Roger J.; Dohnalek, Zdenek

    2012-12-20

    Adsorption, binding, and diffusion of CO2 molecules on rutile TiO2(110) model surfaces was investigated experimentally using scanning tunneling microscopy, infrared reflection adsorption spectroscopy (IRAS), temperature programmed desorption and theoretically via dispersion corrected density functional theory and ab initio molecular dynamics. In accord with previous studies, bridging oxygen (Ob) vacancies (VO’s) are found to be the most stable binding sites. Additional CO2 adsorbs on 5-coordinated Ti sites (Ti5c) with the initial small fraction is stabilized by CO2 on VO sites. The Ti5c-bound CO2 is found to be highly mobile at 50 K at coverages of up to 1/2 monolayer (ML). Theoretical studies show that the CO2 diffusion on Ti5c rows proceeds via a rotation-tumbling mechanism with extremely low barrier of 0.06 eV. The Ti5c-bound CO2 molecules are found to bind preferentially to a single Ti5c with the O=C=O axis tilted away from the surface normal. The binding energy of tilted CO2 molecules changes only slightly with changes in the azimuth of the CO2 tilt angle. At 2/3 ML, CO2 diffusion is hindered and at 1 ML an ordered (2×2) overlayer with a zigzag arrangement of tilted CO2 molecules develops along the Ti5c rows. Out of phase arrangement of the zigzag chains is observed across the rows. An additional 0.5 ML of CO2 can be adsorbed at Ob sites with a binding energy only slightly lower than that on Ti5c sites due to quadrupole-quadrupole interactions with the Ti5c-bound CO2 molecules.

  16. The mobility of Nb in rutile-saturated NaCl- and NaF-bearing aqueous fluids from 1–6.5 GPa and 300–800 °C

    SciTech Connect

    Tanis, Elizabeth A.; Simon, Adam; Tschauner, Oliver; Chow, Paul; Xiao, Yuming; Burnley, Pamela; Cline II, Christopher J.; Hanchar, John M.; Pettke, Thomas; Shen, Guoyin; Zhao, Yusheng

    2015-08-26

    Rutile (TiO₂) is an important host phase for high field strength elements (HFSE) such as Nb in metamorphic and subduction zone environments. The observed depletion of Nb in arc rocks is often explained by the hypothesis that rutile sequesters HFSE in the subducted slab and overlying sediment, and is chemically inert with respect to aqueous fluids evolved during prograde metamorphism in the forearc to subarc environment. However, field observations of exhumed terranes, and experimental studies, indicate that HFSE may be soluble in complex aqueous fluids at high pressure (i.e., >0.5 GPa) and moderate to high temperature (i.e., >300 °C). In this study, we investigated experimentally the mobility of Nb in NaCl- and NaF-bearing aqueous fluids in equilibrium with Nb-bearing rutile at pressure-temperature conditions applicable to fluid evolution in arc environments. Niobium concentrations in aqueous fluid at rutile saturation were measured directly by using a hydrothermal diamond-anvil cell (HDAC) and synchrotron X-ray fluorescence (SXRF) at 2.1 to 6.5 GPa and 300–500 °C, and indirectly by performing mass loss experiments in a piston-cylinder (PC) apparatus at ~1 GPa and 700–800 °C. The concentration of Nb in a 10 wt% NaCl aqueous fluid increases from 6 to 11 μg/g as temperature increases from 300 to 500 °C, over a pressure range from 2.1 to 2.8 GPa, consistent with a positive temperature dependence. The concentration of Nb in a 20 wt% NaCl aqueous fluid varies from 55 to 150 μg/g at 300 to 500 °C, over a pressure range from 1.8 to 6.4 GPa; however, there is no discernible temperature or pressure dependence. The Nb concentration in a 4 wt% NaF-bearing aqueous fluid increases from 180 to 910 μg/g as temperature increases from 300 to 500 °C over the pressure range 2.1 to 6.5 GPa. The data for the F-bearing fluid indicate that the Nb content of the fluid exhibits a dependence on temperature between 300 and 500 °C at ≥2 GPa, but there is no observed

  17. Growth and termination of a rutile IrO2(100) layer on Ir(111)

    NASA Astrophysics Data System (ADS)

    Rai, Rahul; Li, Tao; Liang, Zhu; Kim, Minkyu; Asthagiri, Aravind; Weaver, Jason F.

    2016-10-01

    We investigated the oxidation of Ir(111) by gas-phase oxygen atoms at temperatures between 500 and 625 K using temperature programmed desorption (TPD), low energy electron diffraction (LEED), low energy ion scattering spectroscopy (LEISS) and density functional theory (DFT) calculations. We find that a well-ordered surface oxide with (√ 3 × √ 3)R30° periodicity relative to Ir(111) develops prior to the formation of a rutile IrO2(100) layer. The IrO2(100) layer reaches a saturation thickness of about four oxide layers under the oxidation conditions employed, and decomposes during TPD to produce a single, sharp O2 desorption peak at ~ 770 K. Favorable lattice matching at the oxide-metal interface is likely responsible for the preferential growth of the IrO2(100) facet during the initial oxidation of Ir(111), with the resulting coincidence lattice generating a clear (6 × 1) moiré pattern in LEED. Temperature programmed reaction spectroscopy (TPRS) experiments reveal that CO and H2O molecules bind only weakly on the IrO2(100) surface and LEISS measurements show that the oxide surface is highly enriched in O-atoms. These characteristics provide strong evidence that the rutile IrO2(100) layer is oxygen-terminated, and thus lacks reactive Ir atoms that can strongly bind molecular adsorbates. Oxygen binding energies predicted by DFT suggest that on-top O-atoms will remain adsorbed on IrO2(100) at temperatures up to ~ 625 K, thus supporting the conclusion that the rutile IrO2 layer grown in our experiments is oxygen-terminated. As such, the appearance of only a single O2 TPD peak indicates that the singly coordinate, on-top O-atoms remain stable on the IrO2(100) surface up to temperatures at which the oxide layer begins to thermally decompose.

  18. Preparation of atomically flat rutile TiO2(001) surfaces for oxide film growth

    SciTech Connect

    Wang, Yang; Lee, Shinbuhm; Vilmercati, P.; Lee, Ho Nyung; Weitering, Hanno; Snijders, Paul C.

    2016-01-01

    The availability of low-index rutile TiO2 single crystal substrates with atomically flat surfaces is essential for enabling epitaxialgrowth of rutile transition metal oxide films. The high surface energy of the rutile (001) surface often leads to surface faceting, which precludes the sputter and annealing treatment commonly used for the preparation of clean and atomically flat TiO2(110) substrate surfaces. In this work, we reveal that stable and atomically flat rutile TiO2(001) surfaces can be prepared with an atomically ordered reconstructedsurface already during a furnace annealing treatment in air. We tentatively ascribe this result to the decrease in surface energy associated with the surface reconstruction, which removes the driving force for faceting. Despite the narrow temperature window where this morphology can initially be formed, we demonstrate that it persists in homoepitaxialgrowth of TiO2(001) thin films. The stabilization of surface reconstructions that prevent faceting of high-surface-energy crystal faces may offer a promising avenue towards the realization of a wider range of high quality epitaxial transition metal oxide heterostructures.

  19. Efficient phyto-synthesis and structural characterization of rutile TiO2 nanoparticles using Annona squamosa peel extract

    NASA Astrophysics Data System (ADS)

    Roopan, Selvaraj Mohana; Bharathi, A.; Prabhakarn, A.; Abdul Rahuman, A.; Velayutham, K.; Rajakumar, G.; Padmaja, R. D.; Lekshmi, Mohan; Madhumitha, G.

    2012-12-01

    In the present study, the biosynthesis of rutile TiO2 nanoparticles (TiO2 NPs) was achieved by a novel, biodegradable and convenient procedure using fruit peel Annona squamosa aqueous extract. This is the first report on the new, simple, rapid, eco-friendly and cheaper methods for the synthesis of rutile TiO2 NPs at lower temperature using agricultural waste. Rutile TiO2 NPs were characterized by UV, XRD, SEM, TEM and EDS studies. The UV-Vis spectrophotometer results were promising and showed a rapid production of TiO2 NPs with a surface plasmon resonance occurring at 284 nm. The formation of the TiO2 NPs as observed from the XRD spectrum is confirmed to be TiO2 particles in the rutile form as evidenced by the peaks at 2θ = 27.42°, 36.10°, 41.30° and 54.33° when compared with the literature. The TEM images showed polydisperse nanoparticles with spherical shapes and size 23 ± 2 nm ranges.

  20. Defects in rutile and anatase polymorphs of TiO2: kinetics and thermodynamics near grain boundaries.

    PubMed

    Uberuaga, Blas P; Bai, Xian-Ming

    2011-11-01

    The direct consequence of irradiation on a material is the creation of point defects-typically interstitials and vacancies, and their aggregates-but it is the ultimate fate of these defects that determines the material's radiation tolerance. Thus, understanding how defects migrate and interact with sinks, such as grain boundaries, is crucial for predicting the evolution of the material. We examine defect properties in two polymorphs of TiO(2)-rutile and anatase-to determine how these materials might respond differently to irradiation. Using molecular statics and temperature accelerated dynamics, we focus on two issues: how point defects interact with a representative grain boundary and how they migrate in the bulk phase. We find that grain boundaries in both polymorphs are strong sinks for all point defects, though somewhat stronger in rutile than anatase. Further, the defect kinetics are very different in the two polymorphs, with interstitial species diffusing quickly in rutile while oxygen defects-both interstitials and vacancies-are fast diffusers in anatase. These results allow us to speculate on how grain boundaries will modify the radiation tolerance of these materials. In particular, grain boundaries in rutile will lead to a space charge layer at the boundary and a vacancy-rich damage structure, while in anatase the damage structure would likely be more stoichiometric, but with larger defects consisting primarily of Ti ions.

  1. In situ loading of CuS nanoflowers on rutile TiO2 surface and their improved photocatalytic performance

    NASA Astrophysics Data System (ADS)

    Lu, Y. Y.; Zhang, Y. Y.; Zhang, J.; Shi, Y.; Li, Z.; Feng, Z. C.; Li, C.

    2016-05-01

    CuS nanoflowers, fabricated by an element-direct-reaction route using copper and sulfur powder, were loaded on rutile TiO2 (CuS/TiO2) at low temperature. CuS/TiO2 composites were utilized as the photocatalysts for the degradation of Methylene Blue (MB) and 4-chlorophenol (4-CP). X-ray diffraction (XRD), UV Raman spectroscopy, transmission electron microscopy (TEM), XPS, and UV-visible diffuse reflectance spectra were used to characterize the crystalline phase, morphology, particle size, and the optical properties of CuS/TiO2 samples. It is found that CuS/TiO2 photocatalyst, which CuS are loaded on the surface of rutile TiO2, exhibited enhanced photocatalytic degradation of MB (or 4-CP) than TiO2 or CuS. This indicates that CuS can enhance effectively the photocatalytic activity of rutile TiO2 by forming heterojunction between CuS and rutile TiO2, which is confirmed by photoluminescence (PL) spectra and TEM. Moreover, CuS content has a significant influence on photocatalytic activity and 2 wt% CuS/TiO2 showed the maximum photocatalytic activity for degradation of MB.

  2. Distinct Effects of Humic Acid on Transport and Retention of TiO2 Rutile Nanoparticles in Saturated Sand Columns

    EPA Science Inventory

    The distinct effects of humic acid (HA, 0−10 mg L−1) on the transport of titanium dioxide (rutile) nanoparticles (nTiO2) through saturated sand columns were observed under conditions of environmental relevance (ionic strength 3−200 mM NaCl, pH 5.7 and 9.0). Specifically, the tra...

  3. Distinct Effects of Humic Acid on Transport and Retention of TiO2 Rutile Nanoparticles in Saturated Sand Column

    EPA Science Inventory

    Distinct effects of humic acid (HA, 0 – 10 mg L-1) on the transport of titanium dioxide (rutile) nanoparticles (nTiO2) through saturated sand columns were observed under conditions of environmental relevance (ionic strength 3 – 200 mM NaCl, pH 5.7 and 9.0). Specifical...

  4. Efficient phyto-synthesis and structural characterization of rutile TiO2 nanoparticles using Annona squamosa peel extract.

    PubMed

    Roopan, Selvaraj Mohana; Bharathi, A; Prabhakarn, A; Rahuman, A Abdul; Velayutham, K; Rajakumar, G; Padmaja, R D; Lekshmi, Mohan; Madhumitha, G

    2012-12-01

    In the present study, the biosynthesis of rutile TiO(2) nanoparticles (TiO(2) NPs) was achieved by a novel, biodegradable and convenient procedure using fruit peel Annona squamosa aqueous extract. This is the first report on the new, simple, rapid, eco-friendly and cheaper methods for the synthesis of rutile TiO(2) NPs at lower temperature using agricultural waste. Rutile TiO(2) NPs were characterized by UV, XRD, SEM, TEM and EDS studies. The UV-Vis spectrophotometer results were promising and showed a rapid production of TiO(2) NPs with a surface plasmon resonance occurring at 284 nm. The formation of the TiO(2) NPs as observed from the XRD spectrum is confirmed to be TiO(2) particles in the rutile form as evidenced by the peaks at 2θ=27.42°, 36.10°, 41.30° and 54.33° when compared with the literature. The TEM images showed polydisperse nanoparticles with spherical shapes and size 23±2 nm ranges.

  5. Characterization of individual molecular adsorption geometries by atomic force microscopy: Cu-TCPP on rutile TiO{sub 2} (110)

    SciTech Connect

    Jöhr, Res; Hinaut, Antoine; Pawlak, Rémy; Saha, Santanu; Goedecker, Stefan; Meyer, Ernst Glatzel, Thilo; Sadeghi, Ali; Such, Bartosz; Szymonski, Marek

    2015-09-07

    Functionalized materials consisting of inorganic substrates with organic adsorbates play an increasing role in emerging technologies like molecular electronics or hybrid photovoltaics. For such applications, the adsorption geometry of the molecules under operating conditions, e.g., ambient temperature, is crucial because it influences the electronic properties of the interface, which in turn determine the device performance. So far detailed experimental characterization of adsorbates at room temperature has mainly been done using a combination of complementary methods like photoelectron spectroscopy together with scanning tunneling microscopy. However, this approach is limited to ensembles of adsorbates. In this paper, we show that the characterization of individual molecules at room temperature, comprising the determination of the adsorption configuration and the electrostatic interaction with the surface, can be achieved experimentally by atomic force microscopy (AFM) and Kelvin probe force microscopy (KPFM). We demonstrate this by identifying two different adsorption configurations of isolated copper(II) meso-tetra (4-carboxyphenyl) porphyrin (Cu-TCPP) on rutile TiO{sub 2} (110) in ultra-high vacuum. The local contact potential difference measured by KPFM indicates an interfacial dipole due to electron transfer from the Cu-TCPP to the TiO{sub 2}. The experimental results are verified by state-of-the-art first principles calculations. We note that the improvement of the AFM resolution, achieved in this work, is crucial for such accurate calculations. Therefore, high resolution AFM at room temperature is promising for significantly promoting the understanding of molecular adsorption.

  6. Tuning anatase and rutile phase ratios and nanoscale surface features by anodization processing onto titanium substrate surfaces.

    PubMed

    Roach, M D; Williamson, R S; Blakely, I P; Didier, L M

    2016-01-01

    Both the anatase (A) and rutile (R) phases of titanium oxide have shown enhanced antimicrobial and bioactivity levels but the specific A/R phase ratio needed for the best results is still unknown. In this study titanium samples were anodized to produce specific ratios of anatase and rutile phases within the oxide layers. Specific ratios produced included maximum A minimum R, minimum A maximum R, 50% A 50% R, minimum A minimum R, and a non-anodized titanium control group. Samples were characterized for phase distributions within the oxide layers, surface porosity, corrosion resistance, and bioactivity. Results indicated the targeted phase ratios were reproducibly achieved during the anodization process. Samples containing the highest levels of anatase showed the largest individual pore sizes, but a lower overall percent porosity value compared to samples containing higher rutile levels. EBSD examination of the anodized layer cross-sections provided valuable new spatial information on the distribution of anatase and rutile phases within the anodized layers. Highly porous oxide layers showed significantly higher corrosion rates compared to non-anodized titanium, but no significant differences were shown in the icorr values between samples containing primarily anatase phase, samples containing primarily rutile phase, and samples containing an approximate 50:50 mixture of the two phases. Minimum A minimum R samples showed substantially less porosity compared to the other anodization groups, a significantly lower oxide thickness, and comparable corrosion rates to non-anodized titanium. All samples within the study showed apatite production in simulated body fluid within the seven day test period indicating enhanced bioactivity.

  7. Optical studies of cobalt implanted rutile TiO2 (110) surfaces

    NASA Astrophysics Data System (ADS)

    Joshi, Shalik Ram; Padmanabhan, B.; Chanda, Anupama; Mishra, Indrani; Malik, V. K.; Mishra, N. C.; Kanjilal, D.; Varma, Shikha

    2016-11-01

    Present study investigates the photoabsorption properties of single crystal rutile TiO2 (110) surfaces after they have been implanted with low fluences of cobalt ions. The surfaces, after implantation, demonstrate fabrication of nanostructures and anisotropic nano-ripple patterns. Creation of oxygen vacancies (Ti3+ states), development of cobalt nano-clusters as well as band gap modifications have also been observed. Results presented here demonstrate that fabrication of self organized nanostructures, upon implantation, along with the development of oxygen vacancies and ligand field transitions of cobalt ion promote the enhancement of photo-absorbance in both UV (∼2 times) and visible (∼5 times) regimes. These investigations on nanostructured TiO2 surfaces can be important for photo-catalysis.

  8. Crystal-facet-dependent metallization in electrolyte-gated rutile TiO2 single crystals.

    PubMed

    Schladt, Thomas D; Graf, Tanja; Aetukuri, Nagaphani B; Li, Mingyang; Fantini, Andrea; Jiang, Xin; Samant, Mahesh G; Parkin, Stuart S P

    2013-09-24

    The electric-field-induced metallization of insulating oxides is a powerful means of exploring and creating exotic electronic states. Here we show by the use of ionic liquid gating that two distinct facets of rutile TiO2, namely, (101) and (001), show clear evidence of metallization, with a disorder-induced metal-insulator transition at low temperatures, whereas two other facets, (110) and (100), show no substantial effects. This facet-dependent metallization can be correlated with the surface energy of the respective crystal facet and, thus, is consistent with oxygen vacancy formation and diffusion that results from the electric fields generated within the electric double layers at the ionic liquid/TiO2 interface. These effects take place at even relatively modest gate voltages.

  9. Critical evaluation of the colossal Seebeck coefficient of nanostructured rutile MnO2

    NASA Astrophysics Data System (ADS)

    Music, Denis; Schneider, Jochen M.

    2015-03-01

    We have explored the correlation between the Seebeck coefficient and the electronic structure of nanostructured rutile MnO2 using density functional theory to critically appraise the three orders of magnitude scatter in literature data. Our hypothesis is that the microstructure and morphology on the nanoscale is causing this behaviour, which we have tested by comparing the Seebeck coefficient of bulk MnO2 with two low-energy surfaces: MnO2(1 1 0) and MnO2(0 0 1). From these data, it is evident that variations over two orders of magnitude in the Seebeck coefficient can be attained by affecting domain size and texture on the nanoscale. This may be understood by analysing the electronic structure. Surface hybridized Mn d-O p states fill the band gap of MnO2 and thus substantially alter the transport properties.

  10. Critical evaluation of the colossal Seebeck coefficient of nanostructured rutile MnO2.

    PubMed

    Music, Denis; Schneider, Jochen M

    2015-03-25

    We have explored the correlation between the Seebeck coefficient and the electronic structure of nanostructured rutile MnO2 using density functional theory to critically appraise the three orders of magnitude scatter in literature data. Our hypothesis is that the microstructure and morphology on the nanoscale is causing this behaviour, which we have tested by comparing the Seebeck coefficient of bulk MnO2 with two low-energy surfaces: MnO2(1 1 0) and MnO2(0 0 1). From these data, it is evident that variations over two orders of magnitude in the Seebeck coefficient can be attained by affecting domain size and texture on the nanoscale. This may be understood by analysing the electronic structure. Surface hybridized Mn d-O p states fill the band gap of MnO2 and thus substantially alter the transport properties.

  11. Electrochemical Properties of Rutile TiO2 Nanorod Array in Lithium Hydroxide Solution

    NASA Astrophysics Data System (ADS)

    Yu, Yan; Sun, Dan; Wang, Haibo; Wang, Haiyan

    2016-10-01

    In this paper, rutile TiO2 nanorod arrays are fabricated by a template-free method and proposed as a promising anode for aqueous Li-ion battery. The as-prepared TiO2 nanorod arrays exhibited reversible Li-ion insertion/extraction ability in aqueous LiOH electrolyte. Moreover, galvanostatic charge/discharge test results demonstrated that the reversible capacity of TiO2 nanorods could reach about 39.7 mC cm-2, and 93.8 % of initial capacity was maintained after 600 cycles at a current density of 1 mA cm-2 (=240 C rate), indicating excellent cycling stability and rate capability.

  12. Diffusion of CO{sub 2} on Rutile TiO{sub 2}(110) Surface

    SciTech Connect

    Lee, Junseok; Sorescu, Dan C.; Deng, Xingyi; Jordan, Kenneth D.

    2011-12-15

    The diffusion of CO{sub 2} molecules on a reduced rutile TiO{sub 2}(110)-(1×1) surface has been investigated using scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. The STM feature associated with a CO{sub 2} molecule at an oxygen vacancy (V{sub O}) becomes increasingly streaky with increasing temperature, indicating thermally activated CO{sub 2} diffusion from the V{sub O} site. From temperature-dependent tunneling current measurements, the barrier for diffusion of CO{sub 2} from the V{sub O} site is estimated to be 3.31 ± 0.23 kcal/mol. The corresponding value from the DFT calculations is 3.80 kcal/mol. In addition, the DFT calculations give a barrier for diffusion of CO{sub 2} along Ti rows of only 1.33 kcal/mol.

  13. First-principles DFT +GW study of oxygen vacancies in rutile TiO2

    NASA Astrophysics Data System (ADS)

    Malashevich, Andrei; Jain, Manish; Louie, Steven G.

    2014-02-01

    We perform first-principles calculations of the quasiparticle defect states, charge transition levels, and formation energies of oxygen vacancies in rutile titanium dioxide. The calculations are done within the recently developed combined DFT +GW formalism, including the necessary electrostatic corrections for the supercells with charged defects. We find the oxygen vacancy to be a negative U defect, where U is the defect electron addition energy. For Fermi level values below ˜2.8 eV (relative to the valence-band maximum), we find the +2 charge state of the vacancy to be the most stable, while above 2.8 eV we find that the neutral charge state is the most stable.

  14. Enhanced performance of natural dye sensitised solar cells fabricated using rutile TIO2 nanorods

    NASA Astrophysics Data System (ADS)

    Akila, Y.; Muthukumarasamy, N.; Agilan, S.; Mallick, Tapas K.; Senthilarasu, S.; Velauthapillai, Dhayalan

    2016-08-01

    Due to the lower cost, natural dye molecules are good alternatives for the ruthenium based sensitizers in the dye-sensitized solar cells. In this article, we have reported the natural sensitizer based dye-sensitized solar cells fabricated using TiO2 nanorods. Rutile phase TiO2 nanorods have been synthesized by template free hydrothermal method which results in TiO2 nanorods in the form of acropora corals. These TiO2 nanorods have been sensitized by flowers of Sesbania grandiflora, leaves of Camellia sinensis and roots of Rubia tinctorum. The maximum conversion efficiency of 1.53% has been obtained for TiO2 nanorods based solar cells sensitized with the leaves of Camellia sinensis. The flowers of Sesbania grandiflora and roots of Rubia tinctorum sensitized TiO2 nanorods based solar cells exhibited an efficiency of 0.65% and 1.28% respectively.

  15. Evolution of electronic correlations across the rutile, perovskite, and Ruddelsden-Popper iridates with octahedral connectivity

    NASA Astrophysics Data System (ADS)

    Kawasaki, Jason K.; Uchida, Masaki; Paik, Hanjong; Schlom, Darrell G.; Shen, Kyle M.

    2016-09-01

    The confluence of electron correlations and spin-orbit interactions is critical to realizing quantum phases in 5 d transition metal oxides. Here, we investigate how the strength of the effective electron correlations evolve across a series of d5 iridates comprised of IrO6 octahedra, ranging from the layered correlated insulator Sr2IrO4 , to the three-dimensional perovskite semimetal SrIrO3, to metallic rutile IrO2 in which the octahedra are arranged in a mixed edge and corner sharing network. Through a combination of reactive oxide molecular-beam epitaxy, in situ angle-resolved photoemission spectroscopy, core level photoemission, and density functional theory, we show how the effective electron correlations weaken as a function of increasing connectivity of the IrO6 network and p -d hybridization. Our results demonstrate how structure and connectivity can be used to control the strength of correlations in the iridates.

  16. Boron-tuning transition temperature of vanadium dioxide from rutile to monoclinic phase

    SciTech Connect

    Zhang, J. J.; He, H. Y.; Xie, Y.; Pan, B. C.

    2014-11-21

    The effect of the doped boron on the phase transition temperature between the monoclinic phase and the rutile phase of VO{sub 2} has been studied by performing first-principles calculations. It is found that the phase transition temperature decreases linearly with increasing the doping level of B in each system, no matter where the B atom is in the crystal. More importantly, the descent of the transition temperature is predicted to be as large as 83 K/at. % B, indicating that the boron concentration of only 0.5% can cause the phase transition at room temperature. These findings provide a new routine of modulating the phase transition of VO{sub 2} and pave a way for the practicality of VO{sub 2} as an energy-efficient green material.

  17. Formaldehyde adsorption and decomposition on rutile (110): A first-principles study

    NASA Astrophysics Data System (ADS)

    Liu, Liming; Zhao, Jin

    2016-10-01

    We investigated the adsorption and decomposition of formaldehyde (HCHO) molecule on stoichiometric rutile TiO2(110) surface using first principles-calculations. By comparing the adsorption energy of one bidentate and two monodentate configurations, we found the bidentate configuration is the most stable one because of an additional C-O bond formation. The monodentate configuration can change into the bidentate configuration by overcoming a small barrier less than 0.1 eV. Then, we investigated the decomposition of HCHO which involves two deprotonation processes starting from different adsorption structures. The energy barrier of the first deprotonation is 1.3 eV and 1.1 eV for bidentate and monodentate configurations. After the first deprotonation, an adsorbed formate HCOO specie is formed. The second deprotonation needs 1.74 eV and 1.64 eV for bidentate and monodentate configurations, respectively. After that, an adsorbed CO2 is formed. It can desorb from the surface after overcoming a small barrier of 0.12 eV. In principle, it is also possible to obtain a CO molecule from the surface. Yet a large energy barrier higher than 1.74 eV needs to be overcome. By analyzing the energy level alignment of molecular orbitals with TiO2 energy band edges, we discussed the photocatalytic activity of the reactants and intermediates during the decomposition process. Our results give a clear description of the adsorption structure and thermal decomposition process of HCHO on rutile TiO2(110) surface. The discussion of photocatalytic reactivity based on energy level alignment provides valuable insights to understand the combined photocatalytic and thermally catalytic reactions.

  18. High photocatalytic activity of mixed anatase-rutile phases on commercial TiO2 nanoparticles

    NASA Astrophysics Data System (ADS)

    Ruu Siah, Wai; Lintang, Hendrik O.; Shamsuddin, Mustaffa; Yuliati, Leny

    2016-02-01

    Titanium dioxide (TiO2) is well-known as an active photocatalyst for degradation of various organic pollutants. Over the years, a wide range of TiO2 nanoparticles with different phase compositions, crystallinities, and surface areas have been developed. Due to the different methods and conditions used to synthesize these commercial TiO2 nanoparticles, the properties and photocatalytic performance would also be different from each other. In this study, the photocatalytic removal of 2,4-dichlorophenoxyacetic acid (2,4-D) and 2,4,5- trichlorophenoxyacetic acid (2,4,5-T) was investigated on commercial Evonik P25, Evonik P90, Hombikat UV100 and Hombikat N100 TiO2 nanoparticles. Upon photocatalytic tests, it was found that overall, the photocatalytic activities of the P25 and the P90 were higher than the N100 and the UV100 for the removal of both 2,4-D and 2,4,5-T. The high activities of the P25 and the P90 could be attributed to their phase compositions, which are made up of a mixture of anatase and rutile phases of TiO2. Whereas, the UV100 and the N100 are made up of 100% anatase phase of TiO2. The synergistic effect of the anatase/rutile mixture was reported to slow down the recombination rate of photogenerated electron-hole pairs. Consequently, the photocatalytic activity was increased on these TiO2 nanoparticles.

  19. Heterogeneity and Disorder in Ti{1-x}Fe{y}O{2-d) Nanocrystal Rutile-based Flower Like Aggregates: Detection of Anatase

    SciTech Connect

    Bozin, E.S.; Kremenovic, A.; Antic, B.; Blanusa, J.; Comor, M.; Columban, P.; Mazerolles, L.

    2011-03-24

    Here we report results of systematic investigation of heterogeneity and disorder in Ti{sub 1-x}Fe{sub y}O{sub 2-d} nanorod rutile-based flowerlike aggregates. It was found that Ti{sub 1-x}Fe{sub y}O{sub 2-d} aggregates are composed of two crystalline phases: rutile as a dominant and anatase as a minor phase. Flowerlike aggregates were found to grow from an isometric core ca. 5-10 nm in diameter that was built from anatase and rutile nanorods ca. 5 x 100 nm that were grown on the anatase surface having base plane (001) intergrowth with an anatase plane. The direction of rutile nanorods growth, i.e., direction of the nanorod elongation, was [001]. Highly nonisometric rutile crystals produce anisotropic X-ray powder diffraction line broadening and doubling of vibrational bands in Raman spectra. Both these techniques confirmed nonisometric character of rutile crystals and gave a quantitative measure of crystal shape anisotropy in excellent agreement with high-resolution transmission electron microscopy measurements. In addition, from the atomic pair distribution function and Raman spectral analyses the level of vacancy concentration was determined in rutile and anatase phases of investigated samples.

  20. Fe(II)Ti(IV)O3 mixed oxide monolayer at rutile TiO2(011): Structures and reactivities

    NASA Astrophysics Data System (ADS)

    Wen, Zhan-Hui; Halpegamage, Sandamali; Gong, Xue-Qing; Batzill, Matthias

    2016-11-01

    Mixed-metal oxide monolayer grown at an oxide support is of great potential in applications like heterogeneous catalysis. In this work, the experimentally obtained ordered mixed FeTiO3 oxide monolayer supported by rutile TiO2(011) surface has been carefully studied with density functional theory calculations. The genetic algorithm based optimization scheme has been employed to improve the searching capacity for possible structures, and a well ordered mixed Fe(II)Ti(IV)O3 monolayer oxide structure much more stable than the one proposed previously has been successfully located. The new surface structure consists of uniformly distributed Ti and Fe cations in the ratio of 2:1. The simulated Scanning Tunneling Microscopy image based on this model is well consistent with the experimental one. Our calculations have shown that the O vacancy formation energy is rather high at the surface. We have also studied the adsorption of O2 and CO at the exposed Fe sites on the surface as well as their reactions. The adsorption energies of O2 are generally higher than those of CO. The catalytic cycle of CO oxidation following an Eley-Rideal type mechanism has been located for CO to react with surface adsorbed O2 and O.

  1. Zirconium-in-Rutile thermometry: increasing resolution of temperatures in the Dulan ultrahigh-pressure region, northwest China

    NASA Astrophysics Data System (ADS)

    Regel, M. E.; Mattinson, C. G.

    2012-12-01

    The North Qaidam ultrahigh-pressure (UHP) terrane in northwestern China contains the approximately 140 km2 Dulan UHP region, with UHP eclogites outcropping in the east and high-pressure (HP) granulites outcropping in the west. Zirconium (Zr)-in-Rutile (Rt) thermometry of six representative samples (five eclogites and one granulite) was completed to determine the spatial variation of temperatures within the east-west oriented Dulan UHP belt. Previous Fe2+-Mg exchange thermometry from the Dulan UHP and HP rocks provides a temperature range of 620 - 930 °C, however; the large range of temperatures and large uncertainty prevented a detailed understanding of P-T histories and exhumation paths. Peak eclogite pressures have been estimated at 26-32 kbars, and granulite pressures at ~14 kbars. 20 - 40 electron microprobe spots from both matrix and inclusion Rt crystals were selected from polished thin sections. Fe content increases weakly with temperature, while Si decreases weakly with increasing temperature. Cr and Nb do not show consistent temperature trends. Inclusion rutiles in two samples record temperatures ~40-50 °C lower than matrix rutiles of the same samples. This preservation of prograde metamorphic conditions suggests that the temperatures increased during development of the peak eclogite assemblage. Inclusion rutile temperatures in four samples match the matrix rutile, suggesting recrystallization of the eclogites during peak metamorphic conditions. The granulite shows two temperature populations: 1) ~800 °C, and 2) ~750 - 800 °C. The lower temperature rutiles are located near a retrogressed fracture filled with secondary minerals. From the east to the west, the eclogites show peak temperatures of 670 °C, 662 °C, 691 °C, and 711 °C, respectively, while the granulite sample has an average peak temperature of ~800 °C. The UHP eclogites preserve a small temperature gradient, but the temperature discontinuity between the UHP eclogites in the east and the

  2. Comparative study of phase transition and textural changes upon calcination of two commercial titania samples: A pure anatase and a mixed anatase-rutile

    NASA Astrophysics Data System (ADS)

    Kordouli, Eleana; Dracopoulos, Vassileios; Vaimakis, Tiverios; Bourikas, Kyriakos; Lycourghiotis, Alexis; Kordulis, Christos

    2015-12-01

    The effect of calcination temperature and time on structural and textural changes of two commercial TiO2 samples (pure anatase and a mixture of anatase and rutile) has been investigated using N2 physisorption, ex-situ and in-situ X-ray powder diffraction, differential scanning calorimetry and UV-vis diffuse reflectance spectroscopy. The increase of the calcination temperature (up to 700 °C) and time (up to 8 h) causes only textural changes in the pure anatase, whereas a transformation of the anatase to rutile takes place, in addition, in the mixed titania (containing anatase and rutile). The textural changes observed in pure anatase sample were attributed to solid state diffusion leading to an increase in the size of anatase nanocrystals, through sintering. Thus, the mean pore diameter shifts to higher values and the pore volume and specific surface area decrease. The successful application of the Johnson-Mehl-Avrami-Kolmogorov model in the kinetic data concerning the pure anatase indicates a mass transfer control of sintering process. Similar textural changes were also observed upon calcination of the sample containing anatase and rutile. In this case not only sintering but the anatase to rutile transformation contributes also to the textural changes. Kinetic analysis showed that the rutile nanocrystals in the mixed titania served as seed for by-passing the high energy barrier nucleation step allowing/facilitating thus the anatase to rutile transformation. A fine control of the anatase to rutile ratio and thus of energy-gap and the population of hetero-junctions may be obtained by adjusting the calcination temperature and time.

  3. Hydrofluoric Acid Controlled TiO2 Phase Transformation from Rutile to Anatase at Room Temperature and Their Photocatalytic Performance.

    PubMed

    Ge, Suxiang; Li, Dapeng; Jia, Gaoyang; Wang, Beibei; Yang, Zhen; Yang, Zongyang; Qiao, Hui; Zhang, Yange; Zheng, Zhi

    2015-09-01

    In this study, we first present rutile TiO2 superstructures could be successfully transformed into anatase TiO2 nanoparticles at room temperature by adjusting the amount of hydrofluoric acid (HF) used in aqueous solution. Photocatalytic experiments demonstrated that the as prepared anatase TiO2 exhibited better photocatalytic performance than that of rutile TiO2. We further studied the photocatalytic degradation of RhB on different TiO2 via active species trapping experiments and confirmed that the presence of surface F- on TiO2 was beneficial for the formation of *OH, which was thought to be mainly responsible for the enhancement of photocatalytic performance.

  4. Photocatalytic Activity of Bulk TiO{sub 2} Anatase and Rutile Single Crystals Using Infrared Absorption Spectroscopy

    SciTech Connect

    Xu Mingchun; Gao Youkun; Moreno, Elias Martinez; Kunst, Marinus; Muhler, Martin; Wang Yuemin; Idriss, Hicham; Woell, Christof

    2011-04-01

    A systematic study on the photocatalytic activity of well-defined, macroscopic bulk single-crystal TiO{sub 2} anatase and rutile samples has been carried out, which allows us to link photoreactions at surfaces of well-defined oxide semiconductors to an important bulk property with regard to photochemistry, the life time of e-h pairs generated in the bulk of the oxides by photon absorption. The anatase (101) surface shows a substantially higher activity, by an order of magnitude, for CO photo-oxidation to CO{sub 2} than the rutile (110) surface. This surprisingly large difference in activity tracks the bulk e-h pair lifetime difference for the two TiO{sub 2} modifications as determined by contactless transient photoconductance measurements on the corresponding bulk materials.

  5. A novel and efficient surfactant-free synthesis of Rutile TiO2 microflowers with enhanced photocatalytic activity

    NASA Astrophysics Data System (ADS)

    Nair, Radhika V.; Jijith, M.; Gummaluri, Venkata Siva; Vijayan, C.

    2016-05-01

    Rutile TiO2 microflowers with three-dimensional spiky flower like architecture at the nanometer level are obtained by a fast single step surfactant free ethylene glycol based solvothermal scheme of synthesis. These structures are characterized by X-ray Diffraction (XRD), Field emission scanning electron microscopy (FESEM), Transmission electron microscopy (TEM) and Raman spectroscopy. These measurements confirm Rutile phase of TiO2 flowers with very high crystallinity. Photodegradation of Rhodamine B with UV exposure is investigated by UV-Visible spectroscopy measurements in the presence of these samples. They are shown to have high photocatalytic activity due to the large surface area contributed by the highly dense spiky nanostructures. The plasmonic (Au) loading in these structures are shown to significantly enhance the photocatalytic activity.

  6. Spectroscopic properties of electrochemically populated electronic states in nanostructured TiO2 films: anatase versus rutile.

    PubMed

    Berger, Thomas; Anta, Juan A; Morales-Flórez, Víctor

    2013-09-01

    A thorough characterization of nanostructured materials under application-relevant conditions is a prerequisite for elucidating the interplay between their physicochemical nature and their functional properties in practical applications. Here, we use a spectroelectrochemical approach to study the population of electronic states in different types of nanostructured anatase and rutile TiO2 films in contact with an aqueous electrolyte. The spectroscopic properties of the two polymorphs were addressed under Fermi level control in the energy range between the fundamental absorption threshold and the onset of lattice absorption (3.3-0.1 eV). The results evidence the establishment of an equilibrium between localized Ti(3+) centers absorbing in the vis/NIR and shallow (e(-))(H(+)) traps absorbing in the MIR upon electron accumulation in anatase electrodes. The absence of the MIR-active (e(-))(H(+)) traps on all rutile electrodes points to a crystal structure-dependent electron population in the films.

  7. Room temperature synthesized rutile TiO(2) nanoparticles induced by laser ablation in liquid and their photocatalytic activity.

    PubMed

    Liu, Peisheng; Cai, Weiping; Fang, Ming; Li, Zhigang; Zeng, Haibo; Hu, Jinlian; Luo, Xiangdong; Jing, Weiping

    2009-07-15

    TiO(2) nanoparticles were prepared by one-step pulsed laser ablation of a titanium target immersed in a poly-(vinylpyrrolidone) solution at room temperature. The products were systematically characterized by x-ray diffraction (XRD), transmission electron microscopy (TEM), Raman spectroscopy and x-ray photoelectron spectroscopy (XPS). The results indicated that the rutile TiO(2) nanocrystalline particles were one-step synthesized at room temperature and the mean size in diameter is about 50 nm with a narrow size distribution. A probable formation process was proposed on the basis of the microstructure and the instantaneous plasma plume induced by the laser. Photocatalytic activity was monitored by degradation of a methylene blue solution. The as-prepared rutile TiO(2) nanoparticles demonstrate a good photocatalytic performance. This work shows that pulsed laser ablation in liquid media is a good method to synthesize some nanosized materials which are difficult to produce by other conventional methods.

  8. Electronic properties of atomic layer deposition films, anatase and rutile TiO2 studied by resonant photoemission spectroscopy

    NASA Astrophysics Data System (ADS)

    Das, C.; Richter, M.; Tallarida, M.; Schmeisser, D.

    2016-07-01

    The TiO2 films are prepared by atomic layer deposition (ALD) method using titanium isopropoxide precursors at 250 °C and analyzed using resonant photoemission spectroscopy (resPES). We report on the Ti2p and O1s core levels, on the valence band (VB) spectra and x-ray absorption spectroscopy (XAS) data, and on the resonant photoelectron spectroscopy (resPES) profiles at the O1s and the Ti3p absorption edges. We determine the elemental abundance, the position of the VB maxima, the partial density of states (PDOS) in the VB and in the conduction band (CB) and collect these data in a band scheme. In addition, we analyze the band-gap states as well as the intrinsic states due to polarons and charge-transfer excitations. These states are found to cause multiple Auger decay processes upon resonant excitation. We identify several of these processes and determine their relative contribution to the Auger signal quantitatively. As our resPES data allow a quantitative analysis of these defect states, we determine the relative abundance of the PDOS in the VB and in CB and also the charge neutrality level. The anatase and rutile polymorphs of TiO2 are analyzed in the same way as the TiO2 ALD layer. The electronic properties of the TiO2 ALD layer are compared with the anatase and rutile polymorphs of TiO2. In our comparative study, we find that ALD has its own characteristic electronic structure that is distinct from that of anatase and rutile. However, many details of the electronic structure are comparable and we benefit from our spectroscopic data and our careful analysis to find these differences. These can be attributed to a stronger hybridization of the O2p and Ti3d4s states for the ALD films when compared to the anatase and rutile polymorphs.

  9. Low temperature one-step synthesis of rutile TiO{sub 2}/BiOCl composites with enhanced photocatalytic activity

    SciTech Connect

    Duo, Fangfang; Wang, Yawen Fan, Caimei; Mao, Xiaoming; Zhang, Xiaochao; Wang, Yunfang; Liu, Jianxin

    2015-01-15

    The rutile TiO{sub 2}/BiOCl composites were successfully fabricated by a facile one-step hydrolysis method at low temperature (50 °C). The X-ray diffraction, scanning electron microscopy, transmission electron microscopy, UV–vis diffuse reflectance spectra, Fourier transform infrared spectroscopy, Brunauer–Emmett–Teller, and X-ray photoelectron spectroscopy measurements were employed to characterize the phase structures, morphologies, optical properties, surface areas, and electronic state of the samples. The rutile TiO{sub 2}/BiOCl composites exhibited higher photocatalytic activity than pure BiOCl and rutile TiO{sub 2} for the degradation of phenol under artificial solar light irradiation. In addition, the photocatalytic mechanism has also been investigated and discussed. The enhanced photocatalytic performance of rutile TiO{sub 2}/BiOCl composites is closely related to the heterojunctions between BiOCl and rutile TiO{sub 2}, which can not only broaden the light adsorption range of BiOCl but also improve the electron–hole separation efficiency under artificial solar light irradiation. - Highlights: • Rutile TiO{sub 2}/BiOCl was prepared by a low temperature one-step hydrolysis method. • The synthetic method is quite convenient and energy-saving. • The composites exhibit enhanced photocatalytic activity on phenol degradation. • The high photocatalytic activity relates to the heterojunctions of BiOCl and TiO{sub 2}.

  10. Effect of gas flow rates on the anatase-rutile transformation temperature of nanocrystalline TiO2 synthesised by chemical vapour synthesis.

    PubMed

    Ahmad, Md Imteyaz; Bhattacharya, S S; Fasel, Claudia; Hahn, Horst

    2009-09-01

    Of the three crystallographic allotropes of nanocrystalline titania (rutile, anatase and brookite), anatase exhibits the greatest potential for a variety of applications, especially in the area of catalysis and sensors. However, with rutile being thermodynamically the most stable phase, anatase tends to transform into rutile on heating to temperatures in the range of 500 degrees C to 700 degrees C. Efforts made to stabilize the anatase phase at higher temperatures by doping with metal oxides suffer from the problems of having a large amorphous content on synthesis as well as the formation of secondary impurity phases on doping. Recent studies have suggested that the as-synthesised phase composition, crystallite size, initial surface area and processing conditions greatly influence the anatase to rutile transformation temperature. In this study nanocrystalline titania was synthesised in the anatase form bya chemical vapour synthesis (CVS) method using titanium tetra iso-propoxide (TTIP) as a precursor under varying flow rates of oxygen and helium. The anatase to rutile transformation was studied using high temperature X-ray diffraction (HTXRD) and simultaneous thermogravimetric analysis (STA), followed by transmission electron microscopy (TEM). It was demonstrated that the anatase-rutile transformation temperatures were dependent on the oxygen to helium flow rate ratio during CVS and the results are presented and discussed. PMID:19928267

  11. Degradation of polycyclic aromatic hydrocarbons in crumb tyre rubber catalysed by rutile TiO2 under UV irradiation.

    PubMed

    Yu, Kai; Huang, Linyue; Lou, Lan-Lan; Chang, Yue; Dong, Yanling; Wang, Huan; Liu, Shuangxi

    2015-01-01

    The polycyclic aromatic hydrocarbons (PAHs) in crumb tyre rubber were firstly degraded under UV irradiation in the presence of rutile TiO2 and hydrogen peroxide. The effects of light intensity, catalyst amount, oxidant amount, initial pH value, co-solvent content, and reaction time on degradation efficiency of typical PAHs in crumb tyre rubber were studied. The results indicated that UV irradiation, rutile TiO2, and hydrogen peroxide were beneficial to the degradation of PAHs and co-solvent could accelerate the desorption of PAHs from crumb tyre rubber. Up to 90% degradation efficiency of total 16 PAHs could be obtained in the presence of rutile TiO2 (1 wt%) and hydrogen peroxide (1.0 mL) under 1800 µW cm(-2) UV irradiation for 48 h. The high molecular weight PAHs (such as benz(a)pyrene) were more difficult to be degraded than low molecular weight PAHs (such as phenanthrene, chrysene). Moreover, through the characterization of reaction solution and degradation products via GC-MS, it was proved that the PAHs in crumb tyre rubber were successfully degraded.

  12. TiO2 nanocrystals coated rutile nanorod microspheres as the scattering layers for dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Gao, Mengyu; Wang, Hongzhi; Li, Yaogang; Zhang, Qinghong

    2013-12-01

    Anatase TiO2 nanocrystals were deposited on the rutile TiO2 nanorod microspheres (NCRNMs) via the controlled hydrolysis and condensation of titanium (IV) bis(ammonium lactato) dihydroxide (TALH) in the presence of polyethyleneimine (PEI). The anatase TiO2 nanocrystals prevented the growth of rutile TiO2 nanorod microspheres from sintering process. By coating of anatase nanocrystals, the decreasing of specific surface area of rutile TiO2 nanorod microspheres (RNMs) were efficiently inhibited. The specific surface area of NCRNM was 47.0 m2/g after sintering at 500 °C,which was 50% increment compared to RNM. The dye sensitized solar cells (DSSCs) were assembled using the semitransparent underlayers and NCRNM scattering layers as the photoanodes. The incident photon to current conversion efficiency (IPCE) analysis showed the DSSCs in the presence of NCRNMs adsorbed more dye molecules while kept a high light-harvesting efficiency. The cell covered with the NCRNM scattering layer had the efficiency of 7.33%, which was 20% increment compared to that of the absence one.

  13. A simple and low temperature process for super-hydrophilic rutile TiO 2 thin films growth

    NASA Astrophysics Data System (ADS)

    Mane, R. S.; Joo, Oh-Shim; Min, Sun-Ki; Lokhande, C. D.; Han, Sung-Hwan

    2006-11-01

    We investigate an environmentally friendly aqueous solution system for rutile TiO 2 violet color nanocrystalline thin films growth on ITO substrate at room temperature. Film shows considerable absorption in visible region with excitonic maxima at 434 nm. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected area electron diffraction (SAED), UV-vis, water surface contact angle and energy dispersive X-ray analysis (EDX) techniques in addition to actual photo-image that shows purely rutile phase of TiO 2 with violet color, super-hydrophilic and densely packed nanometer-sized spherical grains of approximate diameter 3.15 ± 0.4 nm, characterize the films. Band gap energy of 4.61 eV for direct transition was obtained for the rutile TiO 2 films. Film surface shows super-hydrophilic behavior, as exhibited water contact angle was 7°. Strong visible absorption (not due to chlorine) leaves future challenge to use these films in extremely thin absorber (ETA) solar cells.

  14. Self assembled DC sputtered nanostructured rutile TiO₂ platform for bisphenol A detection.

    PubMed

    Singh, Nawab; Reza, K Kamil; Ali, Md Azahar; Agrawal, Ved Varun; Biradar, A M

    2015-06-15

    A novel biosensor platform comprising of the functionalized sputtered rutile nanostructured titanium dioxide (nTiO2) for rapid detection of estrogenic substance (bisphenol A) has been proposed. The direct current (DC) sputtering of titanium (Ti) on glass substrate has been converted to ordered nanostructured TiO2 film via oxidation. The nanostructured TiO2 surface was functionalized with self-assembled monolayer (SAM) of 3-aminopropyltriethoxysilane (APTES) and glutaraldehyde. The enzyme molecule, tyrosinase (Tyrs) has been covalently immobilized on the surface of APTES modified nanostructured TiO2 film. To investigate the crystalline structure and surface morphology of functionalized nTiO2/Ti electrode, the X-ray diffraction, scanning electron microscopy, atomic force microscopy and Fourier transform infrared spectroscopy have been carried out. This impedimetric biosensor exhibits a comparable sensitivity (361.9 kΩ/µM) in a wide range of detection (0.01-1.0 µM) and a response time of 250 s for bisphenol A (BPA) monitoring. This novel manufacturing process for nTiO2 film is cheap, practical and safer for functionalization with SAM and glutaraldehyde to improve the biosensor efficacy. The strong protein absorption capability of the nTiO2 surface demonstrates an excellent electrochemical biosensor and could be useful for the detection of other phenolic compounds. PMID:25656780

  15. Enhanced Raman spectroscopy of 2,4,6-TNT in anatase and rutile titania nanocrystals

    NASA Astrophysics Data System (ADS)

    De La Cruz-Montoya, Edwin; Jeréz, Jaqueline I.; Balaguera-Gelves, Marcia; Luna-Pineda, Tatiana; Castro, Miguel E.; Hernández-Rivera, Samuel P.

    2006-05-01

    The majority of explosives found in antipersonnel and antitank landmines contain 2,4,6-trinitrotoluene (TNT). Chemical sensing of landmines and Improvised Explosive Devices (IED) requires detecting the chemical signatures of the explosive components in these devices. Nanotechnology is ideally suited to needs in microsensors development by providing new materials and methods that can be employed for trace explosive detection. This work is focused on modification of nano-scaled colloids of titanium dioxide (Titania: anatase, rutile and brookite) and thin layer of the oxides as substrates for use in Enhanced Raman Scattering (ERS) spectroscopy. Ultrafine particles have been generated by hydrothermally treating the sol-gel derived hydrous oxides. ERS spectra of nanocrystalline anatase Titania samples prepared with different average sizes: 38 nm (without acid), 24 nm (without acid) and 7 nm (with HCl). Bulk phase (commercial) and KBr were also used to prepare mixtures with TNT to look for Enhanced Raman Effect of the nitroaromatic explosive on the test surfaces. The studies clearly indicated that the anatase crystal size affects the enhancement of the TNT Raman signal. This enhancement was highest for the samples with Titania average crystal size of 7 nm.

  16. First-principles thermochemistry for gas phase species in an industrial rutile chlorinator.

    PubMed

    Shirley, Raphael; Phadungsukanan, Weerapong; Kraft, Markus; Downing, Jim; Day, Nick E; Murray-Rust, Peter

    2010-11-01

    This work presents thermochemical data for possible gas phase intermediate species in an industrial rutile chlorinator. An algorithm developed for previous work is employed to ensure that all possible species are considered, reducing the number of important species neglected. Thermochemical data and enthalpies of formation are calculated for 22 new species using density functional theory, post Hartree-Fock coupled cluster calculations, and statistical mechanics. Equilibrium calculations are performed to identify whether any Ti/C intermediates are likely to be important to the high temperature industrial process. These new species are not present at high concentration in the exit stream. It is therefore likely that the two chemical processes do not interact. Rather, the Cl₂ rapidly reacts with the solid TiO₂ to form TiCl₄ and O₂. The latter then reacts with the solid C to form CO and CO₂ and provide the heat. Data for all the new species is provided as Supporting Information. Finally, a new methodology for data collaboration is investigated in which the data is made openly accessible using the resource description framework. Example scripts are provided to demonstrate how to query and retrieve the data automatically.

  17. Adsorption of small hydrocarbons on rutile TiO2(110)

    NASA Astrophysics Data System (ADS)

    Chen, Long; Smith, R. Scott; Kay, Bruce D.; Dohnálek, Zdenek

    2016-08-01

    Temperature programmed desorption and molecular beam scattering were used to study the adsorption and desorption of small hydrocarbons (n-alkanes, 1-alkenes and 1-alkynes of C1-C4) on rutile TiO2(110). We show that the sticking coefficients for all the hydrocarbons are close to unity (> 0.95) at an adsorption temperature of 60 K. The desorption energies for hydrocarbons of the same chain length increase from n-alkanes to 1-alkenes and to 1-alkynes. This trend is likely a consequence of additional dative bonding of the alkene and alkyne π system to the coordinatively unsaturated Ti5c sites. Similar to previous studies on the adsorption of n-alkanes on metal and metal oxide surfaces, we find that the desorption energies within each group (n-alkanes vs. 1-alkenes vs. 1-alkynes) from Ti5c sites increase linearly with the chain length. The absolute saturation coverages of each hydrocarbon on Ti5c sites were also determined. The saturation coverage of CH4, is found to be ~ 2/3 monolayer (ML). The saturation coverages of C2-C4 hydrocarbons are found nearly independent of the chain length with values of ~ 1/2 ML for n-alkanes and 1-alkenes and 2/3 ML for 1-alkynes. This result is surprising considering their similar sizes.

  18. Localized states induced by an oxygen vacancy in rutile TiO{sub 2}

    SciTech Connect

    Lin, Chungwei; Shin, Donghan; Demkov, Alexander A.

    2015-06-14

    Using density functional theory and model Hamiltonian analysis, we investigate the localized states induced by an oxygen vacancy in rutile TiO{sub 2}. We identify two classes of localized states—the hybrid and the polaron. The hybrid state is caused by the orbital overlap between three Ti atoms next to a vacancy and is mainly derived from the Ti e{sub g} orbitals. The polaron state is caused by the local lattice distortion and is mainly composed of one particular t{sub 2g} orbital from a single Ti atom. The first principles calculation shows that the polaron state is energetically favored, and the tight-binding analysis reveals the underlying connection between the bulk band structure and the orbital character of the polaron. The magnetic coupling between two nearby polaron states is found to be ferromagnetic. Using this picture, we analyze the results of recent theoretical calculations and experiments and discuss the connection to vacancies in SrTiO{sub 3}.

  19. Adsorption of small hydrocarbons on rutile TiO2(110)

    DOE PAGES

    Chen, Long; Smith, R. Scott; Kay, Bruce D.; Dohnalek, Zdenek

    2015-11-21

    Here, temperature programmed desorption and molecular beam scattering were used to study the adsorption and desorption of small hydrocarbons (n-alkanes, 1-alkenes and 1-alkynes of C1–C4) on rutile TiO2(110). We show that the sticking coefficients for all the hydrocarbons are close to unity (> 0.95) at an adsorption temperature of 60 K. The desorption energies for hydrocarbons of the same chain length increase from n-alkanes to 1-alkenes and to 1-alkynes. This trend is likely a consequence of additional dative bonding of the alkene and alkyne π system to the coordinatively unsaturated Ti5c sites. Similar to previous studies on the adsorption ofmore » n-alkanes on metal and metal oxide surfaces, we find that the desorption energies within each group (n-alkanes vs. 1-alkenes vs. 1-alkynes) from Ti5c sites increase linearly with the chain length. The absolute saturation coverages of each hydrocarbon on Ti5c sites were also determined. The saturation coverage of CH4, is found to be ~ 2/3 monolayer (ML). The saturation coverages of C2–C4 hydrocarbons are found nearly independent of the chain length with values of ~ 1/2 ML for n-alkanes and 1-alkenes and 2/3 ML for 1-alkynes. This result is surprising considering their similar sizes.« less

  20. Characterization of CO2 behavior on rutile TiO2 (110) surface

    SciTech Connect

    Yoon, Yeohoon

    2013-06-03

    The dynamic behavior of carbon dioxide (CO2) adsorbed on the rutile TiO2 (110) surface is studied by dispersion-corrected density functional theory (DFT) and combined ab initio molecular dynamics (AIMD). Understanding he behavior of CO2 is important regarding possible applications for treating CO2 in current environmental problems along with the consideration as a renewable energy source. Concerning the ability as a redusible support of TiO2 surface, a fundamental understanding of the interaction between CO2 and TiO2 surface will help extending the possibile applications. In the current study, CO2 interaction and dynamics behavior on the TiO2 surface is characterized including he effect of the oxygen vacancy (OV) defect. Also the coverage dependence of CO2 behavior is investigated since more contribution of the intermolecular interaction among CO2 molecules can be expected as the coverage increasing. This work is supported by the US Department of Energy (DOE), Office of Basic Science, Division of Chemical Sciences, Geosicences and Biosciences. Pacific Northwest National Laboratory (PNNL) is multiprogram national laboratory operated for DOE by Battelle. A portion of the research was performed using EMSL, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory.

  1. Effective dose in SMAW and FCAW welding processes using rutile consumables.

    PubMed

    Herranz, M; Rozas, S; Idoeta, R; Alegría, N

    2014-03-01

    The shielded metal arc welding (SMAW) and flux cored arc welding (FCAW) processes use covered electrodes and flux cored wire as consumables. Among these consumables, ones containing rutile are the most widely used, and since they have a considerable natural radioactive content, they can be considered as NORM (naturally occurring radioactive material). To calculate the effective dose on workers during their use in a conservative situation, samples of slag and aerosols and particles emitted or deposited during welding were taken and measured by gamma, alpha and beta spectrometry. An analytical method was also developed for estimating the activity concentration of radionuclides in the inhaled air. (222)Rn activity concentration was also assessed. With all these data, internal and external doses were calculated. The results show that external doses are negligible in comparison with internal ones, which do not exceed 1 mSv yr(-1), either in this conservative situation or in any other more favourable one. Radionuclides after Rn in the radioactive natural series are emitted at the same activity concentration to the atmosphere, this being around 17 times higher than that corresponding to radionuclides before Rn. Taking into account these conclusions and the analytical method developed, it can be concluded that one way to assess the activity concentration of natural radionuclides in inhaled air and hence effective doses could be the early gamma-ray spectrometry of aerosols and particles sampled during the welding process. PMID:24334773

  2. Vacancy Assisted Diffusion of Alkoxy Species on Rutile TiO2(110)

    SciTech Connect

    Zhang, Zhenrong; Rousseau, Roger J.; Gong, Jinlong; Li, Shao-Chun; Kay, Bruce D.; Ge, Qingfeng; Dohnalek, Zdenek

    2008-10-10

    The catalytic and photocatalytic properties of TiO2 have attracted widespread interest in a variety of applications, such as air purification, self-cleaning glass, water splitting, solar cells and wastewater treatment. In many cases the catalytic chemistry of reducible oxides is dominated by oxygen vacancy sites. For reduced rutile TiO2(110)-1×1, the bridge-bonded oxygen (BBO) vacancies (BBOV’s) are the most prevalent surface defects and, as has been shown, they can readily dissociate small molecules such as H2O, O2, and alcohols.Here we demonstrate for the first time that BBOV’s can also catalyze the transport of adsorbed species which is a key ingredient in heterogeneous catalytic processes. Specifically, we show that at elevated temperatures (≥ 400 K), mobile BBOV’s can assist the diffusion of alkoxy groups formed by the dissociation of alcohols at BBOV’s. This type of mechanism is likely applicable to other adsorbates bound to BBO atoms of TiO2(110).

  3. Dehydration and Dehydrogenation of Ethylene Glycol on Rutile TiO2(110)

    SciTech Connect

    Li, Zhenjun; Kay, Bruce D.; Dohnalek, Zdenek

    2013-08-07

    The interactions of ethylene glycol (EG) with partially reduced rutile TiO2(110) surface have been studied using temperature programmed desorption (TPD). The saturation coverage on the surface Ti rows is determined to be 0.43 monolayer (ML), slightly less than one EG per two Ti sites. Most of the adsorbed ethanol (~80%) undergoes further reactions to other products. Two major channels are observed, dehydration yielding ethylene and water and dehydrogenation yielding acetaldehyde and hydrogen. Hydrogen formation is rather surprising as it has not been observed previously on TiO2(110) from simple organic molecules. The coverage dependent yields of ethylene and acetaldehyde correlate well with that of water and hydrogen, respectively. Dehydration dominates at lower EG coverages (< 0.2 ML) and plateaus as the coverage is increased to saturation. Dehydrogenation is observed primarily at higher EG coverages (>0.2 ML). Our results suggest that the observed dehydration and dehydrogenation reactions proceed via different surface intermediates.

  4. Effective dose in SMAW and FCAW welding processes using rutile consumables.

    PubMed

    Herranz, M; Rozas, S; Idoeta, R; Alegría, N

    2014-03-01

    The shielded metal arc welding (SMAW) and flux cored arc welding (FCAW) processes use covered electrodes and flux cored wire as consumables. Among these consumables, ones containing rutile are the most widely used, and since they have a considerable natural radioactive content, they can be considered as NORM (naturally occurring radioactive material). To calculate the effective dose on workers during their use in a conservative situation, samples of slag and aerosols and particles emitted or deposited during welding were taken and measured by gamma, alpha and beta spectrometry. An analytical method was also developed for estimating the activity concentration of radionuclides in the inhaled air. (222)Rn activity concentration was also assessed. With all these data, internal and external doses were calculated. The results show that external doses are negligible in comparison with internal ones, which do not exceed 1 mSv yr(-1), either in this conservative situation or in any other more favourable one. Radionuclides after Rn in the radioactive natural series are emitted at the same activity concentration to the atmosphere, this being around 17 times higher than that corresponding to radionuclides before Rn. Taking into account these conclusions and the analytical method developed, it can be concluded that one way to assess the activity concentration of natural radionuclides in inhaled air and hence effective doses could be the early gamma-ray spectrometry of aerosols and particles sampled during the welding process.

  5. One-step synthesis of titanium oxide nanocrystal- rutile by hydrothermal method

    SciTech Connect

    Yan, Evyan Yang Chia; Zakaria, Sarani; Chia, Chin Hua

    2014-09-03

    Pure rutile phase titanium oxides (TiO{sub 2}) nanocrystals were synthesized via hydrothermal method with titanium tetrachloride (TiCl{sub 4}) and water (H{sub 2}O) treated in an autoclave. The particle size and phase assemblages were characterized using Scanning electron microscopy (SEM) and X-ray diffraction (XRD) respectively. Band gap energy (E{sub g}) of the nanocrystals was estimated from the Ultra violet – visible light (UV-vis) absorption spectra. It was demonstrated that TiO{sub 2} nanocrystals can be prepared through increasing of temperature and period of treatment. It is believed that the presence of acid chloride (HCl) as by-product during the hydrolysis played an important role in controlling the growth of morphology and crystal structures. The E{sub g} of the samples were estimated from the plot of modified Kubelka-Munk function were in the range of 3.04 – 3.26eV for the samples synthesized at temperature ranging from 50 to 200°C for 16 hours.

  6. Adsorption of water on reconstructed rutile TiO2(011)-(2 x 1): Ti=O double bonds and surface reactivity.

    PubMed

    Di Valentin, Cristiana; Tilocca, Antonio; Selloni, Annabella; Beck, T J; Klust, Andreas; Batzill, Matthias; Losovyj, Yaroslav; Diebold, Ulrike

    2005-07-13

    Recent combined experimental and theoretical studies (Beck et al., Phys. Rev. Lett. 2004, 93, 036104) have provided evidence for Ti=O double-bonded titanyl groups on the reconstructed rutile TiO(2)(011)-(2 x 1) surface. The adsorption of water on the same surface is now investigated to further probe the properties of these groups, as well as to confirm their existence. Ultraviolet photoemission experiments show that water is adsorbed in molecular form at a sample temperature of 110 K. At the same time, the presence of a 3sigma state in the photoemission spectra and work function measurements indicate a significant amount of hydroxyls within the first monolayer of water. At room temperature, scanning tunneling microscopy (STM) suggests that dissociated water is present, and about 30% of the surface active sites are hydroxylated. These findings are well explained by total energy density functional theory calculations and Car-Parrinello molecular dynamics simulations for water adsorption on the titanyl model of TiO(2)(011)-(2 x 1). The theoretical results show that a mixed molecular/dissociative layer is the most stable configuration in the monolayer regime at low temperatures, while complete dissociation takes place at 250 K. The arrangement of the protonated mono-coordinated oxygens in the mixed molecular/dissociated layer is consistent with the observed short-range order of the hydroxyls in the STM images.

  7. Promoter effect of hydration on the nucleation of nanoparticles: direct observation for gold and copper on rutile TiO2 (110).

    PubMed

    Iachella, Mathilde; Wilson, Axel; Naitabdi, Ahmed; Bernard, Romain; Prévot, Geoffroy; Loffreda, David

    2016-09-28

    Direct observation of the promoting effect of hydration on the nucleation of gold and copper nanoparticles supported on partially reduced rutile TiO2 (110) is achieved by combined scanning tunneling microscopy experiments and density functional theory calculations. The experiments show a clear difference between the two metals. Gold nanoparticles grow at the vicinity of the surface hydroxyl domains, whereas the nucleation of copper is not substantially affected by hydration. The nucleation of gold on surface oxygen vacancies is observed although this is not the only preferential site. Theoretical calculations of the coadsorbed phases of gold, copper and hydroxyl species on stoichiometric and reduced TiO2 (110) surfaces under relevant conditions of temperature and pressure support the experimental interpretation. Surface hydration tends to stabilize significantly gold adsorption on the stoichiometric support, while its influence on copper adsorption is not pronounced. The theoretical analysis shows that the early stages of the nucleation on hydrated stoichiometric surfaces correspond to mono-hydroxylated metallic species co-chemisorbed with hydroxyl species, whereas those on hydrated reduced surfaces are metallic atoms bound to oxygen vacancies and weakly perturbed by surface hydration. PMID:27603921

  8. Combined toxicity of two crystalline phases (anatase and rutile) of Titania nanoparticles towards freshwater microalgae: Chlorella sp.

    PubMed

    Iswarya, V; Bhuvaneshwari, M; Alex, Sruthi Ann; Iyer, Siddharth; Chaudhuri, Gouri; Chandrasekaran, Prathna Thanjavur; Bhalerao, Gopalkrishna M; Chakravarty, Sujoy; Raichur, Ashok M; Chandrasekaran, N; Mukherjee, Amitava

    2015-04-01

    In view of the increasing usage of anatase and rutile crystalline phases of titania NPs in the consumer products, their entry into the aquatic environment may pose a serious risk to the ecosystem. In the present study, the possible toxic impact of anatase and rutile nanoparticles (individually and in binary mixture) was investigated using freshwater microalgae, Chlorella sp. at low exposure concentrations (0.25, 0.5 and 1mg/L) in freshwater medium under UV irradiation. Reduction of cell viability as well as a reduction in chlorophyll content were observed due to the presence of NPs. An antagonistic effect was noted at certain concentrations of binary mixture such as (0.25, 0.25), (0.25, 0.5), and (0.5, 0.5) mg/L, and an additive effect for the other combinations, (0.25, 1), (0.5, 0.25), (0.5, 1), (1, 0.25), (1, 0.5), and (1, 1) mg/L. The hydrodynamic size analyses in the test medium revealed that rutile NPs were more stable in lake water than the anatase and binary mixtures [at 6h, the sizes of anatase (1mg/L), rutile NPs (1mg/L), and binary mixture (1, 1mg/L) were 948.83±35.01nm, 555.74±19.93nm, and 1620.24±237.87nm, respectively]. The generation of oxidative stress was found to be strongly dependent on the crystallinity of the nanoparticles. The transmission electron microscopic images revealed damages in the nucleus and cell membrane of algal cells due to the interaction of anatase NPs, whereas rutile NPs were found to cause chloroplast and internal organelle damages. Mis-shaped chloroplasts, lack of nucleus, and starch-pyrenoid complex were noted in binary-treated cells. The findings from the current study may facilitate the environmental risk assessment of titania NPs in an aquatic ecosystem.

  9. Precipitation of Oriented Rutile and Ilmenite Needles in Garnet, Northeastern Connecticut, USA: Evidence for Extreme Metamorphic Conditions?

    NASA Astrophysics Data System (ADS)

    Ague, J. J.; Eckert, J. O.

    2011-12-01

    We report the discovery of oriented needles of rutile and, less commonly, ilmenite in the cores of garnets from northeastern CT, USA. The rocks preserve granulite facies mineral assemblages, form part of the Merrimack Synclinorium, and underwent metamorphism and deformation during the Acadian orogeny. The needles appear identical to those reported from a number of extreme P-T environments worldwide, including UHP metamorphic rocks, high-P granulites, and garnet peridotites. The needles are predominantly oriented along <111> directions in garnet. The long axes of the rutile needles commonly do not go extinct parallel to the cross hairs under cross-polarized light (e.g., Griffin et al., 1971). This anomalous extinction indicates that the needles do not preserve a specific crystallographic relationship with their garnet hosts (e.g., Hwang et al., 2007). The needles range from a few hundred nm to a few um in diameter, and can be mm-scale in length. Micrometer-scale plates of rutile, srilankite and crichtonite have also been observed in some garnets together with the Fe-Ti oxide needles. Several origins for the needles have been proposed in the literature; we investigate the hypothesis that they precipitated in situ from originally Ti-rich garnet. Chemical profiles across garnets indicate that some retain Ti zoning, with elevated-Ti concentrations in the cores dropping to low values in the rims. For these zoned garnets, high-resolution, 2-D chemical mapping using the JEOL JXA-8530F field emission gun electron microprobe at Yale University reveals that the needles are surrounded by well-defined Ti-depletion halos. Chemical profiles also document strong depletions of Cr (which is present in both rutile and ilmenite) directly adjacent to needles. The observed Ti-depletions demonstrate that the needles precipitated from Ti-bearing garnet, probably during cooling and/or decompression associated with exhumation. The rutile precipitates must be largely incoherent with respect

  10. Searching for active binary rutile oxide catalyst for water splitting from first principles.

    PubMed

    Chen, Dong; Fang, Ya-Hui; Liu, Zhi-Pan

    2012-12-28

    Water electrolysis is an important route to large-scale hydrogen production using renewable energy, in which the oxygen evolution reaction (OER: 2H(2)O → O(2) + 4H(+) + 4e(-)) causes the largest energy loss in traditional electrocatalysts involving Ru-Ir mixed oxides. Following our previous mechanistic studies on the OER on RuO(2)(110) (J. Am. Chem. Soc. 2010, 132, 18214), this work aims to provide further insight into the key parameters relevant to the activity of OER catalysts by investigating a group of rutile-type binary metal oxides, including RuNiO(2), RuCoO(2), RuRhO(2), RuIrO(2) and OsIrO(2). Two key aspects are focused on, namely the surface O coverage at the relevant potential conditions and the kinetics of H(2)O activation on the O-covered surfaces. The O coverage for all the oxides investigated here is found to be 1 ML at the concerned potential (1.23 V) with all the exposed metal cations being covered by terminal O atoms. The calculated free energy barrier for the H(2)O dissociation on the O covered surfaces varies significantly on different surfaces. The highest OER activity occurs at RuCoO(2) and RuNiO(2) oxides with a predicted activity about 500 times higher than pure RuO(2). On these oxides, the surface bridging O near the terminal O atom has a high activity for accepting the H during H(2)O splitting. It is concluded that while the differential adsorption energy of the terminal O atom influences the OER activity to the largest extent, the OER activity can still be tuned by modifying the electronic structure of surface bridging O.

  11. Modeling localized photoinduced electrons in rutile-TiO2 using periodic DFT+U methodology.

    PubMed

    Jedidi, Abdesslem; Markovits, Alexis; Minot, C; Bouzriba, Sarra; Abderraba, Manef

    2010-11-01

    We propose a theoretical model for photocatalytic processes on titanium dioxide, described by its most stable phase and surface, rutile-TiO(2)(110). The excitation induced by light promotes electrons from the valence band to the conduction band. In this context, one important requirement is having a correct value of the magnitude of the electronic gap. The use of GGA+U or LDA+U functional with an appropriate U value allows this. The U correction has little consequence on the adsorption strength itself on the TiO(2)(110) surface. For the ground state, it only yields a slight increase of the interaction strength of some test molecules; the surface basicity is somewhat enhanced. This is interpreted by the shift of TiO(2) vacant levels. Photoexcitation is taken into account by imposing two unpaired electrons per cell of the same spin. The size of the cell therefore determines the number of excitations per surface area; the larger the cell, the smaller the electron-hole surface concentration and the smaller the energy for electronic excitation. For the excited state, careful attention must be focused on the localization of the excited electron and of the hole which are crucial for the determination of the lowest electronic states and for the surface reactivity. We found that the excited electron is localized on a pentacoordinated surface titanium atom while the hole is shared by two surface oxygen atoms not too far from it. The electronic levels associated to the reduced titanium atoms are low in energy; the projected density of states is superposed onto the valence band.

  12. Ultrafast Multiphoton Pump-probe Photoemission Excitation Pathways in Rutile TiO2(110)

    SciTech Connect

    Argondizzo, Adam; Cui, Xuefeng; Wang, Cong; Sun, Huijuan; Shang, Honghui; Zhao, Jin; Petek, Hrvoje

    2015-04-27

    We investigate the spectroscopy and photoinduced electron dynamics within the conduction band of reduced rutile TiO2(110) surface by multiphoton photoemission (mPP) spectroscopy with wavelength tunable ultrafast (!20 fs) laser pulse excitation. Tuning the mPP photon excitation energy between 2.9 and 4.6 eV reveals a nearly degenerate pair of new unoccupied states located at 2.73 ± 0.05 and 2.85 ± 0.05 eV above the Fermi level, which can be analyzed through the polarization and sample azimuthal orientation dependence of the mPP spectra. Based on the calculated electronic structure and optical transition moments, as well as related spectroscopic evidence, we assign these resonances to transitions between Ti 3d bands of nominally t2g and eg symmetry, which are split by crystal field. The initial states for the optical transition are the reduced Ti3+ states of t2g symmetry populated by formation oxygen vacancy defects, which exist within the band gap of TiO2. Furthermore,we studied the electron dynamics within the conduction band of TiO2 by three-dimensional time-resolved pump-probe interferometric mPP measurements. The spectroscopic and time-resolved studies reveal competition between 2PP and 3PP processes where the t2g-eg transitions in the 2PP process saturate, and are overtaken by the 3PP process initiated by the band-gap excitation from the valence band of TiO2.

  13. Role of Water in Methanol Photochemistry on Rutile TiO2(110)

    SciTech Connect

    Shen, Mingmin; Henderson, Michael A.

    2012-08-07

    Photochemistry of the molecularly and dissociatively adsorbed forms of methanol on the vacuum-annealed rutile TiO2(110) surface was explored using temperature programmed desorption (TPD), both with and without coadsorbed water. Methoxy, and not methanol, was confirmed as the photochemically active form of adsorbed methanol on this surface. UV irradiation of methoxy-covered TiO2(110) lead to depletion of the methoxy coverage and formation of formaldehyde and a surface OH group. Coadsorbed water did not promote either molecular methanol photochemistry or thermal decomposition of methanol to methoxy. However, terminal OH groups (OHt), prepared by coadsorption of water and oxygen atoms, thermally converted molecularly adsorbed methanol to methoxy at 120 K, thus enabling photoactivity. While chemisorbed water molecules had no influence on methoxy photochemistry, water molecules hydrogen-bonded in the second layer to bridging oxygen (Obr) sites inhibited the methoxy photodecomposition to formaldehyde. From this we conclude that Obr sites accept protons from the hole-mediated conversion of methoxy to formaldehyde. These results provide new fundamental understanding of the hole-scavenging role of methanol in photochemical processes on TiO2-based materials and how water influences this photochemistry. This work was supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle under contract DEAC05-76RL01830. The research was performed using EMSL, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory.

  14. Construction of hydrophobic wood surfaces by room temperature deposition of rutile (TiO2) nanostructures

    NASA Astrophysics Data System (ADS)

    Zheng, Rongbo; Tshabalala, Mandla A.; Li, Qingyu; Wang, Hongyan

    2015-02-01

    A convenient room temperature approach was developed for growing rutile TiO2 hierarchical structures on the wood surface by direct hydrolysis and crystallization of TiCl3 in saturated NaCl aqueous solution. The morphology and the crystal structure of TiO2 coated on the wood surface were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD), respectively. The TiO2 morphology on the wood surface could be tuned by simply changing either the reaction time or pH value of the reaction mixture. After modification with perfluorodecyltriethoxysilane (PFDTS), the water contact angle (WCA) of the TiO2-treated wood (T1) surface increased to 140.0 ± 4.2°, which indicated a highly hydrophobic wood surface. In addition, compared with untreated control wood, PFDTS-TiO2 treatment (PFDTS-T1-treated) not only reduced liquid water uptake, but also delayed the onset of water saturation point of the wood substrate. The weight change of PFDTS-T1-treated wood after 24 h of water immersion was 19.3%, compared to 81.3% for the untreated control wood. After 867 h of water immersion, the weight change for the treated and untreated wood specimens was 117.1%, and 155.1%, respectively. The untreated control wood reached the steady state after 187 h, while the PFDTS-T1-treated wood did not reach the steady state until after 600 h of immersion.

  15. Interaction of CO2 with Oxygen Adatoms on Rutile TiO2(110)

    SciTech Connect

    Lin, Xiao; Wang, Zhitao; Lyubinetsky, Igor; Kay, Bruce D.; Dohnalek, Zdenek

    2013-01-10

    The interactions of CO2 with oxygen adatoms (Oa’s) on rutile TiO2(110) surfaces have been studied using scanning tunneling microscopy. At 50 K CO2 is found to adsorb preferentially on five-coordinated Ti sites (Ti5c’s) next to Oa’s rather than on oxygen vacancies (VO’s) (the most stable adsorption sites on reduced TiO2(110)). Temperature dependent studies show that after annealing to 100 - 150 K, VO’s become preferentially populated indicating the presence of a kinetic barrier for CO2 adsorption into the VO’s. The difference between the CO2 binding energy on VO’s and Ti5c sites next to the Oa’s are found to be only 0.009 - 0.025 eV. The barrier for CO2 diffusion away from Oa’s is estimated to be ~0.17 eV. Crescent-like feature of the images of CO2 adsorbed on Ti5c’s next to Oa’s are interpreted as a time average of terminally bound CO2 molecules switching between the configurations that are tilted towards Oa and/or towards one of the two neighboring bridging oxygen (Ob) rows. In the presence of VO defects, CO2 is found to tilt preferentially away from the VO containing Ob row. If another CO2 is present on the neighboring Ti5c row, both CO2 molecules tilt towards the common Ob row that separates them.

  16. Adsorption of small hydrocarbons on rutile TiO2(110)

    SciTech Connect

    Chen, Long; Smith, R. Scott; Kay, Bruce D.; Dohnalek, Zdenek

    2015-11-21

    Here, temperature programmed desorption and molecular beam scattering were used to study the adsorption and desorption of small hydrocarbons (n-alkanes, 1-alkenes and 1-alkynes of C1–C4) on rutile TiO2(110). We show that the sticking coefficients for all the hydrocarbons are close to unity (> 0.95) at an adsorption temperature of 60 K. The desorption energies for hydrocarbons of the same chain length increase from n-alkanes to 1-alkenes and to 1-alkynes. This trend is likely a consequence of additional dative bonding of the alkene and alkyne π system to the coordinatively unsaturated Ti5c sites. Similar to previous studies on the adsorption of n-alkanes on metal and metal oxide surfaces, we find that the desorption energies within each group (n-alkanes vs. 1-alkenes vs. 1-alkynes) from Ti5c sites increase linearly with the chain length. The absolute saturation coverages of each hydrocarbon on Ti5c sites were also determined. The saturation coverage of CH4, is found to be ~ 2/3 monolayer (ML). The saturation coverages of C2–C4 hydrocarbons are found nearly independent of the chain length with values of ~ 1/2 ML for n-alkanes and 1-alkenes and 2/3 ML for 1-alkynes. This result is surprising considering their similar sizes.

  17. First-Principles Study on Electronic Structure and Spin State of Rutile (Ti,Co)O2 by Self-Interaction-Corrected Local Density Approximation: Role of Oxygen Vacancy

    NASA Astrophysics Data System (ADS)

    Kizaki, Hidetoshi; Toyoda, Masayuki; Sato, Kazunori; Katayama-Yoshida, Hiroshi

    2009-05-01

    Electronic structure of rutile-TiO2 based dilute magnetic semiconductors (DMS) are investigated within self-interaction-corrected local density approximation (SIC-LDA). These results are compared with those calculated within standard LDA. We employ the Korringa-Kohn-Rostoker method combined with coherent potential approximation. It is found that high-spin state in (Ti,Co)O2 with O vacancy is predicted in the SIC-LDA. This result is in good agreement with the experimental results. As a result, we find that O vacancy in (Ti,Co)O2 is the origin of Co2+ high-spin state and SIC-LDA is indispensable to describe the correct electronic structure and spin state of TiO2-based DMS.

  18. In situ rutile petrochronology: texture-related T, Paleoproterozoic inheritance and a Pan-African overprint in the oldest subduction-related eclogites, Usagaran Orogen, Tanzania

    NASA Astrophysics Data System (ADS)

    Moeller, A.; Kraus, K.; Herms, P.; Appel, P.; Raase, P.

    2014-12-01

    Rutile U-Pb thermochronology is applied successfully by both TIMS and beam methods to date cooling events in mafic and metapelitic rocks, as well as in detrital studies. The Zr-in-rutile thermometer is very robust to thermal diffusion, and generally requires complete recrystallization to change recorded crystallization temperatures. Evidence for diffusion of HFSE elements in rutile is sparse; whereas U-Pb chronology generally records diffusion controlled cooling from the last event. This study follows conventional thermobarometry and U-Pb TIMS results on monazite, sphene and rutile of Möller et al. (1995) establishing a 2 Ga eclogite facies event from MORB-like metabasic, and metapelitic rocks in the Usagaran Orogen of Tanzania, interpreted to be the oldest outcrops of subduction-related eclogites. Rutile from both rock types were discordant near a ca. 500 Ma lower intercept, confirming a thermal overprint postulated on the basis of K-Ar and Rb-Sr mica ages by e.g. Wendt et al. (1972). The age of the eclogite-facies event was confirmed by U-Pb zircon dating of a 1991±2 Ma crosscutting pegmatite (Collins et al., 1999). We present in situ LA-ICP-MS rutile petrochronology on five metabasic and metapelitic eclogite facies samples with variable retrograde amphibolite-facies recrystallization. Thermometry confirms conventional Fe-Mg results, including higher peak temperatures in metabasites. Traverses on rutile inclusions in large garnet prophyroblasts in metapelites show increasing temperatures from cores outwards and a slight decrease towards outermost rims, with peak T coinciding with highest Mg# and highest grossular content, hence consistent with preservation of prograde zoning in the garnets and a brief eclogite facies event. Large rutiles (800μm) in recrystallized samples record temperature zoning profiles. U-Pb results show inheritance of near concordant 2 Ga domains, but dominantly confirm the ca. 490 Ma amphibolite facies overprint. The study is an excellent

  19. Quantitative orientation analysis by sum frequency generation in the presence of near-resonant background signal: acetonitrile on rutile TiO2 (110).

    PubMed

    Jang, Joon Hee; Lydiatt, Francis; Lindsay, Rob; Baldelli, Steven

    2013-07-25

    Sum frequency generation (SFG) spectroscopic techniques are used to investigate the molecular orientation of adsorbed acetonitrile on rutile TiO2 (110) at the solid-vapor interface. Generally, most molecular orientation analyses using SFG have been performed on dielectric substrates, to avoid the spectral interference between resonant and the near-resonant background signal. Although rutile crystal can be treated as a dielectric substrate, its electronic state contributes to the intensity and interferes with the resonant signal when the SFG frequency is close to its band gap energy. In addition, the rutile crystal is a uniaxial birefringent material, and the (110) surface is anisotropic, which further complicates the spectral analysis. In this study, various SFG measurement techniques were applied, and quantitative analytical methods were established to interpret the surface orientation of an adsorbed molecule. SFG vibrational spectra of acetonitrile on rutile TiO2 (110) surface have been measured using distinct polarization combinations, polarization mapping, and null angle method. By varying the polarization combinations of SFG, the magnitude and shape of the spectra undergo substantial change, which originate from the interference between the near-resonant signal from the rutile substrate and the resonance signal from the acetonitrile. Theory, simulation, and analytical methods for obtaining quantitative orientation information of a molecule on an anisotropic semiconductor substrate in the presence of a near-resonant signal are presented.

  20. Evolution of structural and optical properties of rutile TiO2 thin films synthesized at room temperature by chemical bath deposition method

    NASA Astrophysics Data System (ADS)

    Mayabadi, A. H.; Waman, V. S.; Kamble, M. M.; Ghosh, S. S.; Gabhale, B. B.; Rondiya, S. R.; Rokade, A. V.; Khadtare, S. S.; Sathe, V. G.; Pathan, H. M.; Gosavi, S. W.; Jadkar, S. R.

    2014-02-01

    Nanocrystalline thin films of TiO2 were prepared on glass substrates from an aqueous solution of TiCl3 and NH4OH at room temperature using the simple and cost-effective chemical bath deposition (CBD) method. The influence of deposition time on structural, morphological and optical properties was systematically investigated. TiO2 transition from a mixed anatase-rutile phase to a pure rutile phase was revealed by low-angle XRD and Raman spectroscopy. Rutile phase formation was confirmed by FTIR spectroscopy. Scanning electron micrographs revealed that the multigrain structure of as-deposited TiO2 thin films was completely converted into semi-spherical nanoparticles. Optical studies showed that rutile thin films had a high absorption coefficient and a direct bandgap. The optical bandgap decreased slightly (3.29-3.07 eV) with increasing deposition time. The ease of deposition of rutile thin films at low temperature is useful for the fabrication of extremely thin absorber (ETA) solar cells, dye-sensitized solar cells, and gas sensors.

  1. Solar light decomposition of DFP on the surface of anatase and rutile TiO 2 prepared by hydrothermal treatment of microemulsions

    NASA Astrophysics Data System (ADS)

    Kiselev, A.; Andersson, M.; Mattson, A.; Shchukarev, A.; Sjöberg, S.; Palmqvist, A.; Österlund, L.

    2005-06-01

    The photocatalytic decomposition of diisopropylfluorophosphate (DFP) over nanostructured anatase and rutile TiO 2 powder was investigated by FTIR and XPS. Upon irradiation with artificial solar light DFP decomposed on both polymorphs as evidenced by FTIR. For both crystalline structures acetone and subsequently coordinated formate and carbonate were observed on the surface during the photocatalytic reaction as the isopropyl groups dissociated from DFP. XPS revealed that small amounts of phosphates and inorganic fluoride (Ti sbnd F) gradually built up on both TiO 2 surfaces, while organic F was present only on the rutile phase. From repeated cycles of intermittent DFP adsorption and irradiation measurements, the decomposition rates and formation of residuals on the surface were deduced. It was found that the overall oxidation yield is higher on anatase than rutile. The oxidation rate decreases with increasing irradiation time, an effect that is more pronounced on rutile. We find that both the difference between the polymorphs and the initial decrease of the oxidation yield can largely be explained by variations in surface area rather than poisoning by PO x or F species. In particular, we observe a dramatic decrease of the specific area of rutile as a function of photocatalytic oxidation cycle.

  2. Adsorption of formic acid on rutile TiO{sub 2} (110) revisited: An infrared reflection-absorption spectroscopy and density functional theory study

    SciTech Connect

    Mattsson, A.; Österlund, L.; Hu, Shuanglin Hermansson, K.

    2014-01-21

    Formic acid (HCOOH) adsorption on rutile TiO{sub 2} (110) has been studied by s- and p-polarized infrared reflection-absorption spectroscopy (IRRAS) and spin-polarized density functional theory together with Hubbard U contributions (DFT+U) calculations. To compare with IRRAS spectra, the results from the DFT+U calculations were used to simulate IR spectra by employing a three-layer model, where the adsorbate layer was modelled using Lorentz oscillators with calculated dielectric constants. To account for the experimental observations, four possible formate adsorption geometries were calculated, describing both the perfect (110) surface, and surfaces with defects; either O vacancies or hydroxyls. The majority species seen in IRRAS was confirmed to be the bridging bidentate formate species with associated symmetric and asymmetric frequencies of the ν(OCO) modes measured to be at 1359 cm{sup −1} and 1534 cm{sup −1}, respectively. The in-plane δ(C–H) wagging mode of this species couples to both the tangential and the normal component of the incident p-polarized light, which results in absorption and emission bands at 1374 cm{sup −1} and 1388 cm{sup −1}. IRRAS spectra measured on surfaces prepared to be either reduced, stoichiometric, or to contain surplus O adatoms, were found to be very similar. By comparisons with computed spectra, it is proposed that in our experiments, formate binds as a minority species to an in-plane Ti{sub 5c} atom and a hydroxyl, rather than to O vacancy sites, the latter to a large extent being healed even at our UHV conditions. Excellent agreement between calculated and experimental IRRAS spectra is obtained. The results emphasize the importance of protonation and reactive surface hydroxyls – even under UHV conditions – as reactive sites in e.g., catalytic applications.

  3. Oxygen-Induced Restructuring of Rutile TiO(2)(110): Formation Mechanism, Atomic Models, and Influence on Surface Chemistry

    SciTech Connect

    Li, Min; Hebenstreit, Wilhelm; Diebold, Ulrike; Henderson, Michael A.; Jennison, Dwight R.

    1999-07-07

    The rutile TiO{sub 2} (110) (1x1) surface is considered the prototypical ''well-defined'' system in the surface science of metal oxides. Its popularity results partly from two experimental advantages: bulk-reduced single crystals do not exhibit charging, and stoichiometric surfaces--as judged by electron spectroscopes--can be prepared reproducibly by sputtering and annealing in oxygen. We present results that show that this commonly-applied preparation procedure may result in a surface structure that is by far more complex than generally anticipated. Flat, (1x1) terminated surfaces are obtained by sputtering and annealing in ultrahigh vacuum. When re-annealed in oxygen at moderate temperatures (470 K to 660 K), irregular networks of partially-connected, pseudohexagonal rosettes (6.5 x 6 {angstrom} wide), one-unit cell wide strands, and small ({approximately} tens of {angstrom}) (1x1) islands appear. This new surface phase is formed through reaction of oxygen gas with interstitial Ti from the reduced bulk. Because it consists of an incomplete, kinetically-limited (1x1) layer, this phenomenon has been termed restructuring. We report a combined experimental and theoretical study that systematically explores this restructuring process. The influence of several parameters (annealing time, temperature, pressure, sample history, gas) on the surface morphology is investigated using STM. The surface coverage of the added phase as well as the kinetics of the restructuring process are quantified by LEIS and SSIMS measurements in combination with annealing in {sup 18}O-enriched gas. Atomic models of the essential structural elements are presented and are shown to be stable with first-principles density functional calculations. The effect of oxygen-induced restructuring on surface chemistry and its importance for TiO{sub 2} and other bulk-reduced oxide materials is briefly discussed.

  4. Capillary zone electrophoresis for U(VI) and short chain carboxylic acid sorption studies on silica and rutile.

    PubMed

    Sladkov, Vladimir; Zhao, Yujia; Mercier-Bion, Florence

    2011-02-15

    Capillary zone electrophoresis was used to study the uranyl and short chain carboxylic acid sorption on silica and rutile. The separation and the simultaneous determination (in a single run) of a number of short chain carboxylic acids (oxalic, formic, acetic and propionic) and U(VI) with direct UV detection is developed for the analysis of solutions after the sorption experiments. The reverse polarity mode is used (the injection is performed at the negative end). The matrix effect of Si(IV) (possible silica dissolution product) and perchlorate (added for constant ionic strength in sorption experiments) on the separation of U(VI) and organic acids is investigated. The influence of methanol addition in carrier electrolyte on the separation selectivity of given analytes is also studied. Under the chosen conditions (carbonate buffer (ionic strength of 0.1M), pH 9.8, 0.15 mM of tetradecyltrimethylammonium bromide, 25% (v/v) of methanol) the calibration curves are plotted. They are linear in two ranges of concentration from ∼1×10(-5) to ∼1×10(-3) M for oxalate, acetate, propionate, U(VI) and ∼1×10(-4) to ∼1×10(-3) for formate. The accuracy of the procedure is checked by the "added-found" method in simulation solutions. The relative standard deviations of the concentrations found are within the range of 1-10% and the recovery is in the range of 90-115%. This method is applied for the analysis of aqueous samples issued from sorption experiments on silica and rutile. The obtained results indicate that the given organic acids decrease uranium sorption both on silica and rutile. These experiments demonstrate that short chain carboxylic acids can influence the mobility and the chemistry of U(VI) in the environment.

  5. Nanocrystalline rutile electron extraction layer enables low-temperature solution processed perovskite photovoltaics with 13.7% efficiency.

    PubMed

    Yella, Aswani; Heiniger, Leo-Philipp; Gao, Peng; Nazeeruddin, Mohammad Khaja; Grätzel, Michael

    2014-05-14

    We demonstrate low-temperature (70 °C) solution processing of TiO2/CH3NH3PbI3 based solar cells, resulting in impressive power conversion efficiency (PCE) of 13.7%. Along with the high efficiency, a strikingly high open circuit potential (VOC) of 1110 mV was realized using this low-temperature chemical bath deposition approach. To the best of our knowledge, this is so far the highest VOC value for solution-processed TiO2/CH3NH3PbI3 solar cells. We deposited a nanocrystalline TiO2 (rutile) hole-blocking layer on a fluorine-doped tin oxide (FTO) conducting glass substrate via hydrolysis of TiCl4 at 70 °C, forming the electron selective contact with the photoactive CH3NH3PbI3 film. We find that the nanocrystalline rutile TiO2 achieves a much better performance than a planar TiO2 (anatase) film prepared by high-temperature spin coating of TiCl4, which produces a much lower PCE of 3.7%. We attribute this to the formation of an intimate junction of large interfacial area between the nanocrystalline rutile TiO2 and the CH3NH3PbI3 layer, which is much more effective in extracting photogenerated electrons than the planar anatase film. Since the complete fabrication of the solar cell is carried out below 100 °C, this method can be easily extended to plastic substrates.

  6. Surface chemistry and flotation behavior of monazite, apatite, ilmenite, quartz, rutile, and zircon using octanohydroxamic acid collector

    NASA Astrophysics Data System (ADS)

    Nduwa Mushidi, Josue

    Global increase in rare earth demand and consumption has led to further understanding their beneficiation and recovery. Monazite is the second most important rare earth mineral that can be further exploited. In this study, the surface chemistry of monazite in terms of zeta potential, adsorption density, and flotation response by microflotation using octanohydroxamic acid is determined. Apatite, ilmenite, quartz, rutile, and zircon are minerals that frequently occur with monazite among other minerals. Hence they were chosen as gangue minerals in this study. The Iso Electric Point (IEP) of monazite, apatite, ilmenite, quartz, rutile, and zircon are 5.3, 8.7, 3.8, 3.4, 6.3, and 5.1 respectively. The thermodynamic parameters of adsorption were also evaluated. Ilmenite, rutile and zircon have high driving forces for adsorption with DeltaGads. = 20.48, 22.10, and 22.4 kJ/mol respectively. The free energy of adsorption is 14.87 kJ/mol for monazite. Adsorption density testing shows that octanohydroxamic acid adsorbs on negatively charged surfaces of monazite and its gangue minerals which indicates chemisorption. This observation was further confirmed by microflotation experiments. Increasing the temperature to 80°C raises the adsorption and flotability of monazite and gangue minerals. This does not allow for effective separation. Sodium silicate appeared to be most effective to depress associated gangue minerals. Finally, the fundamentals learned were applied to the flotation of monazite ore from Mt. Weld. However, these results showed no selectivity due to the presence of goethite as fine particles and due to a low degree of liberation of monazite in the ore sample.

  7. Patterning of rutile TiO2 surface by ion beam lithography through full-solid masks.

    PubMed

    Sanz, R; Jaafar, M; Hernández-Vélez, M; Asenjo, A; Vázquez, M; Jensen, J

    2010-06-11

    In this work we present and discuss the nanopatterning of rutile TiO(2) single crystal surfaces following their irradiation with energetic heavy ions through a stencil mask of Ni filled self-ordered porous anodic alumina. After etching in HF a corrugated surface morphology is obtained composed of parallel alternate furrows and ridges (or nanobars) 50 nm in diameter and with 100 nm pitch. In addition, isolated, but collapsed, TiO(2) nanorods are seen lying on the patterned surface. The stability of the nanopatterned surface under high temperatures treatments and crystalline properties are analyzed. PMID:20463385

  8. Electronic structures and optical properties of rutile TiO2 with different point defects from DFT + U calculations

    NASA Astrophysics Data System (ADS)

    Zhu, H. X.; Zhou, P. X.; Li, X.; Liu, J.-M.

    2014-07-01

    The electronic states and formation energies of four types of lattice point defects in rutile TiO2 are studied using the first-principles calculations. The existence of oxygen vacancy leads to a deep donor defect level in the forbidden band, while the Ti interstitial forms two local states. It is predicted that oxygen vacancy prefers to combine with Ti-interstitial to form VO-Tii dimer by a partial 3d electron transfer from the Tii to its neighboring VO. The charge distribution between a Ti interstitial and its neighboring Ti ions partially shields the Coulomb interactions. Lastly, optical properties of these defective lattices are discussed.

  9. Equilibrium state of anatase to rutile transformation for nano-structured Titanium Dioxide powder using polymer template method.

    NASA Astrophysics Data System (ADS)

    Dam, Tapabrata; Jena, Sidhartha S.; Pradhan, Dillip K.

    2016-02-01

    In this work we report the novel synthesis procedure of phase-pure nano-structured titania in anatase phase using polyacrylamide gel based polymer template method. The evolution of rutile phased titania with increasing temperature has also been investigated. The synthesized nano-materials are characterized using X-ray diffraction, Brunauer - Emmett - Teller surface analysis technique and Scanning electron microscopy. We have used dual phase Rietveld refinement method to analyse the X-Ray diffraction data to get clear picture of crystallographic information of the prepared samples.

  10. Adsorption of dopamine on rutile TiO2 (110): a photoemission and near-edge X-ray absorption fine structure study.

    PubMed

    Jackman, Mark J; Syres, Karen L; Cant, David J H; Hardman, Samantha J O; Thomas, Andrew G

    2014-07-29

    Synchrotron radiation photoelectron spectroscopy and near-edge X-ray absorption fine structure (NEXAFS) techniques have been used to study the adsorption of dopamine on a rutile TiO2 (110) single crystal. Photoemission results suggest that dopamine bonds through the oxygen molecules in a bidentate fashion. From the data, it is ambiguous whether the oxygens bond to the same 5-fold coordinated surface titanium atom or bridges across two, although based on the bonding of pyrocatechol on rutile TiO2 (110), it is likely that the dopamine bridges two titanium atoms. Using the searchlight effect, the carbon K-edge near-edge X-ray absorption fine structure NEXAFS spectra recorded for dopamine on rutile TiO2 (110) show the phenyl ring to be oriented at 78° ± 5° from the surface and twisted 11 ± 10° relative to the (001) direction.

  11. Adsorption of dopamine on rutile TiO2 (110): a photoemission and near-edge X-ray absorption fine structure study.

    PubMed

    Jackman, Mark J; Syres, Karen L; Cant, David J H; Hardman, Samantha J O; Thomas, Andrew G

    2014-07-29

    Synchrotron radiation photoelectron spectroscopy and near-edge X-ray absorption fine structure (NEXAFS) techniques have been used to study the adsorption of dopamine on a rutile TiO2 (110) single crystal. Photoemission results suggest that dopamine bonds through the oxygen molecules in a bidentate fashion. From the data, it is ambiguous whether the oxygens bond to the same 5-fold coordinated surface titanium atom or bridges across two, although based on the bonding of pyrocatechol on rutile TiO2 (110), it is likely that the dopamine bridges two titanium atoms. Using the searchlight effect, the carbon K-edge near-edge X-ray absorption fine structure NEXAFS spectra recorded for dopamine on rutile TiO2 (110) show the phenyl ring to be oriented at 78° ± 5° from the surface and twisted 11 ± 10° relative to the (001) direction. PMID:25003716

  12. Photochemistry of 1,1,1-Trifluoroacetone on Rutile TiO2(110)

    SciTech Connect

    Zehr, Robert T.; Deskins, N. Aaron; Henderson, Michael A.

    2010-10-14

    The ultraviolet (UV) photon-induced photodecomposition of 1,1,1-trifluoroacetone (TFA) adsorbed on the rutile TiO2(110) surface has been investigated with photon stimulated desorption (PSD), temperature programmed desorption (TPD) and density functional theory (DFT). TFA adsorbed molecularly on the reduced surface (8% oxygen vacancies) in states desorbing below 300 K with trace thermal decomposition observed in TPD. Adsorption of TFA on a preoxidized TiO2(110) surface (accomplished by pre-exposure with 20 L O2) led to formation of a new TFA desorption state at 350 K, assigned to decomposition of a TFA-diolate species ((CF3)(CH3)COO). No TFA photochemistry was detected on the reduced surface. UV irradiation of TFA on the oxidized surface depleted TFA in the 350 K state, with TFA molecules in other TPD states unaffected. PSD measurements reveal that both carbonyl substituents (CH3 and CF3), as well as CO, were liberated during UV exposure at 95 K. Post-irradiation TPD showed evidence for both acetate (evolving as ketene at 650 K) and trifluoroacetate (evolving as CO2 at 600 K) as surface-bound photodecomposition products. The CO PSD product was not due to adsorbed CO, to mass spectrometer cracking of a CO-containing PSD product, or from background effects, but originated from complete fragmentation of an unidentified adsorbed TFA species. Thermodynamic analysis using DFT indicated that the photodecomposition of the TFA-diolate was likely not driven by thermodynamics alone as both pathways (CH3+trifluoroacetate and CF3+acetate) were detected when thermodynamics shows a clear preference for only one (CF3+acetate). These observations are in contrast to the photochemical behavior of acetone, butanone and acetaldehyde on TiO2(110), where only one of the two carbonyl substituent groups was observed, with a stoichiometric amount of carboxylate containing the other substituent left on the surface. We conclude that fluorination significantly alters the electronic structure of

  13. Thermal chemistry and photochemistry of hexafluoroacetone on rutile TiO2(110)

    SciTech Connect

    Zehr, Robert T.; Henderson, Michael A.

    2010-07-20

    The ultraviolet (UV) photon-induced decomposition of hexafluoroacetone (HFA) adsorbed on the rutile TiO2(110) surface was investigated using photon stimulated desorption (PSD) and temperature programmed desorption (TPD). The initial 0.2 ML coverage of HFA decomposed when adsorbed on the reduced TiO2(110) surface resulting in the formation of trifluoroacetate (evolving in TPD as CO, CO2, and C2F4 near 600 K). Further HFA exposure resulted in molecular adsorption. No evidence for photochemistry was observed on the reduced surface. HFA adsorbed and desorbed molecularly on a pre-oxidized TiO2(110) surface with only a minor amount (~1%) of thermal decomposition in TPD. A new adsorption state at 350 K was assigned to the reversible formation of a photoactive HFA-diolate species [(CF3)2COO]. UV irradiation depleted the 350 K state and resulted in the formation of surface bound trifluoroacetate. PSD experiments showed that CF3, CO, and CO2 were evolved during irradiation at 95 K. Post-irradiation TPD showed evidence for trifluoroacetate (desorbing as CO, CO2, and C2F4 near 600 K) as surface-bound photodecomposition products. 18O isotope scrambling experiments showed that the origin of the ejected CO2 was from photodecomposition of the HFA-diolate species. CO photodesorption was due to an as-yet unidentified adsorbed HFA species and not due to decomposition of the HFA-diolate. These results are in contrast to the photochemical behavior of acetone, butanone and acetaldehyde on TiO2(110), where UV irradiation resulted in the gas phase ejection of one of the carbonyl substituent groups as well as a stoichiometric amount of carboxylate left on the surface. We conclude that fluorination alters the electronic structure of adsorbed carbonyls on TiO2(110) in such a way as to promote complete fragmentation of the adsorbed carbonyl complex to form gas phase CO2 as well as open up additional photodissociation pathways leading to CO production.

  14. Methylene bromide chemistry and photochemistry on rutile TiO2(110)

    SciTech Connect

    Henderson, Michael A.; Robbins, Matthew D.

    2011-10-01

    The chemistry and photochemistry of methylene bromide (CD2Br2) on the rutile TiO2(110) surface was probed using temperature programmed desorption (TPD). CD2Br2 desorbed in three desorption states at 145, 160 and 250 K tentatively assigned to desorption from the multilayer, from an η1-CD2Br2 species and a bridging η2-CD2Br2 species, respectively. The latter two TPD states presumably involve binding of CD2Br2 molecules to the surface through Br coordination at five-coordinate Ti4+ surface sites. The 160 and 250 K TPD states saturated at coverages of 1.0 and 0.33 ML, respectively, where 1 ML is equivalent to the surface Ti4+ site density (5.2 × 1014 cm- 2). No thermal decomposition of CD2Br2 was observed on either the clean surface or with preadsorbed O2. UV irradiation of CD2Br2 on TiO2(110) resulted in predominately photodesorption, with trace amounts of photodecomposition evidenced in TPD. The rate of CD2Br2 photodesorption from TiO2(110) occurred with a low cross section (~ 2 × 10- 21 cm2) similar to that expected from direct optical excitation of CD2Br2. This observation suggests that charge carriers generated in TiO2(110) were no more effective in activating adsorbed CD2Br2 molecules than would be expected through direct molecular excitation. Finally, these findings suggest that photocatalytic destruction of halocarbons such as CD2Br2 on TiO2 may preferentially occur though indirect processes (such as OH radical attack) as opposed to direct electron transfer processes involving charge carriers generated in TiO2 by bandgap excitation.

  15. A comparative study of optical absorption and photocatalytic properties of nanocrystalline single-phase anatase and rutile TiO{sub 2} doped with transition metal cations

    SciTech Connect

    Kernazhitsky, L.; Shymanovska, V.; Gavrilko, T.; Naumov, V.; Kshnyakin, V.; Khalyavka, T.

    2013-02-15

    The effect of nanocrystalline TiO{sub 2} doping with transition metal cations (Cu{sup 2+}, Fe{sup 3+}, Co{sup 2+}, Cr{sup 3+}) on their optical absorption and photocatalytic properties was investigated. The obtained metal-doped TiO{sub 2} samples were characterized by X-ray diffraction, scanning electron microscopy, and UV-vis absorption spectroscopy. It is shown that doping effect on anatase (A) and rutile (R) properties is quite different, being much stronger and complicated on A than on R. Contrary to doped R, doped A revealed a significant red shift of the absorption edge along with the band gap narrowing. Photocatalytic activity of anatase increases upon doping in the order: Arutile samples decreases upon doping in the series R>R/Co>R/Cu>R/Fe>R/Cr, indicating the inhibitory effect of impurity cations. This fact correlates with the decrease in the UV absorption of the doped rutile in the region of the Hg-lamp irradiation at 4.88 eV. - Graphical abstract: A red shift of the absorption edge of nanocrystalline single-phase anatase after doping with transition metal cations. Highlights: Black-Right-Pointing-Pointer Single-phase anatase and rutile powders surface-doped with transition metal cations. Black-Right-Pointing-Pointer Absorption edge and band gap of rutile do not change with surface doping. Black-Right-Pointing-Pointer Band gap of surface-doped anatase reduces being the lowest for A/Fe. Black-Right-Pointing-Pointer The surface-doping improves photocatalytic activity of anatase. Black-Right-Pointing-Pointer The surface-doping inhibits photocatalytic activity of rutile.

  16. Effects of nano anatase-rutile TiO2 volume fraction with natural dye containing anthocyanin on the dye sensitized solar cell performance

    NASA Astrophysics Data System (ADS)

    Agustini, S.; Wahyuono, R. A.; Sawitri, D.; Risanti, D. D.

    2013-09-01

    Since its first development, efforts to improve efficiency of Dye Sensitized Solar Cell (DSSC) are continuously carried out, either through selection of dye materials, the type of semiconductor, counter electrode design or the sandwiched structure. It is widely known that anatase and rutile are phases of TiO2 that often being used for fabrication of DSSC. Rutile is thermodynamically more stable phase having band-gap suitable for absorption of sunlight spectrum. On the other hand, anatase has higher electrical conductivity, capability to adsorp dye as well as higher electron diffusion coefficient than those of rutile. Present research uses mangosteen pericarp and Rhoeo spathacea extracted in ethanol as natural dye containing anthocyanin. These dyes were characterized by using UV-Vis and FTIR, showing that the absorption maxima peaks obtained at 389 nm and 413 nm, for mangosteen and Rhoeo spathacea, respectively. The nano TiO2 was prepared by means of co-precipitation method. The particle size were 9-11 nm and 54.5 nm for anatase and rutile, respectively, according to Scherrer's equation. DSSCs were fabricated in various volume fractions of anatase and rutile TiO2. The fabricated DSSCs were tested under 17 mW/cm2 of solar irradiation. The current-voltage (I-V) characteristic of DSSCs employing 75%: 25% volume fraction of anatase and rutile TiO2 have outstanding result than others. The highest conversion efficiencies of 0.037% and 0.013% are obtained for DSSC employing natural dye extract from mangosteen pericarp and Rhoeo spathacea, respectively.

  17. A Paleozoic anorthosite massif related to rutile-bearing ilmenite ore deposits, south of the Polochic fault, Chiapas Massif Complex, Mexico

    NASA Astrophysics Data System (ADS)

    Cisneros, A.; Ortega-Gutiérrez, F.; Weber, B.; Solari, L.; Schaaf, P. E.; Maldonado, R.

    2013-12-01

    The Chiapas Massif Complex in the southern Maya terrane is mostly composed of late Permian igneous and meta-igneous rocks. Within this complex in southern Mexico and in the adjacent San Marcos Department of Guatemala, south of the Polochic fault, several small outcrops (~10 km2) of a Phanerozoic andesine anorthosite massif were found following an E-W trend similar to the Polochic-Motagua Fault System. Such anorthosites are related to rutile-bearing ilmenite ore deposits and hornblendite-amphibolite bands (0.1-3 meters thick). The anorthosites show recrystallization and metamorphic retrogression (rutile with titanite rims), but no relicts of high-grade metamorphic minerals such as pyroxene or garnet have been found. In Acacoyagua, Chiapas, anorthosites are spatially related to oxide-apatite rich mafic rocks; in contrast, further to the west in Motozintla, they are related to monzonites. Zircons from these monzonites yield a Permian U-Pb age (271.2×1.4 Ma) by LA-MC-ICPMS. Primary mineral assemblage of the anorthosites include mostly medium to fine-grained plagioclase (>90%) with rutile and apatite as accessory minerals, occasionally with very low amounts of quartz. Massive Fe-Ti oxide lenses up to tens of meters in length and few meters thick are an ubiquitous constituent of these anorthosites and their mineralogy include ilmenite (with exsolution lamellae of Ti-magnetite), rutile, magnetite, clinochlore, ×spinel, ×apatite, ×zircon and srilankite (Ti2ZrO6, first finding of this phase in Mexico). Rutile occurs within the massive ilmenite in two morphological types: (1) fine-grained (5-40 μm) rutile along ilmenite grain boundaries or fractures, and (2) coarse-grained rutile (<5 mm) as discrete grains, whereas magnetite and srilankite only appear as small grains along ilmenite boundaries. Zircon is present as discontinuously aligned small grains (10-40 μm) forming rims around many rutile and ilmenite grains. Attempts to date zircon rims by U-Pb using LA

  18. Pt/TiO2 (Rutile) Catalysts for Sulfuric Acid Decomposition in Sulfur-Based Thermochemical Water-Splitting Cycles

    SciTech Connect

    L. M. Petkovic; D. M. Ginosar; H. W. Rollins; K. C. Burch; P. J. Pinhero; H. H. Farrell

    2008-04-01

    Thermochemical cycles consist of a series of chemical reactions to produce hydrogen from water at lower temperatures than by direct thermal decomposition. All the sulfur-based cycles for water splitting employ the sulfuric acid decomposition reaction. This work reports the studies performed on platinum supported on titania (rutile) catalysts to investigate the causes of catalyst deactivation under sulfuric acid decomposition reaction conditions. Samples of 1 wt% Pt/TiO2 (rutile) catalysts were submitted to flowing concentrated sulfuric acid at 1123 K and atmospheric pressure for different times on stream (TOS) between 0 and 548 h. Post-operation analyses of the spent catalyst samples showed that Pt oxidation and sintering occurred under reaction conditions and some Pt was lost by volatilization. Pt loss rate was higher at initial times but total loss appeared to be independent of the gaseous environment. Catalyst activity showed an initial decrease that lasted for about 66 h, followed by a slight recovery of activity between 66 and 102 h TOS, and a period of slower deactivation after 102 h TOS. Catalyst sulfation did not seem to be detrimental to catalyst activity and the activity profile suggested that a complex dynamical situation involving platinum sintering, volatilization, and oxidation, along with TiO2 morphological changes affected catalyst activity in a non-monotonic way.

  19. The Effect of Excess Electron and hole on CO2 Adsorption and Activation on Rutile (110) surface.

    PubMed

    Yin, Wen-Jin; Wen, Bo; Bandaru, Sateesh; Krack, Matthias; Lau, M W; Liu, Li-Min

    2016-01-01

    CO2 capture and conversion into useful chemical fuel attracts great attention from many different fields. In the reduction process, excess electron is of key importance as it participates in the reaction, thus it is essential to know whether the excess electrons or holes affect the CO2 conversion. Here, the first-principles calculations were carried out to explore the role of excess electron on adsorption and activation of CO2 on rutile (110) surface. The calculated results demonstrate that CO2 can be activated as CO2 anions or CO2 cation when the system contains excess electrons and holes. The electronic structure of the activated CO2 is greatly changed, and the lowest unoccupied molecular orbital of CO2 can be even lower than the conduction band minimum of TiO2, which greatly facilities the CO2 reduction. Meanwhile, the dissociation process of CO2 undergoes an activated CO2(-) anion in bend configuration rather than the linear, while the long crossing distance of proton transfer greatly hinders the photocatalytic reduction of CO2 on the rutile (110) surface. These results show the importance of the excess electrons on the CO2 reduction process. PMID:26984417

  20. Modeling the Interaction between Integrin-Binding Peptide (RGD) and Rutile Surface: The Effect of Na+ on Peptide Adsorption

    SciTech Connect

    Wu, Chunya; Skelton, Adam; Chen, Mingjun; Vlcek, Lukas; Cummings, Peter T

    2011-01-01

    The dynamics of a single tripeptide Arg-Gly-Asp (RGD) adsorbing onto negatively charged hydroxylated rutile (110) surface in aqueous solution was studied using molecular dynamics (MD) simulations. The results indicate that the adsorbed Na{sup +} ions play an important role in determining the binding geometry of RGD. With an initial 'horseshoe' configuration, the charged side groups (COO{sup -} and NH{sub 2}) of the peptide are able to interact with the surface through direct hydrogen bonds (H bonds) in the very early stage of adsorption. The Na{sup +} ions approach the positively charged Arg side chain, competing with the Arg side chain for adsorption to the negatively charged hydroxyl oxygen. In coordination with the structural adjustment of the peptide, the Arg residue is driven to detach from the rutile surface. In contrast, the Na+ ions in close proximity to the negatively charged Asp side chain contribute to the binding of the COO{sup -} group on the surface, helping the carboxyl oxygen not involved in COO{sup -}-surface H bonds to orientate toward the hydroxyl hydrogens. Once both carboxyl oxygens form enough H bonds with the hydroxyl hydrogens, the redundant ions move toward a more favorable adsorption site.

  1. Thermal behaviour of ultra-thin Co overlayers on rutile TiO 2(1 0 0) surface

    NASA Astrophysics Data System (ADS)

    Chai, J. W.; Pan, J. S.; Wang, S. J.; Huan, C. H. A.; Lau, G. S.; Zheng, Y. B.; Xu, S.

    2005-09-01

    Thermal behaviour of ultra-thin Co overlayers on rutile TiO 2(1 0 0) surface has been studied by in situ X-ray photoelectron spectroscopy (XPS). Metal Co overlayers of about 30 Å have been deposited at room temperature on rutile TiO 2(1 0 0) surfaces, followed by annealing to different temperatures. It was found that the interfacial reaction between the Co overlayers and TiO 2(1 0 0) surfaces occurred upon annealing to temperatures above 400 °C. Above these temperatures, all metallic Co atoms were oxidized into the Co 2+ state, while some Ti 4+ were reduced to Ti 3+ with increasing temperature. Ex situ surface morphology studies by atomic force microscopy (AFM) suggest that thermal annealing resulted in the agglomeration of the metal film deposited at room temperature and the formation of islands. Annealing to higher temperature led to the dissociation of the small Co islands due to Co oxidation while the larger islands remained and grew continuously. Two types of island nanostructures were observed by ex situ high-resolution transmission electron microscopy (HRTEM).

  2. Nucleation and stochiometry dependence of rutile-TiO2 thin films grown by plasma-assisted molecular beam epitaxy

    NASA Astrophysics Data System (ADS)

    Constantin, Costel; Sun, Kai; Feenstra, R. M.

    2008-03-01

    Considerable interest has been shown of late in transition-metal oxides. One case is the titanium dioxide system, which can have applications as a high-k dielectric gate insulator for Si-based devicesootnotetextZ. J. Luo et al., Appl. Phys. Lett. 79, 2803. In this study, rutile-TiO2 thin films were grown on GaN(0001) substrates by oxygen plasma-assisted molecular beam epitaxy. Two sets of films were grown, one in which the initial GaN surface is prepared WITH the pseudo 1x1 Ga-rich surface reconstruction, and the other set, WITHOUT the pseudo 1x1. On top of these two type of surfaces, the rutile-TiO2 thin films were grown at Ts˜ 600 ^oC, and with a thickness ˜ 40 - 50 nm. During growth, reflection high-energy electron diffraction indicated a reversible stoichiometry transition from O-rich to Ti-rich growth. Post-growth x-ray diffraction measurements performed on the samples WITHOUT the GaN pseudo 1x1, show the presence of additional peaks at 2θ = 52.9^o, which implies the existence of additional phases. In addition, the high-resolution transmission electron microscopy performed on these samples show a high degree of disorder, as compared to the samples prepared WITH the pseudo 1x1. Work supported by ONR.

  3. The Effect of Excess Electron and hole on CO2 Adsorption and Activation on Rutile (110) surface

    NASA Astrophysics Data System (ADS)

    Yin, Wen-Jin; Wen, Bo; Bandaru, Sateesh; Krack, Matthias; Lau, Mw; Liu, Li-Min

    2016-03-01

    CO2 capture and conversion into useful chemical fuel attracts great attention from many different fields. In the reduction process, excess electron is of key importance as it participates in the reaction, thus it is essential to know whether the excess electrons or holes affect the CO2 conversion. Here, the first-principles calculations were carried out to explore the role of excess electron on adsorption and activation of CO2 on rutile (110) surface. The calculated results demonstrate that CO2 can be activated as CO2 anions or CO2 cation when the system contains excess electrons and holes. The electronic structure of the activated CO2 is greatly changed, and the lowest unoccupied molecular orbital of CO2 can be even lower than the conduction band minimum of TiO2, which greatly facilities the CO2 reduction. Meanwhile, the dissociation process of CO2 undergoes an activated CO2‑ anion in bend configuration rather than the linear, while the long crossing distance of proton transfer greatly hinders the photocatalytic reduction of CO2 on the rutile (110) surface. These results show the importance of the excess electrons on the CO2 reduction process.

  4. Structure of epitaxial (Fe,N) codoped rutile TiO2 thin films by x-ray absorption

    NASA Astrophysics Data System (ADS)

    Kaspar, T. C.; Ney, A.; Mangham, A. N.; Heald, S. M.; Joly, Y.; Ney, V.; Wilhelm, F.; Rogalev, A.; Yakou, F.; Chambers, S. A.

    2012-07-01

    Homoepitaxial thin films of Fe:TiO2 and (Fe,N):TiO2 were deposited on rutile(110) by molecular beam epitaxy. X-ray absorption near edge spectroscopy (XANES) spectra were collected at the Ti L-edge, Fe L-edge, Ti K-edge, O K-edge, and N K-edge. No evidence of structural disorder associated with a high concentration of oxygen vacancies is observed. Substitution of Fe for Ti could be inferred, and secondary phases such as Fe2O3, Fe3O4, and FeTiO3 can be ruled out. The similarity of the N K-edge spectra to O, and the presence of a strong x-ray linear dichroism signal for the N K-edge, indicates that N is substitutional for O in the rutile lattice and is not present as a secondary phase such as TiN. Simulations of the XANES spectra confirm substitution, although N appears to be present in more than one local environment. Neither Fe:TiO2 nor (Fe,N):TiO2 exhibit intrinsic room temperature ferromagnetism, despite the presence of mixed valent Fe(II)/Fe(III) in the reduced (Fe,N):TiO2 film.

  5. The Effect of Excess Electron and hole on CO2 Adsorption and Activation on Rutile (110) surface

    PubMed Central

    Yin, Wen-Jin; Wen, Bo; Bandaru, Sateesh; Krack, Matthias; Lau, MW; Liu, Li-Min

    2016-01-01

    CO2 capture and conversion into useful chemical fuel attracts great attention from many different fields. In the reduction process, excess electron is of key importance as it participates in the reaction, thus it is essential to know whether the excess electrons or holes affect the CO2 conversion. Here, the first-principles calculations were carried out to explore the role of excess electron on adsorption and activation of CO2 on rutile (110) surface. The calculated results demonstrate that CO2 can be activated as CO2 anions or CO2 cation when the system contains excess electrons and holes. The electronic structure of the activated CO2 is greatly changed, and the lowest unoccupied molecular orbital of CO2 can be even lower than the conduction band minimum of TiO2, which greatly facilities the CO2 reduction. Meanwhile, the dissociation process of CO2 undergoes an activated CO2− anion in bend configuration rather than the linear, while the long crossing distance of proton transfer greatly hinders the photocatalytic reduction of CO2 on the rutile (110) surface. These results show the importance of the excess electrons on the CO2 reduction process. PMID:26984417

  6. Gold Cluster Diffusion Kinetics on Stoichiometric and Reduced Surfaces of Rutile TiO 2 (110)

    SciTech Connect

    Goldman, Nir; Browning, Nigel D.

    2011-06-16

    Gold clusters on rutile TiO2 are known to serve as efficient oxidation catalysts for pollutants and environmental contaminants. However, the mechanism by which highly mobile small clusters migrate and aggregate into larger species relevant to gold’s catalytic activity remains unresolved. We report herein on ab initio simulations of the diffusion of atomic gold clusters up to the trimer on rutile TiO2(110) surfaces. We show that, on the stoichiometric surface, both the dimer and the trimer can exhibit relatively low surface mobility due to high energetic barriers for diffusion out of their energetic minima coupled with low barriers for the reverse motion. On the reduced surface, these clusters can diffuse relatively quickly between energetic minima within the oxygen vacancy site due to the large degree of vibrational entropy in their transition states. Our computed diffusion times provide a point of comparison for future experiments and will aid in development of models of gold cluster island sintering.

  7. Apatite, SiO2, rutile and orthopyroxene precipitates in minerals of eclogite xenoliths from Yakutian kimberlites, Russia

    NASA Astrophysics Data System (ADS)

    Alifirova, T. A.; Pokhilenko, L. N.; Korsakov, A. V.

    2015-06-01

    Eclogite mantle xenoliths from the central part of Siberian craton (Udachnaya and Zarnitsa kimberlite pipes) as well as from the northeastern edge of the craton (Obnazhennaya kimberlite) were studied in detail. Garnet and clinopyroxene show evident exsolution textures. Garnet comprises rutile, ilmenite, apatite, and quartz/coesite oriented inclusions. Clinopyroxene contains rutile (± ilmenite) and apatite precipitates. Granular inclusions of quartz in kyanite and garnet usually retain features of their high-pressure origin. According to thermobarometric calculations, the studied eclogitic suite was equilibrated within lithospheric mantle at 3.2-4.9 GPa and 813-1080 °C. The precursor composition of garnets from Udachnaya and Zarnitsa eclogites suggests their stability at depths 210-260 km. Apatite precipitation in clinopyroxenes of Udachnaya and Zarnitsa allows us to declare that original pyroxenes could have been indicative of their high P-T stability. Raman spectroscopic study of quartz and coesite precipitates in garnet porphyroblasts confirms our hypothesis on the origin of the exsolution textures during pressure-temperature decrease. With respect to mineralogical data, we suppose the rocks to be subjected to stepwise decompression and cooling within mantle reservoir.

  8. Insights into acetone photochemistry on rutile TiO₂(110). 2. new photodesorption channel with CH₃ ejection along the surface normal

    SciTech Connect

    Petrik, Nikolay G.; Henderson, Michael A.; Kimmel, Gregory A.

    2015-06-04

    Angle-resolved photon stimulated desorption (PSD) combined with infrared reflection-adsorption spectroscopy and temperature programmed desorption reveal two distinct channels in the photochemistry of acetone on rutile TiO₂(110) surface. During UV irradiation of co-adsorbed oxygen and acetone molecules, methyl radicals (CH₃) are ejected in two different directions: i) normal to the surface and ii) off-normal at ~±66° to the surface normal in the azimuth (i.e. perpendicular to the rows of bridging oxygen and Ti atoms). Both components are relatively narrow and non-cosine, indicating non-thermal evolution of CH₃ radicals. The direction of the “off-normal” PSD component is consistent with orientation of the C–CH₃ bonds in the n²-acetone diolate—a photoactive form of acetone chemisorption on the oxidized TiO₂(110) surface proposed earlier from experimental and theoretical studies. The direction of the “normal” PSD component requires an orientation of a C–CH₃ bond which is not consistent with the n²-acetone diolate structure. The angular distribution of the CH₃ PSD depends on the acetone coverage. The “off-normal” PSD component dominates at lower acetone coverage (< 0.2 ML), but does not increase at higher coverages in accord with the acetone diolate peak intensity in the infrared reflection-absorption spectra. The “normal” PSD component grows with the acetone coverage up to 0.6 ML. The newly discovered “normal” PSD channel is tentatively assigned to a photo-produced n²- acetone enolate as a potential precursor based on the H/D exchange experiments

  9. Comparison of the Activity and the Stability in CO Oxidation of Au-Cu Catalysts Supported on TiO2 in Anatase or Rutile Phase.

    PubMed

    Zanella, Rodolfo; Bokhimi, Xim; Maturano, Viridiana; Morales, Antonio

    2015-09-01

    Au-Cu catalysts supported on anatase or rutile phases were prepared by deposition-precipitation method. The titania polymorph used as the support determined the catalytic behavior. For the Au-Cu/rutile catalysts, the metallic phase had smaller dimensions than for the Au-Cu/anatase catalysts. The catalysts supported on anatase, however, were more active and stable than those supported on rutile. A systematic study of the catalytic activity for CO oxidation as a function of the temperature of activation and the aging time was performed. The catalytic properties were correlated with the properties of the catalysts analyzed with X-ray powder diffraction, refinement of the crystalline structures with the Rietveld method, and transmission electron microscopy. When the support was anatase, a pretreatment at 400 degrees C in air led to the most active catalysts, whereas when the support was rutile, a pretreatment between 200 and 300 degrees C in air led to the most active catalysts; activation under hydrogen generated less active catalysts. The Au-Cu catalysts activated in air were more active for the oxidation of CO than the respective monometallic gold catalysts, indicating a promoting effect between gold and copper to catalyze this reaction.

  10. Transport and Retention of TiO2 Rutile Nanoparticles in Saturated Porous Media: Influence of Solution pH, Ionic Strength, and the Presence of Humic Acid

    EPA Science Inventory

    The influence of solution pH, ionic strength, and varying concentrations of the Suwannee River Humic Acid (SRHA) on the transport of titanium dioxide (TiO2, rutile) nanoparticle aggregates (nTiO2) in saturated porous media was investigated through systematically examining the tra...

  11. Transport and Retention of TiO2 Rutile Nanoparticles in Saturated Porous Media at Low-Ionic-Strength Conditions: Measurements and Mechanisms

    EPA Science Inventory

    The mechanisms governing the transport and retention kinetics of titanium dioxide (TiO2, rutile) nanoparticle (NP) aggregates were investigated in saturated porous media. Experiments were carried out under a range of well-controlled ionic strength (from DI water up to 1 mM) and...

  12. Influence of deposition temperature on the growth of rutile TiO2 nanostructures by CBD method on seed layer prepared by RF magnetron sputtering

    NASA Astrophysics Data System (ADS)

    Selman, Abbas M.; Hassan, Z.

    2013-12-01

    Rutile titanium dioxide (TiO2) nanostructures were successfully fabricated using the simple chemical bath deposition method at various deposition temperatures. These nanostructures were fabricated on (100 ± 10 nm) TiO2 seed layer coated glass, which was prepared via radio frequency (RF) magnetron sputtering at a substrate temperature of 350 °C. The synthesized TiO2 nanostructures were annealed at 550 °C for 2 h and examined via X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), photoluminescence (PL), and Raman spectroscopy. The XRD patterns showed the presence of the peaks characteristic of rutile phase. The band gap of the TiO2 nanostructures was calculated using the UV-vis absorption spectrum and was determined to be between 3.15 and 3.24 eV. The Raman spectra contained three characteristic bands at 232, 446 and 612 cm-1, which correspond to the tetragonal TiO2 rutile. The results showed good quality of nanocrystalline TiO2 rutile phase.

  13. Rutile-TiO2 nanocoating for a high-rate Li4Ti5O12 anode of a lithium-ion battery.

    PubMed

    Wang, Yong-Qing; Gu, Lin; Guo, Yu-Guo; Li, Hong; He, Xiao-Qing; Tsukimoto, Susumu; Ikuhara, Yuichi; Wan, Li-Jun

    2012-05-01

    Well-defined Li(4)Ti(5)O(12) nanosheets terminated with rutile-TiO(2) at the edges were synthesized by a facile solution-based method and revealed directly at atomic resolution by an advanced spherical aberration imaging technique. The rutile-TiO(2) terminated Li(4)Ti(5)O(12) nanosheets show much improved rate capability and specific capacity compared with pure Li(4)Ti(5)O(12) nanosheets when used as anode materials for lithium ion batteries. The results here give clear evidence of the utility of rutile-TiO(2) as a carbon-free coating layer to improve the kinetics of Li(4)Ti(5)O(12) toward fast lithium insertion/extraction. The carbon-free nanocoating of rutile-TiO(2) is highly effective in improving the electrochemical properties of Li(4)Ti(5)O(12), promising advanced batteries with high volumetric energy density, high surface stability, and long cycle life compared with the commonly used carbon nanocoating in electrode materials.

  14. Unravelling Site-Specific Photo-Reactions of Ethanol on Rutile TiO2(110).

    PubMed

    Hansen, Jonas Ø; Bebensee, Regine; Martinez, Umberto; Porsgaard, Soeren; Lira, Estephania; Wei, Yinying; Lammich, Lutz; Li, Zheshen; Idriss, Hicham; Besenbacher, Flemming; Hammer, Bjørk; Wendt, Stefan

    2016-01-01

    Finding the active sites of catalysts and photo-catalysts is crucial for an improved fundamental understanding and the development of efficient catalytic systems. Here we have studied the photo-activated dehydrogenation of ethanol on reduced and oxidized rutile TiO2(110) in ultrahigh vacuum conditions. Utilizing scanning tunnelling microscopy, various spectroscopic techniques and theoretical calculations we found that the photo-reaction proceeds most efficiently when the reactants are adsorbed on regular Ti surface sites, whereas species that are strongly adsorbed at surface defects such as O vacancies and step edges show little reaction under reducing conditions. We propose that regular Ti surface sites are the most active sites in photo-reactions on TiO2. PMID:26915303

  15. Direct view at colossal permittivity in donor-acceptor (Nb, In) co-doped rutile TiO2

    NASA Astrophysics Data System (ADS)

    Mandal, Suman; Pal, Somnath; Kundu, Asish K.; Menon, Krishnakumar S. R.; Hazarika, Abhijit; Rioult, Maxime; Belkhou, Rachid

    2016-08-01

    Topical observations of colossal permittivity (CP) with low dielectric loss in donor-acceptor cations co-doped rutile TiO2 have opened up several possibilities in microelectronics and energy-storage devices. Yet, the precise origin of the CP behavior, knowledge of which is essential to empower the device integration suitably, is highly disputed in the literature. From spectromicroscopic approach besides dielectric measurements, we explore that microscopic electronic inhomogeneities along with the nano-scale phase boundaries and the low temperature polaronic relaxation are mostly responsible for such a dielectric behavior, rather than electron-pinned defect-dipoles/grain-boundary effects as usually proposed. Donor-acceptor co-doping results in a controlled carrier-hopping inevitably influencing the dielectric loss while invariably upholding the CP value.

  16. Tracking Site-specific C-C Coupling of Formaldehyde Molecules on Rutile TiO2(110)

    SciTech Connect

    Zhu, Ke; Xia, Yaobiao; Tang, Miru; Wang, Zhitao; Jan, Bryan; Lyubinetsky, Igor; Ge, Qingfeng; Dohnalek, Zdenek; Park, Kenneth T.; Zhang, Zhenrong

    2015-06-25

    Direct imaging of site-specific reactions of individual mole-cules as a function of temperature is a long-sought goal in molecular science. Here, we report the direct visualization of molecular coupling of formaldehyde on reduced rutile TiO2(110) surfaces as we track the same set of molecules when the temperature is increased from 75 to 170 K using scanning tunneling microscope (STM). Our recent study showed that formaldehyde preferably adsorbs on bridging-bonded oxygen (Ob) vacancy (VO) defect site. Herein, images from the same area as the temperature is increased show that VO-bound formaldehyde couples with Ti-bound formaldehyde forming a diolate intermediate. Exposure of formaldehyde at room temperature leads to diolate as the majority species on the surface and no VO-bound formaldehyde is observed. The diolate species are the key reaction intermediates in the formation of ethylene reported in previous ensemble-averaged studies.

  17. Rutile to anatase phase transition induced by N doping in highly oriented TiO2 films.

    PubMed

    Breeson, Andrew C; Sankar, Gopinathan; Goh, Gregory Kia Liang; Palgrave, Robert G

    2016-09-21

    Highly oriented TiO2 thin films were deposited onto Al2O3(0001), SrTiO3(001), and LaAlO3(001) substrates by spin coating a titanium alkoxide precursor solution followed by annealing. The films were nitrogen doped by two different routes: either by adding tetramethyethylenediamine (TMEDA) to the precursor solution or alternatively by high temperature ammonolysis. Undoped TiO2 films were highly oriented and the phase was dependent on the substrate. N doping by ammonolysis led to transformation of rutile films to anatase, confirmed by XRD and by XPS valence band spectroscopy. Significant differences were observed in the spatial distribution of the nitrogen dopant depending upon which synthesis method was used. These two factors may shed light on the increased photocatalytic efficiencies reported in N doped TiO2. PMID:27546382

  18. Ordered heteromolecular overlayers formed by metal phthalocyanines and porphyrins on rutile titanium dioxide surface studied at room temperature

    NASA Astrophysics Data System (ADS)

    Zając, Łukasz; Olszowski, Piotr; Godlewski, Szymon; Such, Bartosz; Jöhr, Res; Pawlak, Rémy; Hinaut, Antoine; Glatzel, Thilo; Meyer, Ernst; Szymonski, Marek

    2015-12-01

    Molecular heterostructures are formed from meso-tetraphenyl porphyrins-Zn(ii) (ZnTPP) and Cu(ii)-phthalocyanines (CuPc) on the rutile TiO2(011) surface. We demonstrate that ZnTPP molecules form a quasi-ordered wetting layer with flat-lying molecules, which provides the support for growth of islands comprised of upright CuPc molecules. The incorporation of the ZnTPP layer and the growth of heterostructures increase the stability of the system and allow for room temperature scanning tunneling microscopy (STM) measurements, which is contrasted with unstable STM probing of only CuPc species on TiO2. We demonstrate that within the CuPc layer the molecules arrange in two phases and we identify molecular dimers as basic building blocks of the dominant structural phase.

  19. Half-metallic behaviour in doped TiO2 (rutile) with double impurities: ab initio calculation

    NASA Astrophysics Data System (ADS)

    Fakhim Lamrani, A.; Belaiche, M.; Benyoussef, A.; El Kenz, A.

    2013-12-01

    Dilute magnetic oxides are without doubt among the most interesting classes of magnetic materials. However, the nature of their electronic structure and magnetic exchange is far from understood. Here, we apply the ab initio augmented spherical wave (ASW) method, with corrected generalised gradient approximation to study the electronic structure and magnetic properties of doped TiO2 rutile with double impurities. The study reveals a half-metallic ferromagnetic behaviour for Ti1-2x Cr x Mo x O2, and the local magnetic moments of the impurities and their oxidation states agree with the charge transfer between Cr and Mo, which would lead to the ferromagnetic state through the double-exchange mechanism in transition metal oxides.

  20. Three-dimensional interaction force and tunneling current spectroscopy of point defects on rutile TiO2(110)

    NASA Astrophysics Data System (ADS)

    Baykara, Mehmet Z.; Mönig, Harry; Schwendemann, Todd C.; Ünverdi, Ã.-zhan; Altman, Eric I.; Schwarz, Udo D.

    2016-02-01

    The extent to which point defects affect the local chemical reactivity and electronic properties of an oxide surface was evaluated with picometer resolution in all three spatial dimensions using simultaneous atomic force/scanning tunneling microscopy measurements performed on the (110) face of rutile TiO2. Oxygen atoms were imaged as protrusions in both data channels, corresponding to a rarely observed imaging mode for this prototypical metal oxide surface. Three-dimensional spectroscopy of interaction forces and tunneling currents was performed on individual surface and subsurface defects as a function of tip-sample distance. An interstitial defect assigned to a subsurface hydrogen atom is found to have a distinct effect on the local density of electronic states on the surface, but no detectable influence on the tip-sample interaction force. Meanwhile, spectroscopic data acquired on an oxygen vacancy highlight the role of the probe tip in chemical reactivity measurements.

  1. Unravelling Site-Specific Photo-Reactions of Ethanol on Rutile TiO2(110)

    PubMed Central

    Hansen, Jonas Ø.; Bebensee, Regine; Martinez, Umberto; Porsgaard, Soeren; Lira, Estephania; Wei, Yinying; Lammich, Lutz; Li, Zheshen; Idriss, Hicham; Besenbacher, Flemming; Hammer, Bjørk; Wendt, Stefan

    2016-01-01

    Finding the active sites of catalysts and photo-catalysts is crucial for an improved fundamental understanding and the development of efficient catalytic systems. Here we have studied the photo-activated dehydrogenation of ethanol on reduced and oxidized rutile TiO2(110) in ultrahigh vacuum conditions. Utilizing scanning tunnelling microscopy, various spectroscopic techniques and theoretical calculations we found that the photo-reaction proceeds most efficiently when the reactants are adsorbed on regular Ti surface sites, whereas species that are strongly adsorbed at surface defects such as O vacancies and step edges show little reaction under reducing conditions. We propose that regular Ti surface sites are the most active sites in photo-reactions on TiO2. PMID:26915303

  2. Synthesis of Room-Temperature Ferromagnetic Cr-doped TiO₂(110) Rutile Single Crystals using Ion Implantation

    SciTech Connect

    Shutthanandan, V.; Thevuthasan, Suntharampillai; Droubay, Timothy C.; Heald, Steve M.; Engelhard, Mark H.; McCready, David E.; Chambers, Scott A.; Nachimuthu, Ponnusamy; Mun, B. S.

    2006-01-01

    Ferromagnetic Cr-doped rutile TiO₂ single crystals were synthesized by high-temperature ion implantation. The associated structural, compositional and magnetic properties were studied by x-ray photoelectron spectroscopy, Rutherford backscattering spectrometry, proton induced x-ray emission, x-ray diffraction, Cr K- and L-shell near-edge x-ray absorption spectroscopy, and vibrating sample magnetometry. Cr was distributed uniformly to the depth of about 300 nm with an average concentration of ~1 at. %. The samples are semiconducting and ferromagnetic as implanted, with a saturation magnetization of 0.29 B/Cr atom at room temperature. Cr is in a formal oxidation state of +3 throughout the implanted region, and no CrO₂ is detected.

  3. Influence of anatase and rutile phase in TiO2 upon the photocatalytic degradation of methylene blue under solar irradiation in presence of activated carbon.

    PubMed

    Matos, J; Montaña, R; Rivero, E; Escudero, A; Uzcategui, D

    2014-01-01

    The influence of activated carbon (AC) on the photocatalytic activity of different crystalline TiO2 phases was verified in the photocatalytic degradation of methylene blue under UV and solar irradiation. The results showed a volcano trend with a maximum photoactivity for the crystalline phase ratio of anatase:rutile equal to 80:20 both under UV or solar irradiation. By contrast, in presence of AC the photocatalytic activity of the binary materials of TiO2/AC followed an exponential trend, increasing as a function of the increase in anatase proportion in the TiO2 framework. The increase in the photoactivity of the binary material TiO2/AC relative to neat TiO2 was up to 22 and about 17 times higher under UV and visible irradiation, respectively. The present results suggest that AC interacts more efficiently with anatase phase than with rutile phase.

  4. A method for the concentration of fine-grained rutile (TiO2) from sediment and sedimentary rocks by chemical leaching

    USGS Publications Warehouse

    Commeau, Judith A.; Valentine, Page C.

    1991-01-01

    Most of the sample analyzed by the method described were marine muds collected from the Gulf of Maine (Valentine and Commeau, 1990). The silt and clay fraction (up to 99 wt% of the sediment) is composed of clay minerals (chiefly illite-mica and chlorite), silt-size quartz and feldspar, and small crystals (2-12 um) of rutile and hematite. The bulk sediment samples contained an average of 2 to 3 wt percent CaCO3. Tiher samples analyzed include red and gray Carboniferous and Triassic sandstones and siltstones exposed around the Bay of Fundy region and Paleozoic sandstones, siltstones, and shales from northern Maine and New Brunswick. These rocks are probable sources for the fine-grained rutile found in the Gulf of Maine.

  5. Dielectric properties of some MM‧O4 and MTiM‧O6 (M=Cr, Fe, Ga; M‧=Nb, Ta, Sb) rutile-type oxides

    NASA Astrophysics Data System (ADS)

    Mani, Rohini; Achary, S. N.; Chakraborty, Keka R.; Deshpande, S. K.; Joy, Joby E.; Nag, Abanti; Gopalakrishnan, J.; Tyagi, A. K.

    2010-06-01

    We describe an investigation of the structure and dielectric properties of MM'O 4 and MTi M'O 6 rutile-type oxides for M=Cr, Fe, Ga and M'=Nb, Ta and Sb. All the oxides adopt a disordered rutile structure ( P4 2/ mnm) at ambient temperature. A partial ordered trirutile-type structure is confirmed for FeTaO 4 from the low temperature (17 K) neutron diffraction studies. While both the MM'O 4 oxides (CrTaO 4 and FeTaO 4) investigated show a normal dielectric property MTi M'O 6 oxides for M=Fe, Cr and M'=Nb/Ta/Sb display a distinct relaxor/relaxor-like response. Significantly the corresponding gallium analogs, GaTiNbO 6 and GaTiTaO 6, do not show a relaxor response at T<500 K.

  6. Effective charge separation in the rutile TiO2 nanorod-coupled α-Fe2O3 with exceptionally high visible activities

    PubMed Central

    Luan, Peng; Xie, Mingzheng; Liu, Dening; Fu, Xuedong; Jing, Liqiang

    2014-01-01

    Herein, we have fabricated rutile TiO2 nanorod-coupled α-Fe2O3 by a wet-chemical process. It is demonstrated that the visible activities for photoelectrochemical water oxidation and for degrading pollutant of α-Fe2O3 are greatly enhanced after coupling a proper amount of rutile nanorods. The enhanced activity is attributed to the prolonged lifetime and improved separation of photogenerated charges mainly by the transient surface photovoltage responses. Interestingly, the observed EPR signals (with g⊥ = 1.963 and g|| = 1.948) of Ti3+ in the fabricated TiO2-Fe2O3 nanocomposite at ultra low temperature (1.8 k) after visible laser excitation, along with the electrochemical impedance spectra and the normalized photocurrent action spectra, testify evidently that the spacial transfers of visible-excited high-energy electrons of α-Fe2O3 to TiO2 could happen. Moreover, it is confirmed that it is more favorable for the uncommon electron transfers of α-Fe2O3 to rutile than to anatase. This is responsible for the much obvious enhancement of visible activity of Fe2O3 after coupling with rutile TiO2, compared with anatase and phase-mixed P25 ones. This work would help us to deeply understand the uncommon photophysical processes, and also provide a feasible route to improve the photocatalytic performance of visible-response semiconductor photocatalyst for water splitting and pollutant degradation. PMID:25154460

  7. Rutile-structured TiO{sub 2} deposited by plasma enhanced atomic layer deposition using tetrakis(dimethylamino)titanium precursor on in-situ oxidized Ru electrode

    SciTech Connect

    Pointet, John; Gonon, Patrice; Latu-Romain, Lawrence; Bsiesy, Ahmad Vallée, Christophe

    2014-01-15

    In this work, tetrakis(dimethylamino)titanium precursor as well as in-situ oxidized ruthenium bottom electrode were used to grow rutile-structured titanium dioxide thin layers by plasma enhanced atomic layer deposition. Metal–insulator–metal capacitors have been elaborated in order to study the electrical properties of the device. It is shown that this process leads to devices exhibiting excellent results in terms of dielectric constant and leakage current.

  8. Luminescence of SiO2 and GeO2 crystals with rutile structure. Comparison with α-quartz crystals and relevant glasses (Review Article)

    NASA Astrophysics Data System (ADS)

    Trukhin, A. N.

    2016-07-01

    Luminescence properties of SiO2 in different structural states are compared. Similar comparison is made for GeO2. Rutile and α-quartz structures as well as glassy state of these materials are considered. Main results are that for α-quartz crystals the luminescence of self-trapped exciton is the general phenomenon that is absent in the crystal with rutile structure. In rutile structured SiO2 (stishovite) and GeO2 (argutite) the main luminescence is due to a host material defect existing in as-received (as-grown) samples. The defect luminescence possesses specific two bands, one of which has a slow decay (for SiO2 in the blue and for GeO2, in green range) and another, a fast ultraviolet (UV) band (4.75 eV in SiO2 and at 3 eV in GeO2). In silica and germania glasses, the luminescence of self-trapped exciton coexists with defect luminescence. The latter also contains two bands: one in the visible range and another in the UV range. The defect luminescence of glasses was studied in details during last 60-70 years and is ascribed to oxygen deficient defects. Analogous defect luminescence in the corresponding pure nonirradiated crystals with α-quartz structure is absent. Only irradiation of a α-quartz crystal by energetic electron beam, γ-rays and neutrons provides defect luminescence analogous to glasses and crystals with rutile structure. Therefore, in glassy state the structure containing tetrahedron motifs is responsible for existence of self-trapped excitons and defects in octahedral motifs are responsible for oxygen deficient defects.

  9. Photochemical Properties, Composition, and Structure in Molecular Beam Epitaxy Grown Fe “Doped” and (Fe,N) Codoped Rutile TiO2(110)

    SciTech Connect

    Mangham, Andrew N.; Govind, Niranjan; Bowden, Mark E.; Shutthanandan, V.; Joly, Alan G.; Henderson, Michael A.; Chambers, Scott A.

    2011-08-11

    We have investigated the surface photochemical properties of Fe "doped" and (Fe,N) co-doped homoepitaxial rutile TiO2 (110) films grown by plasma assisted molecular beam epitaxy. Fe does not incorporate as an electronic dopant in the rutile lattice, but rather segregates to the film surface. However, co-deposition of Fe with N enhances the solubility of Fe, and DFT calculations suggest that co-dopant complex formation is the driving force behind the enhanced solubility. The co-doped films, in which a few atomic percent of Ti (O) are replaced with Fe (N), exhibit significant disorder compared to undoped films grown under the same conditions, presumably due to dopant-induced strain. Co-doping redshifts the rutile bandgap into the visible. However, the film surfaces are photochemically inert with respect to hole-mediated decomposition of adsorbed trimethyl acetate. The absence of photochemical activity may result from dopant-induced trap and/or recombination sites within the film. This study indicates that enhanced visible light absorptivity in TiO2 does not necessarily result in visible light initiated surface photochemistry.

  10. Hierarchical chlorine-doped rutile TiO{sub 2} spherical clusters of nanorods: Large-scale synthesis and high photocatalytic activity

    SciTech Connect

    Xu Hua; Zheng Zhi; Zhang Lizhi Zhang Hailu; Deng Feng

    2008-09-15

    In this study, we report the synthesis of hierarchical chlorine-doped rutile TiO{sub 2} spherical clusters of nanorods photocatalyst on a large scale via a soft interface approach. This catalyst showed much higher photocatalytic activity than the famous commercial titania (Degussa P25) under visible light ({lambda}>420 nm). The resulting sample was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), nitrogen adsorption, X-ray photoelectron spectroscopy (XPS), UV-vis diffuse reflectance spectroscopy, {sup 1}H solid magic-angle spinning nuclear magnetic resonance (MAS-NMR) and photoluminescence spectroscopy. On the basis of characterization results, we found that the doping of chlorine resulted in red shift of absorption and higher surface acidity as well as crystal defects in the photocatalyst, which were the reasons for high photocatalytic activity of chlorine-doped TiO{sub 2} under visible light ({lambda}>420 nm). These hierarchical chlorine-doped rutile TiO{sub 2} spherical clusters of nanorods are very attractive in the fields of environmental pollutants removal and solar cell because of their easy separation and high activity. - Graphical abstract: Hierarchical chlorine-doped rutile TiO{sub 2} spherical clusters of nanorods photocatalyst were synthesized on a large scale via a soft interface approach. This catalyst showed much higher photocatalytic activity than the famous commercial titania (Degussa P25) under visible light ({lambda}>420 nm)

  11. Role of the crystalline form of titanium dioxide nanoparticles: Rutile, and not anatase, induces toxic effects in Balb/3T3 mouse fibroblasts.

    PubMed

    Uboldi, Chiara; Urbán, Patricia; Gilliland, Douglas; Bajak, Edyta; Valsami-Jones, Eugenia; Ponti, Jessica; Rossi, François

    2016-03-01

    The wide use of titanium dioxide nanoparticles (TiO2 NPs) in industrial applications requires the investigation of their effects on human health. In this context, we investigated the effects of nanosized and bulk titania in two different crystalline forms (anatase and rutile) in vitro. By colony forming efficiency assay, a dose-dependent reduction of the clonogenic activity of Balb/3T3 mouse fibroblasts was detected in the presence of rutile, but not in the case of anatase NPs. Similarly, the cell transformation assay and the micronucleus test showed that rutile TiO2 NPs were able to induce type-III foci formation in Balb/3T3 cells and appeared to be slightly genotoxic, whereas anatase TiO2 NPs did not induce any significant neoplastic or genotoxic effect. Additionally, we investigated the interaction of TiO2 NPs with Balb/3T3 cells and quantified the in vitro uptake of titania using mass spectrometry. Results showed that the internalization was independent of the crystalline form of TiO2 NPs but size-dependent, as nano-titania were taken up more than their respective bulk materials. In conclusion, we demonstrated that the cytotoxic, neoplastic and genotoxic effects triggered in Balb/3T3 cells by TiO2 NPs depend on the crystalline form of the nanomaterial, whereas the internalization is regulated by the particle size.

  12. Anatase/rutile bi-phasic titanium dioxide nanoparticles for photocatalytic applications enhanced by nitrogen doping and platinum nano-islands.

    PubMed

    Bear, Joseph C; Gomez, Virginia; Kefallinos, Nikolaos S; McGettrick, James D; Barron, Andrew R; Dunnill, Charles W

    2015-12-15

    Titanium dioxide (TiO2) bi-phasic powders with individual particles containing an anatase and rutile hetero-junction have been prepared using a sequential layer sol-gel deposition technique to soluble substrates. Sequential thin films of rutile and subsequently anatase TiO2 were deposited onto sodium chloride substrates yielding extremely fragile composite layered discs that fractured into "Janus-like" like powders on substrate dissolution. Nitrogen doped and platinum sputtered analogues were also prepared, and analysed for photocatalytic potential using the photodegradation of Rhodamine B, a model organic pollutant under UV and visible light irradiation. The materials were characterised using X-ray diffraction, X-ray photoelectron spectroscopy, energy dispersive X-ray spectroscopy, Raman spectroscopy and scanning electron microscopy. This paper sheds light on the relationship between anatase and rutile materials when in direct contact and demonstrates a robust method for the synthesis of bi-phasic nanoparticles, ostensibly of any two materials, for photocatalytic reactions or otherwise.

  13. Phonon quarticity induced by changes in phonon-tracked hybridization during lattice expansion and its stabilization of rutile TiO2

    DOE PAGES

    Lan, Tian; Li, Chen W.; Hellman, O.; Kim, D. S.; Muñoz, Jorge A.; Smith, Hillary; Abernathy, Douglas L.; Fultz, B.

    2015-08-11

    Although the rutile structure of TiO2 is stable at high temperatures, the conventional quasiharmonic approximation predicts that several acoustic phonons decrease anomalously to zero frequency with thermal expansion, incorrectly predicting a structural collapse at temperatures well below 1000 K. In this paper, inelastic neutron scattering was used to measure the temperature dependence of the phonon density of states (DOS) of rutile TiO2 from 300 to 1373 K. Surprisingly, these anomalous acoustic phonons were found to increase in frequency with temperature. First-principles calculations showed that with lattice expansion, the potentials for the anomalous acoustic phonons transform from quadratic to quartic, stabilizingmore » the rutile phase at high temperatures. In these modes, the vibrational displacements of adjacent Ti and O atoms cause variations in hybridization of 3d electrons of Ti and 2p electrons of O atoms. Finally, with thermal expansion, the energy variation in this “phonon-tracked hybridization” flattens the bottom of the interatomic potential well between Ti and O atoms, and induces a quarticity in the phonon potential.« less

  14. Analysis of the Temperature Dependence of the Capacitance-Voltage and Conductance-Voltage Characteristics of Au/TiO2(rutile)/ n-Si Structures

    NASA Astrophysics Data System (ADS)

    KInacI, BarIş; Özçelik, Süleyman

    2013-06-01

    The capacitance-voltage-temperature ( C- V- T) and the conductance/angular frequency-voltage-temperature ( G/ω- V- T) characteristics of Au/TiO2(rutile)/ n-Si Schottky barrier diodes (SBDs) were investigated over the temperature range from 200 K to 380 K by considering the series resistance effect. Titanium dioxide (TiO2) was deposited on n-type silicon (Si) substrate using a direct-current (DC) magnetron sputtering system at 200°C. To improve the crystal quality, the deposited film was annealed at 900°C to promote a phase transition from the amorphous to rutile phase. The C -2 versus V plots gave a straight line in the reverse-bias region. The main electrical parameters, such as the doping concentration ( N D), Fermi energy level ( E F), depletion layer width ( W D), barrier height ( ф CV), and series resistance ( R S), of Au/TiO2(rutile)/ n-Si SBDs were calculated from the C- V- T and the G/ω- V- T characteristics. The obtained results show that ф CV, R S, and W D values decrease, while E F and N D values increase, with increasing temperature.

  15. Spontaneous formation of suboxidic coordination around Co in ferromagnetic rutile Ti0.95Co0.5O2 film

    DOE PAGES

    Hu, Wen; Hayaski, Kouichi; Fukumura, Tomoteru; Akagi, Kazuto; Tsukada, Masaru; Happo, Naohisa; Hosokawa, Shinya; Ohwada, Kenji; Takahasi, Masamitu; Suzuki, Motohiro; et al

    2015-06-02

    To evaluate local atomic structures around Co in high temperature diluted ferromagnetic semiconductor Co-doped TiO2, x-ray fluorescence holography and x-ray absorption fine structure experiments were carried out on rutile paramagnetic Ti0.99Co0.01O2 and ferromagnetic Ti0.95Co0.05O2 films. The Co atoms in the Ti0.99Co0.01O2 simply substituted for Ti sites in the rutile structure, whereas a suboxidic arrangement of CoO2Ti4 formed around Co in the Ti0.95Co0.05O2 films. A theoretical investigation based on a series of first-principles calculations indicated the stability of the aggregated suboxidic clusters in the rutile TiO2, supporting our hypothesis for the formation of suboxidic coordination in the highly Co-doped sample. Asmore » a result, the suboxidic coordination may be the source of strong exchange interaction, resulting in the high Curie temperature in Co-doped TiO2.« less

  16. Rutile TiO2 Mesocrystals/Reduced Graphene Oxide with High-Rate and Long-Term Performance for Lithium-Ion Batteries

    PubMed Central

    Lan, Tongbin; Qiu, Heyuan; Xie, Fengyan; Yang, Jie; Wei, Mingdeng

    2015-01-01

    An in situ hydrothermal route is developed for fabricating rutile TiO2 mesocrystals/reduced graphene oxide nanosheets (TGR) hybrids in the presence of dodecylbenzenesulphonic acid (ADBS). These rutile TiO2 mesocrystals with a Wulff shape are composed of ultra-tiny rod-like subunits with the same oriented direction and closely wrapped by the nanosheets of reduced graphene oxide (RGO). It is found that ADBS played a key role for the formation of mesocrystals during the self-assembly process, which pillared the graphene oxide (GO) nanosheets and involved the aggregation of the mesocrystal subunits. Furthermore, the TGR hybrids are used as an anode material and exhibited a large capacity over 150 mA h g−1 at 20 C after 1000 cycles, and high rate capability up to 40 C. These high performance characteristics may be due to the intrinsic characteristics of rutile TiO2 mesocrystals constructed from ultra-tiny subunits and hybridized with super conductive RGO nanosheets. PMID:25688035

  17. Structural characterization of mineral with rutile inclusions (TiO2) and manganocolumbite (MnNb2O6) by means of X-ray

    NASA Astrophysics Data System (ADS)

    Arcila, J. F.; Hincapié, A. F.

    2013-11-01

    A sample of mineral obtained in the department of Vichada was characterized by the technique of X-ray diffraction in powder samples, in order to determine the crystallographic phases present. After analyzing diffraction patterns, as a result, the mineral had inclusions of Rutile (86.3%) and Manganocolumbita (13.7%). Next, a simulation of the crystal structure of these minerals from the data entered in the databases was carried on. Later, the Rietveld method was used, from this refinement, the new diffraction pattern and the new network parameters were obtained. For the Rutile it was obtained a tetragonal structure, and for the Manganocolumbita an orthorhombic structure was obtained. The characterization is justified among other aspects due to the important applications of these materials in industry and technology, such as Rutile is used in welding rod coatings, in Industries cardboard paper and ink impression among many other uses, the Manganocolumbita is used in special alloys resistant to high temperatures, it also is directly related to the tantalite in coltan formation.

  18. Spontaneous formation of suboxidic coordination around Co in ferromagnetic rutile Ti{sub 0.95}Co{sub 0.05}O{sub 2} film

    SciTech Connect

    Hu, Wen; Hayashi, Kouichi; Fukumura, Tomoteru; Akagi, Kazuto; Tsukada, Masaru; Happo, Naohisa; Hosokawa, Shinya; Ohwada, Kenji; Takahasi, Masamitu; Suzuki, Motohiro

    2015-06-01

    To evaluate local atomic structures around Co in high temperature diluted ferromagnetic semiconductor Co-doped TiO{sub 2}, x-ray fluorescence holography and x-ray absorption fine structure experiments were carried out on rutile paramagnetic Ti{sub 0.99}Co{sub 0.01}O{sub 2} and ferromagnetic Ti{sub 0.95}Co{sub 0.05}O{sub 2} films. The Co atoms in the Ti{sub 0.99}Co{sub 0.01}O{sub 2} simply substituted for Ti sites in the rutile structure, whereas a suboxidic arrangement of CoO{sub 2}Ti{sub 4} formed around Co in the Ti{sub 0.95}Co{sub 0.05}O{sub 2} films. A theoretical investigation based on a series of first-principles calculations indicated the stability of the aggregated suboxidic clusters in the rutile TiO{sub 2}, supporting our hypothesis for the formation of suboxidic coordination in the highly Co-doped sample. The suboxidic coordination may be the source of strong exchange interaction, resulting in the high Curie temperature in Co-doped TiO{sub 2}.

  19. A DFT study of water adsorption on rutile TiO2 (110) surface: The effects of surface steps.

    PubMed

    Zheng, Ting; Wu, Chunya; Chen, Mingjun; Zhang, Yu; Cummings, Peter T

    2016-07-28

    The associative and dissociative adsorption of water molecules at low-coverage situations on rutile TiO2 (110) surface with step defects was investigated by the density functional theory calculations. Structural optimization of the hydroxylated/hydrated configurations at step edges along the 11̄1 crystal directions and the dynamic process of water dissociation were discussed to get a better description of the water/TiO2 interface. Our results indicate that steps on the TiO2 (110) surface could be an active site for water dissociation. The results of geometry optimization suggest that the stability of hydroxylated configuration is largely dependent on the locations of the H species and the recombination of water molecules from hydroxyls is observed in the fully hydroxylated condition. However, these hydroxyls can be stabilized by the associatively absorbed water nearby by forming competitive intermolecular hydrogen bonds. The dynamics of water dissociation and hydrogen diffusion were studied by the first principles molecular dynamics simulation and our results suggest that the hydrogen released by water dissociation can be transferred among the adsorbates, such as the unsaturated oxygen atoms-H2O-hydroxyl (TiO-H2O-OH) complex at step edges, or gradually diffuses to the bulk water system in the form of hydronium (H3O(+)) at higher water coverage. PMID:27475381

  20. TiO₂ (rutile) embedded inulin--A versatile bio-nanocomposite for photocatalytic degradation of methylene blue.

    PubMed

    Jayanthi Kalaivani, G; Suja, S K

    2016-06-01

    Inulin, a water soluble carbohydrate polymer, was extracted from Allium sativum L. by hot water diffusion method. A novel bio-nanocomposite was prepared by embedding TiO2 (rutile) onto the inulin matrix. The extracted inulin and the prepared bio-nanocomposite were characterized using UV-vis, FT-IR, XRD, SEM, TEM and TGA techniques. The photocatalytic activity of the bio-nanocomposite for the degradation of methylene blue was studied under UV illumination in batch mode experiment and was found to be twice as high as that of pristine TiO2. The kapp for inulin-TiO2 (0.0449 min(-1)) was higher than that for TiO2 (0.0325 min(-1)) which may be due to the synergistic action of inulin and TiO2. The stabilization of photo excited electron suppressed the electron-hole pair recombination thereby inducing the electrons and the holes to participate in the photo reduction and oxidation processes, respectively and enhancing the photocatalytic activity. PMID:27083343

  1. Carbon-coated rutile titanium dioxide derived from titanium-metal organic framework with enhanced sodium storage behavior

    NASA Astrophysics Data System (ADS)

    Zou, Guoqiang; Chen, Jun; Zhang, Yan; Wang, Chao; Huang, Zhaodong; Li, Simin; Liao, Hanxiao; Wang, Jufeng; Ji, Xiaobo

    2016-09-01

    Carbon-coated rutile titanium dioxide (CRT) was fabricated through an in-situ pyrolysis of titanium-based metal organic framework (Ti8O8(OH)4[O2CC6H4CO2]6) crystals. Benefiting from the Tisbnd Osbnd C skeleton structure of titanium-based metal organic framework, the CRT possesses abundant channels and micro/mesopores with the diameters ranging from 1.06 to 4.14 nm, shows larger specific surface area (245 m2 g-1) and better electronic conductivity compared with pure titanium dioxide (12.8 m2 g-1). When applied as anode material for sodium-ion batteries, the CRT electrode exhibits a high cycling performance with a reversible capacity of ∼175 mAh g-1 at 0.5 C-rate after 200 cycles, and obtains an excellent rate capability of ∼70 mAh g-1 after 2000 cycles even at a specific current of 3360 mA g-1(20 C-rate). The outstanding rate capability can be attributed to the carbon-coated structure, which may effectively prevent aggregation of the titanium dioxide nanoparticles, accelerate the mass transfer of Na+ and speed up the charge transfer rate. Considering these advantages of this particular framework structure, the CRT can serve as an alternative anode material for the industrial application of SIBs.

  2. Metastability of anatase: size dependent and irreversible anatase-rutile phase transition in atomic-level precise titania

    PubMed Central

    Satoh, Norifusa; Nakashima, Toshio; Yamamoto, Kimihisa

    2013-01-01

    Since crystal phase dominantly affects the properties of nanocrystals, phase control is important for the applications. To demonstrate the size dependence in anatase-rutile phase transition of titania, we used quantum-size titania prepared from the restricted number of titanium ions within dendrimer templates for size precision purposes and optical wave guide spectroscopy for the detection. Contrary to some theoretical calculations, the observed irreversibility in the transition indicates the metastablity of anatase; thermodynamics cannot explain the formation of metastable states. Therefore, we take into account the kinetic control polymerization of TiO6 octahedral units to explain how the crystal phase of the crystal-nucleus-size titania is dependent on which coordination sites, cis- or trans-, react in the TiO6 octahedra, suggesting possibilities for the synthetic phase control of nanocrystals. In short, the dendrimer templates give access to crystal nucleation chemistry. The paper will also contribute to the creation of artificial metastable nanostructures with atomic-level precision. PMID:23743571

  3. Ordinary and extraordinary dielectric functions of rutile SnO{sub 2} up to 20 eV

    SciTech Connect

    Feneberg, Martin Lidig, Christian; Lange, Karsten; Goldhahn, Rüdiger; Neumann, Maciej D.; Esser, Norbert; Bierwagen, Oliver; White, Mark E.; Tsai, Min Y.; Speck, James S.

    2014-06-09

    Spectroscopic ellipsometry at room temperature is applied in order to determine the ordinary (ε{sub ⊥}) and extraordinary (ε{sub ∥}) dielectric functions (DFs) of rutile SnO{sub 2} corresponding to electric field (E) polarization perpendicular (E⊥c) and parallel (E∥c) to the optical axis (c), respectively. Strong anisotropic behavior is found for the full spectral range from 0.5 up to 20 eV. The onsets of strong absorption are found at 4.28 eV and 5.42 eV for E⊥c and E∥c, respectively. A dipole-forbidden band gap at (3.59 ± 0.2) eV at room temperature is found by line shape fits to the imaginary parts of the DFs. Further high-energy transitions are resolved. Their accurate energy values are obtained by fitting the second derivatives of the DFs. Comparison to published DFs calculated by ab-initio theory demonstrates that the electron-hole interaction in SnO{sub 2} is strong and has to be included for interpretation.

  4. Temperature-programmed desorption study of NO reactions on rutile TiO2(110)-1 × 1

    NASA Astrophysics Data System (ADS)

    Kim, Boseong; Dohnálek, Zdenek; Szanyi, János; Kay, Bruce D.; Kim, Yu Kwon

    2016-10-01

    Systematic temperature-programmed desorption (TPD) studies of NO adsorption and reactions on rutile TiO2(110)-1 × 1 surface reveal several distinct reaction channels in a temperature range of 50-500 K. NO readily reacts on TiO2(110) to form N2O, which desorbs between 50 and 200 K (LT N2O channels), which leaves the TiO2 surface populated with adsorbed oxygen atoms (Oa) as a by-product of N2O formation. In addition, we observe simultaneous desorption peaks of NO and N2O at 270 K (HT1 N2O) and 400 K (HT2 N2O), respectively, both of which are attributed to reaction-limited processes. No N-derived reaction product desorbs from TiO2(110) surface above 500 K or higher, while the surface may be populated with Oa's and oxidized products such as NO2 and NO3. The adsorbate-free TiO2 surface with oxygen vacancies can be regenerated by prolonged annealing at 850 K or higher. Detailed analysis of the three N2O desorption yields reveals that the surface species for the HT channels are likely to be various forms of NO dimers.

  5. Cooperative and competitive adsorption of amino acids with Ca²⁺ on rutile (α-TiO₂).

    PubMed

    Lee, Namhey; Sverjensky, Dimitri A; Hazen, Robert M

    2014-08-19

    The interactions of biomolecules such as amino acids with mineral surfaces in the near-surface environment are an important part of the short and long-term carbon cycles. Amino acid-mineral surface interactions also play an important role in biomineralization, biomedicine, and in assembling the building blocks of life in the prebiotic era. Although the pH effects during adsorption of amino acids onto mineral surfaces have been studied, little is known about the effects of environmentally important divalent cations. In this study, we investigated the adsorption of the oppositely charged amino acids glutamate and lysine with and without the addition of divalent calcium. Without calcium, glutamate shows a maximum in adsorption at a pH of ∼4 and lysine shows a maximum in adsorption at a pH of ∼9.4. In comparison, with calcium present, glutamate showed maxima in adsorption at both low and high pH, whereas lysine showed no adsorption at all. These dramatic effects can be described as cooperative adsorption between glutamate and Ca(2+) and as competitive adsorption between lysine and Ca(2+). The origin of these effects can be attributed to electrostatic phenomena. Adsorption of Ca(2+) at high pH makes the rutile surface more positive, which attracts glutamate and repels lysine. Our results indicate that the interactions of biomolecules with mineral surfaces in the environment will be strongly affected by the major dissolved species in natural waters.

  6. Ammonia formation from NO reaction with surface hydroxyls on rutile TiO2 (110) - 1×1

    SciTech Connect

    Kim, Boseong; Kay, Bruce D.; Dohnalek, Zdenek; Kim, Yu Kwon

    2015-01-15

    The reaction of NO with hydroxylated rutile TiO2(110)-1×1 surface (h-TiO2) was investigated as a function of NO coverage using temperature-programmed desorption. Our results show that NO reaction with h-TiO2 leads to formation of NH3 which is observed to desorb at ~ 400 K. Interestingly, the amount of NH3 produced depends nonlinearly on the coverage of NO. The yield increases up to a saturation value of ~1.3×1013 NH3/cm2 at a NO dose of 5×1013 NO/cm2, but subsequently decreases at higher NO doses. Preadsorbed H2O is found to have a negligible effect on the NH3 desorption yield. Additionally, no NH3 is formed in the absence of surface hydroxyls (HOb’s) upon coadsorption of NO and H2O on a stoichiometric TiO2(110) (s-TiO2(110)). Based on these observations, we conclude that nitrogen from NO has a strong preference to react with HOb’s on the bridge-bonded oxygen rows (but not with H2O) to form NH3. The absolute NH3 yield is limited by competing reactions of HOb species with titanium-bound oxygen adatoms to form H2O. Our results provide new mechanistic insight about the interactions of NO with hydroxyl groups on TiO2(110) .

  7. TiO₂ (rutile) embedded inulin--A versatile bio-nanocomposite for photocatalytic degradation of methylene blue.

    PubMed

    Jayanthi Kalaivani, G; Suja, S K

    2016-06-01

    Inulin, a water soluble carbohydrate polymer, was extracted from Allium sativum L. by hot water diffusion method. A novel bio-nanocomposite was prepared by embedding TiO2 (rutile) onto the inulin matrix. The extracted inulin and the prepared bio-nanocomposite were characterized using UV-vis, FT-IR, XRD, SEM, TEM and TGA techniques. The photocatalytic activity of the bio-nanocomposite for the degradation of methylene blue was studied under UV illumination in batch mode experiment and was found to be twice as high as that of pristine TiO2. The kapp for inulin-TiO2 (0.0449 min(-1)) was higher than that for TiO2 (0.0325 min(-1)) which may be due to the synergistic action of inulin and TiO2. The stabilization of photo excited electron suppressed the electron-hole pair recombination thereby inducing the electrons and the holes to participate in the photo reduction and oxidation processes, respectively and enhancing the photocatalytic activity.

  8. X-ray Induced Reorganization/Polymerization of Resorcinol on the TiO2 Rutile (110) Surface

    NASA Astrophysics Data System (ADS)

    Paliwal, Vinod Kumar; Li, Shao-Chun; Diebold, Ulrike

    2011-03-01

    The room-temperature adsorption of resorcinol (1, 3 benzenediol, C6 H4 (OH)2) on the (110) surface of rutile Ti O2 was investigated with STM and x-ray photoemission (XPS). The saturation coverage of resorcinol is smaller as compared to catechol (1,2 benzenediol) with a C1s/Ti 2 p 3/2 ratio of ~ 7.3 % and 12%, respectively. This indicates that resorcinol occupies on average more than two Ti sites on the surface. STM suggests that resorcinol molecules are mobile at lower coverage, whereas a weakly-ordered overlayer with a periodicity of 3 unit-cells along [001] is observed at higher coverages. Interestingly, exposure of resorcinol-saturated Ti O2 surface to an XPS Mg- K α beam (1253.6 eV) induces a reorganization of adsorbed resorcinol molecules. STM shows well-resolved double chains that run across [001]-oriented rows of Ti O2 (110) surface. These results suggest that irradiation induces a polymerization reaction of adsorbed resorcinol molecules, where neighboring aromatic rings are arranged in a zig-zag configuration.

  9. Ordinary and extraordinary dielectric functions of rutile SnO2 up to 20 eV

    NASA Astrophysics Data System (ADS)

    Feneberg, Martin; Lidig, Christian; Lange, Karsten; Goldhahn, Rüdiger; Neumann, Maciej D.; Esser, Norbert; Bierwagen, Oliver; White, Mark E.; Tsai, Min Y.; Speck, James S.

    2014-06-01

    Spectroscopic ellipsometry at room temperature is applied in order to determine the ordinary (ɛ⊥) and extraordinary (ɛ∥) dielectric functions (DFs) of rutile SnO2 corresponding to electric field (E) polarization perpendicular (E ⊥c) and parallel (E∥c) to the optical axis (c), respectively. Strong anisotropic behavior is found for the full spectral range from 0.5 up to 20 eV. The onsets of strong absorption are found at 4.28 eV and 5.42 eV for E ⊥c and E ∥c, respectively. A dipole-forbidden band gap at (3.59 ± 0.2) eV at room temperature is found by line shape fits to the imaginary parts of the DFs. Further high-energy transitions are resolved. Their accurate energy values are obtained by fitting the second derivatives of the DFs. Comparison to published DFs calculated by ab-initio theory demonstrates that the electron-hole interaction in SnO2 is strong and has to be included for interpretation.

  10. Temperature-programmed desorption study of NO reactions on rutile TiO2(110)-1×1

    DOE PAGES

    Kim, Boseong; Dohnalek, Zdenek; Szanyi, Janos; Kay, Bruce D.; Kim, Yu Kwon

    2016-02-24

    In this study, systematic temperature-programmed desorption (TPD) studies of NO adsorption and reactions on rutile TiO2(110)-1 × 1 surface reveal several distinct reaction channels in a temperature range of 50–500 K. NO readily reacts on TiO2(110) to form N2O, which desorbs between 50 and 200 K (LT N2O channels), which leaves the TiO2 surface populated with adsorbed oxygen atoms (Oa) as a by-product of N2O formation. In addition, we observe simultaneous desorption peaks of NO and N2O at 270 K (HT1 N2O) and 400 K (HT2 N2O), respectively, both of which are attributed to reaction-limited processes. No N-derived reaction productmore » desorbs from TiO2(110) surface above 500 K or higher, while the surface may be populated with Oa's and oxidized products such as NO2 and NO3. The adsorbate-free TiO2 surface with oxygen vacancies can be regenerated by prolonged annealing at 850 K or higher. Detailed analysis of the three N2O desorption yields reveals that the surface species for the HT channels are likely to be various forms of NO dimers.« less

  11. Thin-film growth of (110) rutile TiO2 on (100) Ge substrate by pulsed laser deposition

    NASA Astrophysics Data System (ADS)

    Suzuki, Yoshihisa; Nagata, Takahiro; Yamashita, Yoshiyuki; Nabatame, Toshihide; Ogura, Atsushi; Chikyow, Toyohiro

    2016-06-01

    The deposition conditions of (100) rutile TiO2 grown on p-type (100) Ge substrates by pulsed laser deposition (PLD) were optimized to improve the electrical properties of the TiO2/Ge structure. Increasing the substrate temperature (T sub) enhanced the grain growth, the surface roughness of the film, and Ge diffusion into the TiO2 layer. The growth rate, which was controlled by the laser density in PLD (L d), affected the Ge diffusion. L d of 0.35 J/cm2 (0.37 nm/min) enhanced the Ge diffusion and improved the crystallinity and surface roughness at a temperature of 450 °C, at which GeO x undergoes decomposition and desorption. However, the Ge diffusion into TiO2 degraded the electrical properties. By using the optimized conditions (L d = 0.7 J/cm2 and T sub = 420 °C) with postannealing, the TiO2/Ge structure showed an improvement in the leakage current of 3 orders of magnitude and the capacitance-voltage property characteristics indicated the formation of a p-n junction.

  12. Molecular simulation of C 60 adsorption onto a TiO 2 rutile (1 1 0) surface

    NASA Astrophysics Data System (ADS)

    Carvalho, A. J. Palace; Ramalho, J. P. Prates

    2010-06-01

    A Monte Carlo molecular simulation study is presented on the adsorption and growth of C 60 films on the surface of the (1 1 0) face of rutile. Simulations are performed for a temperature of 600 K using atomistic models both for the fullerene molecules and the TiO 2 surface. It is found in this work that C 60 is adsorbed preferably in an ordered arrangement along the surface depressions over the exposed undercoordinated Ti cations. At low densities adsorption occurs preferably at alternate rows, with locations in consecutive rows being occupied appreciably only at higher C 60 densities. At low densities, the fullerene molecules tend to aggregate into islands in the surface plane. Additional layers of C 60 form only as the density increases, and do so before a monolayer is completed in all consecutive rows. Full monolayer capacity obtained at the highest densities is about 0.9 C 60 molecules per nm 2, but this is only achieved by completing the packing of molecules in interstices at a slightly upper level. The fraction of the molecules that lie closest to the surface only amounts to 0.6 molecules per nm 2.

  13. Electronic structures and ferromagnetism of SnO2 (rutile) doped with double-impurities: First-principles calculations

    NASA Astrophysics Data System (ADS)

    Fakhim Lamrani, A.; Belaiche, M.; Benyoussef, A.; Kenz, El

    2014-01-01

    The electronic and magnetic properties of double-impurities-doped SnO2 (rutile) are explored using first-principles calculations within the generalized gradient approximation to examine their potential use as spintronic system. Calculations are performed for double impurities (M1 and M2) from M1 = Cr, and M2 = Mn, and Re. The origins of ferromagnetism are shown to be different in the two cases. For Sn1-2xCrxMnxO2, the hybridization between Cr-3d and O-2p results in Cr becoming ferromagnetic with a magnetic moment of about 5.0 μB per supercell. The Cr-and Mn-doped SnO2 system exhibits half-metallic ferromagnetism. The strong ferromagnetic couplings between local magnetic moments can be attributed to p-d hybridization. In contrast, in (Cr, Re) codoped TiO2, the local magnetic moments of the impurities and their oxidation states agree with the charge transfer between Cr and Re, which would lead to the ferromagnetic through the double-exchange mechanism in transition metal oxides. Since there are two possible couplings between the impurities, we studied both configurations (ferromagnetic and antiferromagnetic (AF)) for double-impurities-doped SnO2. Our calculations show that a ferromagnetic alignment of the spins is energetically always more stable than simple AF arrangements, which makes these materials possible candidates for spin injection in spintronic devices.

  14. A density functional theory study of atomic steps on stoichiometric rutile TiO{sub 2}(110)

    SciTech Connect

    Stausholm-Møller, Jess; Kristoffersen, Henrik Høgh; Martinez, Umberto; Hammer, Bjørk

    2013-12-21

    We present a detailed theoretical study of the energetics of stoichiometric steps on the (110) surface of rutile TiO{sub 2}. Step structures running along the 〈001〉, 〈11{sup ¯}1〉, and 〈11{sup ¯}0〉 directions including bulk-terminations and possible reconstructions have been considered. A robust method for extracting surface and step energies of vicinal surfaces, where the surface energies converge slowly with respect to slab thickness, is outlined and used. Based on the calculated step energies a 2D Wulff-construction is presented from which it can be concluded that in equilibrium only oxygen terminated steps running along the 〈001〉 directions and reconstructed steps along the 〈11{sup ¯}1〉 directions should be present. Finally it is found that under conditions of stoichiometry the reconstructed 〈11{sup ¯}1〉 steps should be more than twice as abundant as oxygen terminated 〈001〉 steps.

  15. A DFT study of water adsorption on rutile TiO2 (110) surface: The effects of surface steps

    NASA Astrophysics Data System (ADS)

    Zheng, Ting; Wu, Chunya; Chen, Mingjun; Zhang, Yu; Cummings, Peter T.

    2016-07-01

    The associative and dissociative adsorption of water molecules at low-coverage situations on rutile TiO2 (110) surface with step defects was investigated by the density functional theory calculations. Structural optimization of the hydroxylated/hydrated configurations at step edges along the <" separators="1 1 ¯ 1 > crystal directions and the dynamic process of water dissociation were discussed to get a better description of the water/TiO2 interface. Our results indicate that steps on the TiO2 (110) surface could be an active site for water dissociation. The results of geometry optimization suggest that the stability of hydroxylated configuration is largely dependent on the locations of the H species and the recombination of water molecules from hydroxyls is observed in the fully hydroxylated condition. However, these hydroxyls can be stabilized by the associatively absorbed water nearby by forming competitive intermolecular hydrogen bonds. The dynamics of water dissociation and hydrogen diffusion were studied by the first principles molecular dynamics simulation and our results suggest that the hydrogen released by water dissociation can be transferred among the adsorbates, such as the unsaturated oxygen atoms-H2O-hydroxyl (TiO-H2O-OH) complex at step edges, or gradually diffuses to the bulk water system in the form of hydronium (H3O+) at higher water coverage.

  16. Nucleation and growth of Pt nanoparticles on reduced and oxidized rutile TiO{sub 2} (110)

    SciTech Connect

    Rieboldt, F.; Vilhelmsen, L. B.; Koust, S.; Lauritsen, J. V.; Lammich, L.; Besenbacher, F.; Hammer, B.; Wendt, S.; Helveg, S.

    2014-12-07

    The nucleation and growth of Pt nanoparticles (NP’s) on rutile TiO{sub 2} (110) surfaces with O on-top atoms (oxidized TiO{sub 2}), surface O vacancies, and H adatoms, respectively (reduced TiO{sub 2}), was studied by means of scanning tunneling microscopy (STM) experiments and density functional theory calculations. At room temperature, Pt was found to be trapped at O on-top atoms and surface O vacancies, leading to rather small Pt NP’s. In contrast, on surfaces with H adatoms the mobility of Pt was much larger. As a result, large Pt NP's were found at room temperature on TiO{sub 2} (110) surfaces with H adatoms. However, at ∼150 K the diffusion of Pt was kinetically hindered on all TiO{sub 2} (110) surfaces considered. STM data acquired after vacuum-annealing at 800 K showed comparable results on all TiO{sub 2} (110) surfaces because the diffusion of Pt is not influenced by surface defects at such high temperatures.

  17. Diffusion Processes in Water on Oxide Surfaces: Quasielastic Neutron Scattering Study of Hydration Water in Rutile Nano-Powder

    SciTech Connect

    Chu, Xiang-Qiang; Ehlers, Georg; Mamontov, Eugene; Podlesnyak, Andrey A; Wang, Wei; Wesolowski, David J

    2011-01-01

    Quasielastic neutron scattering (QENS) was used to investigate the diffusion dynamics of hydration water on the surface of rutile (TiO{sub 2}) nanopowder. The dynamics measurements utilizing two inelastic instruments, a backscattering spectrometer and a disk chopper spectrometer, probed the fast, intermediate, and slow motions of the water molecules on the time scale of picoseconds to more than a nanosecond. We employed a model-independent analysis of the data collected at each value of the scattering momentum transfer to investigate the temperature dependence of several diffusion components. All of the probed components were present in the studied temperature range of 230-320 K, providing, at a first sight, no evidence of discontinuity in the hydration water dynamics. However, a qualitative change in the elastic scattering between 240 and 250 K suggested a surface freezing-melting transition, when the motions that were localized at lower temperatures became delocalized at higher temperatures. On the basis of our previous molecular dynamics simulations of this system, we argue that interpretation of QENS data from such a complex interfacial system requires at least qualitative input from simulations, particularly when comparing results from spectrometers with very different energy resolutions and dynamic ranges.

  18. Cluster synthesis of monodisperse rutile-TiO2 nanoparticles and dielectric TiO2-vinylidene fluoride oligomer nanocomposites

    SciTech Connect

    Balasubramanian, B; Kraemer, KL; Valloppilly, SR; Ducharme, S; Sellmyer, DJ

    2011-09-13

    The embedding of oxide nanoparticles in polymer matrices produces a greatly enhanced dielectric response by combining the high dielectric strength and low loss of suitable host polymers with the high electric polarizability of nanoparticles. The fabrication of oxide-polymer nanocomposites with well-controlled distributions of nanoparticles is, however, challenging due to the thermodynamic and kinetic barriers between the polymer matrix and nanoparticle fillers. In the present study, monodisperse TiO2 nanoparticles having an average particle size of 14.4 nm and predominant rutile phase were produced using a cluster-deposition technique without high-temperature thermal annealing and subsequently coated with uniform vinylidene fluoride oligomer (VDFO) molecules using a thermal evaporation source, prior to deposition as TiO2-VDFO nanocomposite films on suitable substrates. The molecular coatings on TiO2 nanoparticles serve two purposes, namely to prevent the TiO2 nanoparticles from contacting each other and to couple the nanoparticle polarization to the matrix. Parallel-plate capacitors made of TiO2-VDFO nanocomposite film as the dielectric exhibit minimum dielectric dispersion and low dielectric loss. Dielectric measurements also show an enhanced effective dielectric constant in TiO2-VDFO nanocomposites as compared to that of pure VDFO. This study demonstrates for the first time a unique electroactive particle coating in the form of a ferroelectric VDFO that has high-temperature stability as compared to conventionally used polymers for fabricating dielectric oxide-polymer nanocomposites.

  19. Cluster synthesis of monodisperse rutile-TiO2 nanoparticles and dielectric TiO2-vinylidene fluoride oligomer nanocomposites.

    PubMed

    Balasubramanian, Balamurugan; Kraemer, Kristin L; Valloppilly, Shah R; Ducharme, Stephen; Sellmyer, David J

    2011-10-01

    The embedding of oxide nanoparticles in polymer matrices produces a greatly enhanced dielectric response by combining the high dielectric strength and low loss of suitable host polymers with the high electric polarizability of nanoparticles. The fabrication of oxide-polymer nanocomposites with well-controlled distributions of nanoparticles is, however, challenging due to the thermodynamic and kinetic barriers between the polymer matrix and nanoparticle fillers. In the present study, monodisperse TiO(2) nanoparticles having an average particle size of 14.4 nm and predominant rutile phase were produced using a cluster-deposition technique without high-temperature thermal annealing and subsequently coated with uniform vinylidene fluoride oligomer (VDFO) molecules using a thermal evaporation source, prior to deposition as TiO(2)-VDFO nanocomposite films on suitable substrates. The molecular coatings on TiO(2) nanoparticles serve two purposes, namely to prevent the TiO(2) nanoparticles from contacting each other and to couple the nanoparticle polarization to the matrix. Parallel-plate capacitors made of TiO(2)-VDFO nanocomposite film as the dielectric exhibit minimum dielectric dispersion and low dielectric loss. Dielectric measurements also show an enhanced effective dielectric constant in TiO(2)-VDFO nanocomposites as compared to that of pure VDFO. This study demonstrates for the first time a unique electroactive particle coating in the form of a ferroelectric VDFO that has high-temperature stability as compared to conventionally used polymers for fabricating dielectric oxide-polymer nanocomposites.

  20. In situ scanning tunneling microscopy study of Ca-modified rutile TiO2(110) in bulk water

    PubMed Central

    Bonanni, Beatrice; Kosmala, Tomasz; Di Giovannantonio, Marco; Diebold, Ulrike; Wandelt, Klaus; Goletti, Claudio

    2015-01-01

    Summary Despite the rising technological interest in the use of calcium-modified TiO2 surfaces in biomedical implants, the Ca/TiO2 interface has not been studied in an aqueous environment. This investigation is the first report on the use of in situ scanning tunneling microscopy (STM) to study calcium-modified rutile TiO2(110) surfaces immersed in high purity water. The TiO2 surface was prepared under ultrahigh vacuum (UHV) with repeated sputtering/annealing cycles. Low energy electron diffraction (LEED) analysis shows a pattern typical for the surface segregation of calcium, which is present as an impurity on the TiO2 bulk. In situ STM images of the surface in bulk water exhibit one-dimensional rows of segregated calcium regularly aligned with the [001] crystal direction. The in situ-characterized morphology and structure of this Ca-modified TiO2 surface are discussed and compared with UHV-STM results from the literature. Prolonged immersion (two days) in the liquid leads to degradation of the overlayer, resulting in a disordered surface. X-ray photoelectron spectroscopy, performed after immersion in water, confirms the presence of calcium. PMID:25821684

  1. Effects of variations in precursor concentration on the growth of rutile TiO2 nanorods on Si substrate with fabricated fast-response metal-semiconductor-metal UV detector

    NASA Astrophysics Data System (ADS)

    Selman, Abbas M.; Hassan, Z.

    2015-06-01

    This study aimed to investigate the effects of variations in precursor concentration (TiCl3 solution) on the structural, morphological, and optical properties of rutile titanium dioxide (TiO2) nanorods and fabricated metal-semiconductor-metal UV detector depending on the optimal sample. The nanorods were prepared from an aqueous solution of titanium (III) chloride (TiCl3) on p-type, (1 1 1)-oriented Si substrates at different concentrations of TiCl3 solutions (2, 3, 4, and 5 mM). The experimental results showed that the TiO2 nanorods grown at 4 mM concentration exhibited optimal structural properties. A fast-response metal-semiconductor-metal UV detector was fabricated by depositing Pt contacts on the front of the optimal sample via RF reactive magnetron sputtering. Upon exposure to 365 nm light (2.3 mW/cm2) at 5 V bias voltage, the device showed 44.4 sensitivity. In addition, the internal gain was 1.45, and the photoresponse peak was 70 mA/W. The response and the recovery times were calculated to be 7.8 ms upon illumination to a pulse UV light (365 nm) at 5 V bias voltage.

  2. Infrared spectroscopy study of adsorption and photodecomposition of formic acid on reduced and defective rutile TiO{sub 2} (110) surfaces

    SciTech Connect

    Mattsson, Andreas Österlund, Lars; Hu, Shuanglin; Hermansson, Kersti

    2014-11-01

    Adsorption and photodecomposition of formic acid on rutile TiO{sub 2} (110) have been investigated with infrared reflection–absorption spectroscopy (IRRAS) employing p- and s-polarized light along the [001] and [11{sup ¯}0] crystal directions. The single crystal surfaces were prepared either by sputtering and annealing in ultrahigh vacuum (UHV) to obtain a reduced surface (r-TiO{sub 2}), or by sputtering without annealing to create a rough, highly defective surface (sp-TiO{sub 2}). Results are compared with corresponding measurements on rutile nanocrystals performed in synthetic air. IRRAS spectra obtained on r-TiO{sub 2} and rutile nanocrystals are very similar, and show that in both cases formic acid dissociates and is predominately adsorbed as a bridging bidentate formate species, and that the formate adsorption structure on the nanocrystals is dominated by interactions with majority (110) surfaces. In contrast, the IRRAS spectra on sp-TiO{sub 2} are different, with only minor spectral features associated with (110) surfaces and lost azimuthal symmetry, both of which imply changed adsorption geometry due to bonding to low-coordinated Ti atoms with lower valences. The UV-induced rate of formate photodecomposition is about 30 times higher on rutile nanocrystals in synthetic air compared with sp-TiO{sub 2} under UHV conditions, and even larger than on r-TiO{sub 2}. These differences are explained by the lack of oxygen and limited hydroxyl coverage under UHV conditions. The difference in reactivity between the r-TiO{sub 2} and sp-TiO{sub 2} surfaces is attributed to a high concentration of strongly bonded bridging bidentate formate species on the (110) surface, which lowers its reactivity. The results point to a pressure gap where the availability of molecular oxygen and the hydroxyl concentration limit the photoreactivity in UHV leading to an almost 20-fold decrease of the formate degradation rate in UHV. In contrast, the structure represented by the single

  3. Using Detrital Zircon, Rutile and White Mica Chronometry to Constrain Exhumation and Provenance of the Brahmaputra River in the Eastern Himalaya

    NASA Astrophysics Data System (ADS)

    Bracciali, L.; Parrish, R. R.; Najman, Y.; Carter, A.; Condon, D. J.; Horstwood, M. S.; Wijbrans, J. R.

    2012-12-01

    While geo- and thermo-chronology of detrital minerals from sedimentary basins are routinely applied to constrain sedimentary provenance and hinterland evolution, the importance of a multi-technique approach is not always recognized. Isotopic dating methods sensitive to different temperature ranges can be successfully applied to detrital mineral grains from the same sample in order to obtain a robust dataset capable of providing information on the various thermal events that affected the source terrains. We use three detrital minerals in this study (zircon, rutile and white mica) that are stable and widely distributed in igneous, metamorphic and sedimentary rocks and which together retain source crystallisation and cooling information over the range down to ~200°C and thus record complex metamorphic histories. Similarly to zircon and other U-bearing minerals, rutile can be dated by the U-Pb method, however it has so far received less attention than zircon because of: lower U content which limits measurement quality by in situ methods, often a higher proportion of common (non radiogenic) lead, and a lack of widely available good quality reference materials. We have recently characterized (by high precision ID-TIMS, isotope dilution mass spectrometry, and by LA-MC-ICP-MS two natural rutiles (Sugluk-4 and PCA-S207) and used these as reference materials for LA U-Pb dating of detrital samples, Parrish et al., this meeting, and [1]). Compared to zircon, rutile is characterized by a lower closure T for Pb diffusion (~500°C), hence rutile U-Pb dates primarily indicate the time since the last significant cooling. As it adds an important lower temperature complement to zircon and allows a much more unique isotopic fingerprint of the source region, rutile has the potential to become a key provenance tracer. In order to boost the strength of the double U-Pb detrital chronometer, we apply 40Ar/39Ar dating and zircon fission track dating to detrital grains from the same sample

  4. On the consistency of QCBED structure factor measurements for TiO2 (rutile).

    PubMed

    Jiang, Bin; Zuo, Jian-Min; Friis, Jesper; Spence, John C H

    2003-10-01

    The same Bragg reflection in TiO2 from 12 different (CBED) patterns (from different crystals, orientations, and thicknesses) are analyzed quantitatively to evaluate the consistency of the quantitative CBED method for bond-charge mapping. The standard deviation in the resulting distribution of derived X-ray structure factors is found to be an order of magnitude smaller than that in conventional X-ray work, and the standard error (0.026% for F(x)(110)) is slightly better than obtained by the X-ray Pendellösung method applied to silicon. This is sufficiently accurate to distinguish between atomic, covalent, and ionic models of bonding. We describe the importance of extracting experimental parameters from CCD camera characterization, and of surface oxidation and crystal shape. The current experiments show that the QCBED method is now a robust and powerful tool for low-order structure factor measurement, which does not suffer from the large extinction (multiple scattering) errors that occur in inorganic X-ray crystallography, and may be applied to nanocrystals. Our results will be used to understand the role of d-electrons in the chemical bonding of TiO2.

  5. On the consistency of QCBED structure factor measurements for TiO2 (Rutile)

    SciTech Connect

    Jiang, Bin; Zuo, Jian -Min; Friis, Jesper; Spence, John C. H.

    2003-09-16

    The same Bragg reflection in TiO2 from twelve different CBED patterns (from different crystals, orientations and thicknesses) are analysed quantitatively in order to evaluate the consistency of the QCBED method for bond-charge mapping. The standard deviation in the resulting distribution of derived X-ray structure factors is found to be an order of magnitude smaller than that in conventional X-ray work, and the standard error (0.026% for FX(110)) is slightly better than obtained by the X-ray Pendellosung method applied to silicon. This is sufficiently accuracy to distinguish between atomic, covalent and ionic models of bonding. We describe the importance of extracting experimental parameters from CCD camera characterization, and of surface oxidation and crystal shape. Thus, the current experiments show that the QCBED method is now a robust and powerful tool for low order structure factor measurement, which does not suffer from the large extinction (multiple scattering) errors which occur in inorganic X-ray crystallography, and may be applied to nanocrystals. Our results will be used to understand the role of d electrons in the chemical bonding of TiO2.

  6. On the consistency of QCBED structure factor measurements for TiO2 (Rutile)

    DOE PAGES

    Jiang, Bin; Zuo, Jian -Min; Friis, Jesper; Spence, John C. H.

    2003-09-16

    The same Bragg reflection in TiO2 from twelve different CBED patterns (from different crystals, orientations and thicknesses) are analysed quantitatively in order to evaluate the consistency of the QCBED method for bond-charge mapping. The standard deviation in the resulting distribution of derived X-ray structure factors is found to be an order of magnitude smaller than that in conventional X-ray work, and the standard error (0.026% for FX(110)) is slightly better than obtained by the X-ray Pendellosung method applied to silicon. This is sufficiently accuracy to distinguish between atomic, covalent and ionic models of bonding. We describe the importance of extractingmore » experimental parameters from CCD camera characterization, and of surface oxidation and crystal shape. Thus, the current experiments show that the QCBED method is now a robust and powerful tool for low order structure factor measurement, which does not suffer from the large extinction (multiple scattering) errors which occur in inorganic X-ray crystallography, and may be applied to nanocrystals. Our results will be used to understand the role of d electrons in the chemical bonding of TiO2.« less

  7. Dynamics and structure of hydration water on rutile and cassiterite nanopowders studied by quasielastic neutron scattering and molecular dynamics simulations.

    SciTech Connect

    Mamontov, Eugene; Vlcek, Lukas; Wesolowski, David J

    2007-03-01

    Quasielastic neutron scattering (QENS) experiments carried out using time-of-flight and backscattering neutron spectrometers with widely different energy resolution and dynamic range revealed the diffusion dynamics of hydration water in nanopowder rutile (TiO{sub 2}) and cassiterite (SnO{sub 2}) that possess the rutile crystal structure with the (110) crystal face predominant on the surface. These isostructural oxides differ in their bulk dielectric constants, metal atom electronegativities, and lattice spacings, which may all contribute to differences in the structure and dynamics of sorbed water. When hydrated under ambient conditions, the nanopowders had similar levels of hydration: about 3.5 (OH/H{sub 2}O) molecules per Ti{sub 2}O{sub 4} surface structural unit of TiO{sub 2} and about 4.0 (OH/H{sub 2}O) molecules per Sn{sub 2}O{sub 4} surface unit of SnO{sub 2}. Ab initio optimized classical molecular dynamics (MD) simulations of the (110) surfaces in contact with SPC/E water at these levels of hydration indicate three structurally distinct sorbed water layers L{sub 1}, L{sub 2}, and L{sub 3}, where the L{sub 1} species are either associated water molecules or dissociated hydroxyl groups in direct contact with the surface, L{sub 2} water molecules are hydrogen bonded to L{sub 1} and structural oxygen atoms at the surface, and L{sub 3} water molecules are more weakly bound. At the hydration levels studied, L{sub 3} is incomplete compared with axial oxygen density profiles of bulk SPC/E water in contact with these surfaces, but the structure and dynamics of L{sub 1}-L{sub 3} species are remarkably similar at full and reduced water coverage. Three hydration water diffusion components, on the time scale of a picosecond, tens of picoseconds, and a nanosecond could be extracted from the QENS spectra of both oxides. However, the spectral weight of the faster components was significantly lower for SnO{sub 2} compared to TiO{sub 2}. In TiO{sub 2} hydration water, the

  8. Electronic structures and ferromagnetism of SnO{sub 2} (rutile) doped with double-impurities: First-principles calculations

    SciTech Connect

    Fakhim Lamrani, A.; Belaiche, M.; Benyoussef, A.; and others

    2014-01-07

    The electronic and magnetic properties of double-impurities-doped SnO{sub 2} (rutile) are explored using first-principles calculations within the generalized gradient approximation to examine their potential use as spintronic system. Calculations are performed for double impurities (M1 and M2) from M1 = Cr, and M2 = Mn, and Re. The origins of ferromagnetism are shown to be different in the two cases. For Sn{sub 1-2x}Cr{sub x}Mn{sub x}O2, the hybridization between Cr-3d and O-2p results in Cr becoming ferromagnetic with a magnetic moment of about 5.0 μ{sub B} per supercell. The Cr-and Mn-doped SnO{sub 2} system exhibits half-metallic ferromagnetism. The strong ferromagnetic couplings between local magnetic moments can be attributed to p-d hybridization. In contrast, in (Cr, Re) codoped TiO{sub 2}, the local magnetic moments of the impurities and their oxidation states agree with the charge transfer between Cr and Re, which would lead to the ferromagnetic through the double-exchange mechanism in transition metal oxides. Since there are two possible couplings between the impurities, we studied both configurations (ferromagnetic and antiferromagnetic (AF)) for double-impurities-doped SnO{sub 2}. Our calculations show that a ferromagnetic alignment of the spins is energetically always more stable than simple AF arrangements, which makes these materials possible candidates for spin injection in spintronic devices.

  9. Potential neurological lesion after nasal instillation of TiO(2) nanoparticles in the anatase and rutile crystal phases.

    PubMed

    Wang, Jiangxue; Chen, Chunying; Liu, Ying; Jiao, Fang; Li, Wei; Lao, Fang; Li, Yufeng; Li, Bai; Ge, Cuicui; Zhou, Guoqiang; Gao, Yuxi; Zhao, Yuliang; Chai, Zhifang

    2008-12-15

    Nanoscale titanium dioxide (TiO(2)) is massively produced and widely used in living environment, which hence make the potential risk to human health. Central nervous system (CNS) is the potential susceptible target of inhaled nanoparticles, but the studies on this aspect are limited so far. We report the accumulation and toxicity results in vivo of two crystalline phases of TiO(2) nanoparticles (80nm, rutile and 155nm, anatase; purity >99%). The female mice were intranasally instilled with 500microg of TiO(2) nanoparticles suspension every other day for 30 days. Synchrotron radiation X-ray fluorescence analysis (SRXRF) and inductively coupled plasma mass spectrometry (ICP-MS) were used to determine the contents of titanium in murine brain. Then, the pathological examination of brain tissue, oxidative stress-mediated responses, and levels of neurochemicals in the brain of exposed mice were also analyzed. The obvious morphological changes of hippocampal neurons and increased GFAP-positive astrocytes in the CA4 region were observed, which were in good agreements with higher Ti contents in the hippocampus region. Oxidative stress occurred obviously in whole brain of exposed mice such as lipid peroxidation, protein oxidation and increased activities of catalase, as well as the excessive release of glutamic acid and nitric oxide. These findings indicate anatase TiO(2) nanoparticles exhibited higher concern on some tested biological effects. To summarize, results provided the preliminary evidence that nasal instilled TiO(2) nanoparticles could be translocated into the central nervous system and cause potential lesion of brain, and the hippocampus would be the main target within brain.

  10. Release of phosphorous impurity from TiO2 anatase and rutile nanoparticles in aquatic environments and its implications.

    PubMed

    Liu, Xuyang; Chen, Gexin; Erwin, Justin G; Adam, Nadia K; Su, Chunming

    2013-10-15

    Phosphorus-bearing materials as an additive have been popularly used in nanomaterial synthesis and the residual phosphorus within the nanoparticles (NPs) can be of an environmental concern. For instance, phosphorus within pristine commercial TiO2 NPs greatly influences the surface charge and aggregation behavior of the host TiO2 in aquatic environments; however, it is unknown whether and how fast phosphorus is released. In this study, we focus on the phosphorus release kinetics from five types of TiO2 NPs (i.e., 5, 10, and 50 nm anatase and 10 × 40, 30 × 40 nm rutile) under the influence of varying solution chemistries. The 50 nm anatase has the highest quantity of P (8.05 g/kg) and most leachable P dissolves within the first 2 h (i.e., 5.01 g/kg), which presents a potential pollutant source of P. Higher pH favors the phosphorus release (release order: pH 11.2 > pH 8.2 > pH 2.4), while variations in the environmentally relevant ionic strengths (0.01 M NaCl + 0.01 M NaHCO3 and 0.04 M NaCl + 0.01 M NaHCO3) and the presence of dissolved natural organic matter (10 mg/L) do not affect release rate greatly. X-ray Absorption Near Edge Structure results suggest that phosphate adsorbed on the pristine 50 nm anatase desorbs, and some dissolved phosphate again re-sorbs as a surface precipitate. The findings from this research may have important environmental implications such as accidental release of TiO2 NPs and other nanomaterials that are synthesized using phosphorus containing chemicals as an ingredient.

  11. Rutile-type Co doped SnO2 diluted magnetic semiconductor nanoparticles: Structural, dielectric and ferromagnetic behavior

    NASA Astrophysics Data System (ADS)

    Mehraj, Sumaira; Shahnawaze Ansari, M.; Alimuddin

    2013-12-01

    Nanoparticles of basic composition Sn1-xCoxO2 (x=0.00, 0.01, 0.03, 0.05 and 0.1) were synthesized through the citrate-gel method and were characterized for structural properties using X-ray diffraction (XRD), Scanning electron microscopy (SEM), Energy dispersive X-ray spectroscopy (EDS) and Fourier transform infrared spectroscopy (FT-IR). XRD analysis of the powder samples sintered at 500 °C for 12 h showed single phase rutile type tetragonal structure and the crystallite size decreased as the cobalt content was increased. FT-IR spectrum displayed various bands that came due to fundamental overtones and combination of O-H, Sn-O and Sn-O-Sn entities. The effect of Co doping on the electrical and magnetic properties was studied using dielectric spectroscopy and vibrating sample magnetometer (VSM) at room temperature. The dielectric parameters (ε, tan δ and σac) show their maximum value for 10% Co doping. The dielectric loss shows anomalous behavior with frequency where it exhibits the Debye relaxation. The variation of dielectric properties and ac conductivity with frequency reveals that the dispersion is due to the Maxwell-Wagner type of interfacial polarization in general and hopping of charge between Sn2+ and Sn4+ as well as between Co2+ and Co3+ ions. The complex impedance analysis was used to separate the grain and grain boundary contributions in the system which shows that the conduction process in grown nanoparticles takes place predominantly through grain boundary volume. Hysteresis loops were observed clearly in M-H curves from 0.01 to 0.1% Co doped SnO2 samples. The saturation magnetization of the doped samples increased slightly with increase of Co concentration. However pure SnO2 displayed paramagnetism which vanished at higher values of magnetic field.

  12. The tetragonal-like to rutile structural phase transition in epitaxial VO2/TiO2 (001) thick films

    NASA Astrophysics Data System (ADS)

    Qiu, Hongbo; Yang, Memgmeng; Dong, Yongqi; Xu, Han; Hong, Bin; Gu, Yueliang; Yang, Yuanjun; Zou, Chongwen; Luo, Zhenlin; Gao, Chen

    2015-11-01

    A controllable metal-insulator transition (MIT) of VO2 has been highly desired due to its huge potential applications in memory storage, smart windows or optical switching devices. Recently, interfacial strain engineering has been recognized as an effective approach to tuning the MIT of epitaxial VO2 films. However, the strain-involved structural evolution during the MIT process is still not clear, which prevents comprehensively understanding and utilizing interfacial strain engineering in VO2 films. In this work, we have systematically studied the epitaxial VO2 thick films grown on TiO2 (001) single crystal substrate and the structural transition at the boundary of MIT region. By using in situ temperature-dependent high-resolution x-ray diffractions, a tetragonal-like (‘T-like’) to ‘rutile’ structural phase transition is identified during the MIT process. The room-temperature crystal phase of epitaxial VO2/TiO2(001) thick film is clarified to be tetragonal-like, neither strained-rutile phase nor monoclinic phase. The calculated atomic structure of this T-like phase VO2 resembles that of the M1 phase VO2, which has been verified by their similar Raman spectra. More, the crystal lattices of the coexisted phases in the MIT region were revealed in detail. The current findings will not only show some clues on the MIT mechanism study from the structural point of view, but also favor the interface engineering assisted VO2-based devices and applications in the future.

  13. Preliminary report on the geology and deposits of monazite, thorite and niobium-bearing rutile of the Mineral Hill district, Lemhi County, Idaho

    USGS Publications Warehouse

    Kaiser, Edward Peck

    1956-01-01

    Deposits of minerals containing niobium (columbium), thorium, and rare earths occur in the Mineral Hill district, 30 miles northwest of Salmon, Lemhi County, Idaho. Monazite, thorite, allanite, and niobium-bearing rutile form deposits in metamorphic limestone layers less than 8 feet thick. The known deposits are small, irregular, and typically located in or near small folds. Minor faults are common. Monazite generally is coarsely crystalline and contains less than one percent thorium. Rutile forms massive lumps up to 3 inches across; it contains between 5 and 10 percent niobium. Rutile occurs in the northwestern half of the district, thorite in the central and southeastern parts. Monazite occurs in all deposits. Allanite is locally abundant and contains several percent thorium. Magnetite and ilmenite are also locally abundant. A major thrust fault trending northwest across the map-area separates moderately folded quartzite and phyllitic rocks of Belt age, on the northeast, from more intensely metamorphosed and folded rocks on the southwest. The more metamorphosed rocks include amphibolite, porphyroblastic feldspar gneiss, quartzite, and limestone, all probably of sedimentary origin, and probably also of Belt (late Precambrian) age. The only rocks of definite igneous origin are rhyolite dikes of probable Tertiary age. The more metamorphosed rocks were formed by metasomatic metamorphism acting on clastic sediments, probably of Belt age, although they may be older than Belt. Metamorphism doubtless was part of the episode of emplacement of the Idaho batholith, but the history of that episode is not well understood. The rare-element deposits show no evidence of fracture-controlled hydrothermal introduction, such as special fracture systems, veining, and gangue material. They may, however, be of hydrothermal type. More likely they are metamorphic segregations or secretions, deposited in favorable stratigraphic and structural positions during regional metamorphism.

  14. Structural studies of TiO2/wood coatings prepared by hydrothermal deposition of rutile particles from TiCl4 aqueous solutions on spruce (Picea Abies) wood

    NASA Astrophysics Data System (ADS)

    Pori, Pavel; Vilčnik, Aljaž; Petrič, Marko; Sever Škapin, Andrijana; Mihelčič, Mohor; Šurca Vuk, Angela; Novak, Urban; Orel, Boris

    2016-05-01

    A low temperature approach was developed for the deposition of rutile TiO2 particles on a wood surface by hydrolysis of TiCl4 in aqueous solutions acidified with HCl, and crystallization at 75 and 90 °C (1 h). Prior to hydrothermal treatment, Picea Abies wood was first soaked in a 0.5 mmol/l aqueous solution containing anionic surfactant sodium dodecyl sulphate (SDS, Sigma Aldrich) for 2 h at 80 °C. The crystal structure of the hydrothermally made rutile particles was determined with XRD, while the morphology of the deposited TiO2 particles and their distribution in the wood were examined with SEM and EDX measurements. The penetration and amount of deposited rutile particles could be modified by changing the deposition conditions. Thicker layers were obtained from more concentrated aqueous TiCl4 solutions with and without added HCl, and with longer deposition times and higher temperatures of the hydrothermal treatment. The interaction of TiO2 particles with hemicellulose and lignin in wood was established from infrared attenuated total reflection (FT-IR ATR) and Raman spectra measurements, from which the spectra of wood were subtracted. Analysis of the subtraction spectra showed the presence of titania particles on the wood surface, revealing also the establishment of TiO2-wood coordinative bonds of titanium ions with hemicellulose and lignin. The red frequency shift of the OH stretching modes suggested interaction of the TiO2 particles with water molecules of wood. TiO2 deposited on wood treated with SDS became hydrophobic (water contact angles (WCA) of 150°), contrasting the properties of untreated wood with a deposited TiO2 particle coating, which remained hydrophilic.

  15. U-Pb garnet, sphene, monazite, and rutile ages: Implications for the duration of high-grade metamorphism and cooling histories, Adirondack Mts. , New York

    SciTech Connect

    Mezger, K.; Rawnsley, C.M.; Hanson, G.N. ); Bohlen, S.R. )

    1991-05-01

    Garnet ages for the Lowlands range from 1,168-1,127 Ma, those from the central and southern Highlands from 1,154-1,013 Ma. Metamorphism in the Highlands may not have occurred as a single event but rather in several discrete thermal pulses. An age of 1,153 {plus minus} 3 Ma was determined for garnets in the syn-regional metamorphic contact aureole of the Diana syenite, consistent with that of the syenite intrusion, 1 155 {plus minus} 4 Ma. Garnets just outside the contact aureole give an age of 1,168 {plus minus} 6 Ma. In the Lowlands, monazite yielded an age of 1,161 {plus minus} 1 Ma, rutiles yielded ages of 1,005 {plus minus} 2 Ma and 953 {plus minus} 4 Ma, and sphene ages range from 1,156 to 1,103 Ma. In the Highlands, monazite yielded an age of 1,033 {plus minus} 1 Ma, rutiles yielded ages of 911 {plus minus} 2 Ma and 885 {plus minus} 2 and sphenes from 1,033 Ma to 991 Ma. The rutile and monazite ages indicate that both terranes cooled at time-integrated rates of ca. 1.5C/Ma for at least 150 Ma following the last phase of high-grade metamorphism. The Lowlands cooled to ca. 400C by ca. 1,000 Ma and the Highlands by ca. 900 Ma. The mineral ages indicate that metamorphic pressures and temperatures recorded by thermobarometry correspond to conditions attained polychronically over 150 Ma or more. Mineral ages combined with temperature estimates for peak metamorphism indicate that the closure temperature for the U-Pb system is >800C in garnet, 640-730C in monazite, and 500-670C in sphene.

  16. Determination of Phase Ratio in Polymorphic Materials by X-Ray Absorption Spectroscopy: The Case of Anatase and Rutile Phase Mixture in TiO2

    SciTech Connect

    Smith, M. F.; Klysubun, W.; Kityakarn, S.; Worayingyong, A.; Zhang, S. B.; Wei, S. H.; Onkaw, D.; Songsiriritthigul, P.; Rujirawat, S.; Limpijumnong, S.

    2009-01-01

    We demonstrate that x-ray absorption spectroscopy (XAS) can be used as an unconventional characterization technique to determine the proportions of different crystal phases in polymorphic samples. As an example, we show that ratios of anatase and rutile phases contained in the TiO{sub 2} samples obtained by XAS are in agreement with conventional x-ray diffraction (XRD) measurements to within a few percent. We suggest that XAS measurement is a useful and reliable technique that can be applied to study the phase composition of highly disordered or nanoparticle polymorphic materials, where traditional XRD technique might be difficult.

  17. Theoretical study of absorption of 2,2,6,6-tetramethylpiperidine-1-oxoammonium cation (TEMPO) on TiO₂(110) rutile surface.

    PubMed

    Nieto-López, Israel; Hernández-García, Luis; Bonilla-Cruz, José; Sanchez, Mario

    2014-03-01

    We present a theoretical study of the adsorption of 2,2,6,6-tetramethylpiperidine-1-oxoammonium cation (TEMPO) onto the TiO₂(110) surface rutile, investigating its bonding nature, electron properties and structural stability. Based on the results obtained with the PBE0/def2-SVP method, natural bond orbital (NBO) analysis suggests a bond order for the O--O bond in complexes 5 and 6, of 0.25 and 0.88, respectively. We also described NBOs for the main interactions of the TiO₂-TEMPO complexes.

  18. Self-assembling of Zn porphyrins on a (110) face of rutile TiO2-The anchoring role of carboxyl groups

    NASA Astrophysics Data System (ADS)

    Zajac, Lukasz; Olszowski, Piotr; Godlewski, Szymon; Bodek, Lukasz; Such, Bartosz; Jöhr, Res; Pawlak, Remy; Hinaut, Antoine; Glatzel, Thilo; Meyer, Ernst; Szymonski, Marek

    2016-08-01

    The ordering of zinc containing porphyrin molecules on surface of rutile TiO2(110)-(1×1) has been investigated using scanning tunneling microscopy (STM) in ultra-high vacuum at room temperature. It is demonstrated that a carboxylic group (COOH) has a profound impact on the immobilization of the molecules. At coverages below 0.1 monolayer only molecules equipped with the group COOH could be anchored to the surface and imaged with STM. At higher coverage both species, with and without the carboxyl substituent, assemble into ordered structures, forming complete monolayers. It is found, however, that the rhomboid unit cells of these structures exhibit differences in size.

  19. Adsorption and dissociation of NH3 on clean and hydroxylated TiO2 rutile (110) surfaces: a computational study.

    PubMed

    Chang, Jee-Gong; Chen, Hsin-Tsung; Ju, Shin-Pon; Chang, Ching-Sheng; Weng, Meng-Hsiung

    2011-04-30

    The adsorption and dissociation of NH(3) on the clean and hydroxylated TiO(2) rutile (110) surfaces have been investigated by the first-principles calculations. The monodentate adsorbates such as H(3)N-Ti(a), H(2)N-Ti(a), N-Ti(a), H(2)N-O(a), HN-O(a), N-O(a) and H-O(a), as well as the bidentate adsorbate, Ti-N-Ti(a) can be formed on the clean surface. It is found that the hydroxyl group enhances the adsorption of certain adsorbates on the five-fold-coordinated Ti atoms (5c-Ti), namely H(2)N-Ti(a), HN-Ti(a), N-Ti(a) and Ti-N-Ti(a). In addition, the adsorption energy increases as the number of hydroxyl groups increases. On the contrary, the opposite effect is found for those on the two-fold-coordinated O atoms (2c-O). The enhanced adsorption of NH(x) (x = 1-2) on the 5c-Ti is due to the large electronegativity of the OH group, increasing the acidity of the Ti center. This also contributes to diminish the adsorption of NH(x) (x = 1-2) on the two-fold-coordinated O atoms (2c-O) decreasing its basicity. According to potential energy profile, the NH(3) dissociation on the TiO(2) surface is endothermic and the hydroxyl group is found to lower the energetics of H(2)N-Ti(a)+H-O(a) and HN-Ti(a)+2{H-O(a)}, but slightly raise the energetic of Ti-N-Ti(a)+3{H-O(a)} compare to those on the clean surface. However, the dissociation of NH(3) is found to occur on the hydroxylated surface with an overall endothermic by 31.8 kcal/mol and requires a barrier of 37.5 kcal/mol. A comparison of NH(3) on anatase surface has been discussed. The detailed electronic analysis is also carried out to gain insights into the interaction nature between adsorbate and surface.

  20. Exceptional performance of photoelectrochemical water oxidation of single-crystal rutile TiO2 nanorods dependent on the hole trapping of modified chloride

    NASA Astrophysics Data System (ADS)

    Zhang, Xuliang; Cui, Haiqin; Humayun, Muhammad; Qu, Yang; Fan, Naiying; Sun, Xiaojun; Jing, Liqiang

    2016-02-01

    It is highly desired to effectively trap photogenerated holes for efficient photoelectrochemical (PEC) water oxidation to evolve O2 on oxide semiconductors. Herein, it is found for the first time mainly based on the time-resolved- and atmosphere-controlled- surface photovoltage responses that the modified chloride would effectively trap photogenerated holes so as to prolong the charge lifetime and hence promote charge separation of single-crystal rutile TiO2 nanorods. Its strong capacity to trap holes, comparable to the widely-used methanol and Co(II) phosphate, is well responsible for the exceptional photoactivities for PEC water oxidation to evolve O2 on rutile nanorods with a proper amount of chloride modified, about 2.5-time high as that on the resulting anatase nanoparticles, even 10-time if the surface area is considered. Moreover, it is suggested that the hole trapping role of chemically-adsorbed chloride is related to its lonely-pair electrons, and to the subsequently-produced intermediate Cl atoms with proper electronegativity for evolving O2. Interestingly, this finding is also applicable to the chloride-modified anatase TiO2. This work will provide a feasible strategy to design high-activity nanostructured semiconductor photoanodes for PEC water oxidation, even for overall water splitting.

  1. Coadsorption properties of CO2 and H2O on TiO2 rutile (110): a dispersion-corrected DFT study.

    PubMed

    Sorescu, Dan C; Lee, Junseok; Al-Saidi, Wissam A; Jordan, Kenneth D

    2012-08-21

    Adsorption and reactions of CO(2) in the presence of H(2)O and OH species on the TiO(2) rutile (110)-(1×1) surface were investigated using dispersion-corrected density functional theory and scanning tunneling microscopy. The coadsorbed H(2)O (OH) species slightly increase the CO(2) adsorption energies, primarily through formation of hydrogen bonds, and create new binding configurations that are not present on the anhydrous surface. Proton transfer reactions to CO(2) with formation of bicarbonate and carbonic acid species were investigated and found to have barriers in the range 6.1-12.8 kcal/mol, with reactions involving participation of two or more water molecules or OH groups having lower barriers than reactions involving a single adsorbed water molecule or OH group. The reactions to form the most stable adsorbed formate and bicarbonate species are exothermic relative to the unreacted adsorbed CO(2) and H(2)O (OH) species, with formation of the bicarbonate species being favored. These results are consistent with single crystal measurements which have identified formation of bicarbonate-type species following coadsorption of CO(2) and water on rutile (110).

  2. Surface fluorination of rutile-TiO2 thin films deposited by reactive sputtering for accelerating response of optically driven capillary effect

    NASA Astrophysics Data System (ADS)

    Kobayashi, Taizo; Maeda, Hironobu; Konishi, Satoshi

    2016-06-01

    We report the acceleration of photoresponsive wettability switching by applying surface fluorination to rutile-TiO2 thin films deposited by reactive sputtering. Photoresponsive wettability switchable surfaces can be applied to optically driven liquid manipulation to enable the elimination of the electrical wiring and pneumatic tubing from fluidic systems. In this work, surface fluorination using CF4 plasma treatment is applied to rutile-TiO2 thin films, which exhibit a wider switching range of wettability than that of anatase-TiO2 thin films. Fluorine termination of TiO2 thin films increases the surface acidity and enhances its photocatalytic performance. TiO2 thin films with and without surface fluorination respectively exhibited the transition of contact angles ranging from 73.7 to 12.3°, and from 70.2 to 32° under UV irradiation for 15 min. Liquid introduction into a microchannel is also demonstrated, utilizing the developed TiO2 surface, which can generate a negative capillary pressure difference under ultraviolet light irradiation.

  3. Tm-doped TiO2 and Tm2Ti2O7 pyrochlore nanoparticles: enhancing the photocatalytic activity of rutile with a pyrochlore phase

    PubMed Central

    De los Santos, Desiré M; Aguilar, Teresa; Sánchez-Coronilla, Antonio; Fernández-Lorenzo, Concha; Alcántara, Rodrigo; Piñero, Jose Carlos; Blanco, Ginesa; Martín-Calleja, Joaquín

    2015-01-01

    Summary Tm-doped TiO2 nanoparticles were synthesized using a water-controlled hydrolysis reaction. Analysis was performed in order to determine the influence of the dopant concentration and annealing temperature on the phase, crystallinity, and electronic and optical properties of the resulting material. Various characterization techniques were utilized such as X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy and UV–vis spectroscopy. For the samples annealed at 773 and 973 K, anatase phase TiO2 was obtained, predominantly internally doped with Tm3+. ICP–AES showed that a doping concentration of up to 5.8 atom % was obtained without reducing the crystallinity of the samples. The presence of Tm3+ was confirmed by X-ray photoelectron spectroscopy and UV–vis spectroscopy: the incorporation of Tm3+ was confirmed by the generation of new absorption bands that could be assigned to Tm3+ transitions. Furthermore, when the samples were annealed at 1173 K, a pyrochlore phase (Tm2Ti2O7) mixed with TiO2 was obtained with a predominant rutile phase. The photodegradation of methylene blue showed that this pyrochlore phase enhanced the photocatalytic activity of the rutile phase. PMID:25821701

  4. Constrained Surface Complexation Modeling: Rutile in RbCl, NaCl, and NaCF3SO3 Media to 250 °C

    DOE PAGES

    Machesky, Michael L.; Předota, Milan; Ridley, Moira K.; Wesolowski, David J.

    2015-06-01

    In this paper, a comprehensive set of molecular-level results, primarily from classical molecular dynamics (CMD) simulations, are used to constrain CD-MUSIC surface complexation model (SCM) parameters describing rutile powder titrations conducted in RbCl, NaCl, and NaTr (Tr = triflate, CF3SO3–) electrolyte media from 25 to 250 °C. Rb+ primarily occupies the innermost tetradentate binding site on the rutile (110) surface at all temperatures (25, 150, 250 °C) and negative charge conditions (-0.1 and -0.2 C/m2) probed via CMD simulations, reflecting the small hydration energy of this large, monovalent cation. Consequently, variable SCM parameters (Stern-layer capacitance values and intrinsic Rb+ bindingmore » constants) were adjusted relatively easily to satisfactorily match the CMD and titration data. The larger hydration energy of Na+ results in a more complex inner-sphere distribution, which shifts from bidentate to tetradentate binding with increasing negative charge and temperature, and this distribution was not matched well for both negative charge conditions, which may reflect limitations in the CMD and/or SCM approaches. Finally, in particular, the CMD axial density profiles for Rb+ and Na+ reveal that peak binding distances shift toward the surface with increasing negative charge, suggesting that the CD-MUSIC framework may be improved by incorporating CD or Stern-layer capacitance values that vary with charge.« less

  5. Low-frequency dielectric properties of intrinsic and Al-doped rutile TiO2 thin films grown by the atomic layer deposition technique

    NASA Astrophysics Data System (ADS)

    Kassmi, M.; Pointet, J.; Gonon, P.; Bsiesy, A.; Vallée, C.; Jomni, F.

    2016-06-01

    Dielectric spectroscopy is carried out for intrinsic and aluminum-doped TiO2 rutile films which are deposited on RuO2 by the atomic layer deposition technique. Capacitance and conductance are measured in the 0.1 Hz-100 kHz range, for ac electric fields up to 1 MVrms/cm. Intrinsic films have a much lower dielectric constant than rutile crystals. This is ascribed to the presence of oxygen vacancies which depress polarizability. When Al is substituted for Ti, the dielectric constant further decreases. By considering Al-induced modification of polarizability, a theoretical relationship between the dielectric constant and the Al concentration is proposed. Al doping drastically decreases the loss in the very low frequency part of the spectrum. However, Al doping has almost no effect on the loss at high frequencies. The effect of Al doping on loss is discussed through models of hopping transport implying intrinsic oxygen vacancies and Al related centers. When increasing the ac electric field in the MVrms/cm range, strong voltage non-linearities are evidenced in undoped films. The conductance increases exponentially with the ac field and the capacitance displays negative values (inductive behavior). Hopping barrier lowering is proposed to explain high-field effects. Finally, it is shown that Al doping strongly improves the high-field dielectric behavior.

  6. Origin of colossal dielectric permittivity of rutile Ti₀.₉In₀.₀₅Nb₀.₀₅O₂: single crystal and polycrystalline.

    PubMed

    Song, Yongli; Wang, Xianjie; Sui, Yu; Liu, Ziyi; Zhang, Yu; Zhan, Hongsheng; Song, Bingqian; Liu, Zhiguo; Lv, Zhe; Tao, Lei; Tang, Jinke

    2016-02-12

    In this paper, we investigated the dielectric properties of (In + Nb) co-doped rutile TiO2 single crystal and polycrystalline ceramics. Both of them showed colossal, up to 10(4), dielectric permittivity at room temperature. The single crystal sample showed one dielectric relaxation process with a large dielectric loss. The voltage-dependence of dielectric permittivity and the impedance spectrum suggest that the high dielectric permittivity of single crystal originated from the surface barrier layer capacitor (SBLC). The impedance spectroscopy at different temperature confirmed that the (In + Nb) co-doped rutile TiO2 polycrystalline ceramic had semiconductor grains and insulating grain boundaries, and that the activation energies were calculated to be 0.052 eV and 0.35 eV for grain and grain boundary, respectively. The dielectric behavior and impedance spectrum of the polycrystalline ceramic sample indicated that the internal barrier layer capacitor (IBLC) mode made a major contribution to the high ceramic dielectric permittivity, instead of the electron-pinned defect-dipoles.

  7. Self-induced synthesis of phase-junction TiO2 with a tailored rutile to anatase ratio below phase transition temperature

    PubMed Central

    Wang, Wei-Kang; Chen, Jie-Jie; Zhang, Xing; Huang, Yu-Xi; Li, Wen-Wei; Yu, Han-Qing

    2016-01-01

    The surface phase junction of nanocrystalline TiO2 plays an essential role in governing its photocatalytic activity. Thus, facile and simple methods for preparing phase-junction TiO2 photocatalysts are highly desired. In this work, we show that phase-junction TiO2 is directly synthesized from Ti foil by using a simple calcination method with hydrothermal solution as the precursor below the phase transition temperature. Moreover, the ratio of rutile to anatase in the TiO2 samples could be readily tuned by changing the ratio of weight of Ti foil to HCl, which is used as the hydrothermal precursor, as confirmed by the X-ray diffraction analysis. In the photocatalytic reaction by the TiO2 nanocomposite, a synergistic effect between the two phases within a certain range of the ratio is clearly observed. The results suggest that an appropriate ratio of anatase to rutile in the TiO2 nanocomposite can create more efficient solid-solid interfaces upon calcination, thereby facilitating interparticle charge transfer in the photocatalysis. PMID:26864501

  8. Carbon-decorated Li₄Ti₅O₁₂/rutile TiO₂ mesoporous microspheres with nanostructures as high-performance anode materials in lithium-ion batteries.

    PubMed

    Gao, Lin; Liu, Rujun; Hu, Hao; Li, Guojian; Yu, Ying

    2014-05-01

    Li4Ti5O12/rutile TiO2 (LTO-RT) composites with Li/Ti molar ratios of 3:5, 4:5 and 4.5:5 have been successfully synthesized with TiO2 microspheres as a precursor. Furthermore, C-coated LTO-RT mesoporous microspheres with a molar ratio of 4:5 (C/4-5-LTO-RT) have been prepared based on the LTO-RT composite through a hydrothermal method and high temperature calcination. After various characterizations, it is found that carbon plays a pivotal role in retaining the porous nanostructure of the original as-prepared TiO2 precursor in the overall process. Substantially, C/4-5-LTO-RT still shows a high specific surface area of 63.70 m(2) g(-1) even after high temperature treatment at 800 °C. Since the porous nanostructure offers open and direct channels for the diffusion of Li ions and electrons and carbon decoration also efficiently improves the electrical conductivity, the sample of C/4-5-LTO-RT shows an enhanced electrochemical performance. In addition, the presence of nanosized rutile TiO2 in C/4-5-LTO-RT has an important contribution to the high electrochemical performance, as does the fast lithium ion diffusion along the [001] direction.

  9. Origin of colossal dielectric permittivity of rutile Ti0.9In0.05Nb0.05O2: single crystal and polycrystalline

    PubMed Central

    Song, Yongli; Wang, Xianjie; Sui, Yu; Liu, Ziyi; Zhang, Yu; Zhan, Hongsheng; Song, Bingqian; Liu, Zhiguo; Lv, Zhe; Tao, Lei; Tang, Jinke

    2016-01-01

    In this paper, we investigated the dielectric properties of (In + Nb) co-doped rutile TiO2 single crystal and polycrystalline ceramics. Both of them showed colossal, up to 104, dielectric permittivity at room temperature. The single crystal sample showed one dielectric relaxation process with a large dielectric loss. The voltage-dependence of dielectric permittivity and the impedance spectrum suggest that the high dielectric permittivity of single crystal originated from the surface barrier layer capacitor (SBLC). The impedance spectroscopy at different temperature confirmed that the (In + Nb) co-doped rutile TiO2 polycrystalline ceramic had semiconductor grains and insulating grain boundaries, and that the activation energies were calculated to be 0.052 eV and 0.35 eV for grain and grain boundary, respectively. The dielectric behavior and impedance spectrum of the polycrystalline ceramic sample indicated that the internal barrier layer capacitor (IBLC) mode made a major contribution to the high ceramic dielectric permittivity, instead of the electron-pinned defect-dipoles. PMID:26869187

  10. Exceptional performance of photoelectrochemical water oxidation of single-crystal rutile TiO2 nanorods dependent on the hole trapping of modified chloride

    PubMed Central

    Zhang, Xuliang; Cui, Haiqin; Humayun, Muhammad; Qu, Yang; Fan, Naiying; Sun, Xiaojun; Jing, Liqiang

    2016-01-01

    It is highly desired to effectively trap photogenerated holes for efficient photoelectrochemical (PEC) water oxidation to evolve O2 on oxide semiconductors. Herein, it is found for the first time mainly based on the time-resolved- and atmosphere-controlled- surface photovoltage responses that the modified chloride would effectively trap photogenerated holes so as to prolong the charge lifetime and hence promote charge separation of single-crystal rutile TiO2 nanorods. Its strong capacity to trap holes, comparable to the widely-used methanol and Co(II) phosphate, is well responsible for the exceptional photoactivities for PEC water oxidation to evolve O2 on rutile nanorods with a proper amount of chloride modified, about 2.5-time high as that on the resulting anatase nanoparticles, even 10-time if the surface area is considered. Moreover, it is suggested that the hole trapping role of chemically-adsorbed chloride is related to its lonely-pair electrons, and to the subsequently-produced intermediate Cl atoms with proper electronegativity for evolving O2. Interestingly, this finding is also applicable to the chloride-modified anatase TiO2. This work will provide a feasible strategy to design high-activity nanostructured semiconductor photoanodes for PEC water oxidation, even for overall water splitting. PMID:26906953

  11. Origin of colossal dielectric permittivity of rutile Ti0.9In0.05Nb0.05O2: single crystal and polycrystalline

    NASA Astrophysics Data System (ADS)

    Song, Yongli; Wang, Xianjie; Sui, Yu; Liu, Ziyi; Zhang, Yu; Zhan, Hongsheng; Song, Bingqian; Liu, Zhiguo; Lv, Zhe; Tao, Lei; Tang, Jinke

    2016-02-01

    In this paper, we investigated the dielectric properties of (In + Nb) co-doped rutile TiO2 single crystal and polycrystalline ceramics. Both of them showed colossal, up to 104, dielectric permittivity at room temperature. The single crystal sample showed one dielectric relaxation process with a large dielectric loss. The voltage-dependence of dielectric permittivity and the impedance spectrum suggest that the high dielectric permittivity of single crystal originated from the surface barrier layer capacitor (SBLC). The impedance spectroscopy at different temperature confirmed that the (In + Nb) co-doped rutile TiO2 polycrystalline ceramic had semiconductor grains and insulating grain boundaries, and that the activation energies were calculated to be 0.052 eV and 0.35 eV for grain and grain boundary, respectively. The dielectric behavior and impedance spectrum of the polycrystalline ceramic sample indicated that the internal barrier layer capacitor (IBLC) mode made a major contribution to the high ceramic dielectric permittivity, instead of the electron-pinned defect-dipoles.

  12. Origin of colossal dielectric permittivity of rutile Ti₀.₉In₀.₀₅Nb₀.₀₅O₂: single crystal and polycrystalline.

    PubMed

    Song, Yongli; Wang, Xianjie; Sui, Yu; Liu, Ziyi; Zhang, Yu; Zhan, Hongsheng; Song, Bingqian; Liu, Zhiguo; Lv, Zhe; Tao, Lei; Tang, Jinke

    2016-01-01

    In this paper, we investigated the dielectric properties of (In + Nb) co-doped rutile TiO2 single crystal and polycrystalline ceramics. Both of them showed colossal, up to 10(4), dielectric permittivity at room temperature. The single crystal sample showed one dielectric relaxation process with a large dielectric loss. The voltage-dependence of dielectric permittivity and the impedance spectrum suggest that the high dielectric permittivity of single crystal originated from the surface barrier layer capacitor (SBLC). The impedance spectroscopy at different temperature confirmed that the (In + Nb) co-doped rutile TiO2 polycrystalline ceramic had semiconductor grains and insulating grain boundaries, and that the activation energies were calculated to be 0.052 eV and 0.35 eV for grain and grain boundary, respectively. The dielectric behavior and impedance spectrum of the polycrystalline ceramic sample indicated that the internal barrier layer capacitor (IBLC) mode made a major contribution to the high ceramic dielectric permittivity, instead of the electron-pinned defect-dipoles. PMID:26869187

  13. U-Pb systematics in coexisting zircon, rutile and titanite from granophyres in the Archean Stillwater Complex: metamictization and the fate of radiogenic Pb

    NASA Astrophysics Data System (ADS)

    Friedman, R. M.; Wall, C. J.; Scoates, J. S.; Meurer, W. P.

    2009-12-01

    Self-irradiation of zircon causes structural damage (metamictization) that can result in the loss of radiogenic Pb during interaction with aqueous solutions. To evaluate this behavior in metamict zircon, and in other U-bearing accessory phases like titanite and rutile, we are examining the U-Pb systematics of granophyric rocks from the ca. 2.7 Ga Stillwater layered intrusion, Montana. Four samples were studied in detail, including a pegmatitic ksp-qtz core to a gabbroic pegmatoid in the Lower Banded Series (N1), an alaskite and an amphibole-rich reaction zone between the alaskite and anorthosite (AN1) in the Middle Banded Series, and an amphibole-bearing granophyre from the Upper Banded Series (GN3). Except in the pegmatite, zircon is variably metamict with amorphous zones characterized by distinctive Ca-enrichment. Single zircon grains were analyzed by ID-TIMS following annealing and chemical abrasion, and multi-grain (n=4-5) fractions of titanite and rutile were analyzed by conventional ID-TIMS; the UBC 233-235U-205Pb isotopic tracer is calibrated against mixed U-Pb gravimetric reference solutions made available through the EarthTime initiative. The U-Pb systematics are coherent only for the pegmatite yielding both a Concordia age of 2709.60 ± 0.80 Ma (2σ, including tracer calibration, decay-constant errors not included) for low-U zircon (76-237 ppm) and concordant titanite results with 207Pb/206Pb ages from 2701-2710 Ma. The results for high-U zircon (up to 1438 ppm) for the other three samples are strongly discordant (9-43%, 85-89%, 28-71%, respectively) with a wide range of 207Pb/206Pb ages (2583-2647 Ma, 2210-2357 Ma, 2345-2499 Ma). Given the extreme incompatibility of Pb2+ in zircon and the highly metamict state of zircon in these granophyres, we are investigating the extent to which radiogenic lead is selectively removed during the chemical abrasion and annealing process from step-wise leaching experiments and image analysis (CL, SEM). In contrast

  14. Epitaxial single-crystal thin films of MnxTi1 - xO2 - δ grown on (rutile)TiO2 substrates with pulsed laser deposition: Experiment and theory

    NASA Astrophysics Data System (ADS)

    Ilton, Eugene S.; Droubay, Timothy C.; Chaka, Anne M.; Kovarik, Libor; Varga, Tamas; Arey, Bruce W.; Kerisit, Sebastien N.

    2015-02-01

    Epitaxial rutile-structured single-crystal MnxTi1 - xO2 - δ films were synthesized on rutile- (110) and -(001) substrates using pulsed laser deposition. The films were characterized by reflection high-energy electron diffraction (RHEED), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and aberration-corrected transmission electron microscopy (ACTEM). Under the present conditions, 400 °C and PO2 = 20 mTorr, single crystal epitaxial thin films were grown for x = 0.13, where x is the nominal average mole fraction of Mn. In fact, arbitrarily thick films could be grown with near invariant Mn/Ti concentration profiles from the substrate/film interface to the film surface. In contrast, at x = 0.25, Mn became enriched towards the surface and a secondary nano-scale phase formed which appeared to maintain the basic rutile structure but with enhanced z-contrast in the tunnels, or interstitial sites. Ab initio thermodynamic calculations provided quantitative estimates for the destabilizing effect of expanding the β-MnO2 lattice parameters to those of TiO2-rutile, the stabilizing effect of diluting Mn with increasing Ti concentration, and competing reaction pathways for surface oxide formation.

  15. Epitaxial single-crystal thin films of MnxTi1-xO2-δ grown on (rutile)TiO2 substrates with pulsed laser deposition: Experiment and theory

    SciTech Connect

    Ilton, Eugene S.; Droubay, Timothy C.; Chaka, Anne M.; Kovarik, Libor; Varga, Tamas; Arey, Bruce W.; Kerisit, Sebastien N.

    2015-02-01

    Epitaxial rutile-structured single-crystal MnxTi1-xO2-δ films were synthesized on rutile- (110) and -(001) substrates using pulsed laser deposition. The films were characterized by reflection high-energy electron diffraction (RHEED), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and aberration-corrected transmission electron microscopy (ACTEM). Under the present conditions, 400oC and PO2 = 20 mTorr, single crystal epitaxial thin films were grown for x = 0.13, where x is the nominal average mole fraction of Mn. In fact, arbitrarily thick films could be grown with near invariant Mn/Ti concentration profiles from the substrate/film interface to the film surface. In contrast, at x = 0.25, Mn became enriched towards the surface and a secondary nano-scale phase formed which appeared to maintain the basic rutile structure but with enhanced z-contrast in the tunnels, or tetrahedral interstitial sites. Ab initio thermodynamic calculations provided quantitative estimates for the destabilizing effect of expanding the β-MnO2 lattice parameters to those of TiO2-rutile, the stabilizing effect of diluting Mn with increasing Ti concentration, and competing reaction pathways.

  16. Experimental evidence for the role of accessory phases in magma genesis

    NASA Astrophysics Data System (ADS)

    Green, T. H.

    1981-07-01

    Recent experimental studies have established petrogenetic models based on melting processes involving major phases. The possible residual character of trace-element-enriched accessory phases is not considered for temperatures well above the solidus in these models. In contrast, geochemists, applying trace element data to independently test the experimentally-based models, have concluded that residual (or fractionating) accessory phases may have an essential role in controlling the trace element (especially REE) distributions in magmas. Some recent experimental work provides data on the stability of potentially significant accessories such as sphene, rutile, apatite, zoisite and mica in basaltic compositions at elevated P and T. Sphene is stable to 1000°C with 60% melting of a hydrous tholeiite at 15 kbar. At higher pressure, rutile is the only Ti-rich accessory phase, and is present to at least 1000°C and high degrees of melting. Published REE data on sphene and rutile suggest that these phases may be important in controlling REE distribution in some magmas. For example, island are high-Mg, low-Ca-Ti tholeiites with low REE abundances and U-shaped patterns (Hickey and Frey, 1979) may reflect the role of sphene. In addition to rutile, similar close-packed Ti-rich accessory phases such as priderite, perovskite, crichtonite and loveringite may occur in mantle-derived magmas. These phases readily accommodate the REE but their possible role needs experimental confirmation. Apatite is recorded in hawaiite (1.16% P 2O s) with 2% H 2O added at 5-6 kbar and 1050°C within 30°C of the liquidus, but at present no other experimental data are available on its high P, T stability, although thermodynamic calculations indicate that F may increase its stability markedly. Apatite is well known in high-pressure inclusions and as a phenocryst phase in rocks of the alkaline and calc-alkaline series. Ilmenite is known as a near-liquidus phase in some mafic magmas at ˜5-10 kbar, but

  17. X-ray absorption and photoemission spectroscopy of zinc protoporphyrin adsorbed on rutile TiO{sub 2}(110) prepared by in situ electrospray deposition

    SciTech Connect

    Rienzo, Anna; Mayor, Louise C.; Magnano, Graziano; Satterley, Christopher J.; O'Shea, James N.; Ataman, Evren; Schnadt, Joachim; Schulte, Karina

    2010-02-28

    Zinc-protoporphyrin, adsorbed on the rutile TiO{sub 2}(110) surface, has been studied using photoemission spectroscopy and near-edge absorption fine structure spectroscopy to deduce the nature of the molecule-surface bonding and the chemical environment of the central metal atom. To overcome the difficulties associated with sublimation of the porphyrin molecules, samples were prepared in situ using ultrahigh vacuum electrospray deposition, a technique which facilitates the deposition of nonvolatile and fragile molecules. Monolayers of Zn protoporphyrin are found to bond to the surface via the oxygen atoms of the deprotonated carboxyl groups. The molecules initially lie largely parallel to the surface, reorienting to an upright geometry as the coverage is increased up to a monolayer. For those molecules directly chemisorbed to the surface, the interaction is sufficiently strong to pull the central metal atom out of the molecule.

  18. Micro-Raman study on the softening and stiffening of phonons in rutile titanium dioxide film: Competing effects of structural defects, crystallite size, and lattice strain

    SciTech Connect

    Gautam, Subodh K.; Singh, Fouran Sulania, I.; Kulriya, P. K.; Singh, R. G.; Pippel, E.

    2014-04-14

    Softening and stiffening of phonons in rutile titanium dioxide films are investigated by in situ micro-Raman studies during energetic ion irradiation. The in situ study minimized other possible mechanisms of phonon dynamics. Initial softening and broadening of Raman shift are attributed to the phonon confinement by structural defects and loss of stoichiometry. The stiffening of A{sub 1g} mode is ascribed to large distortion of TiO{sub 6} octahedra under the influence of lattice strain in the (110) plane, which gives rise to lengthening of equatorial Ti-O bond and shortening of apical Ti-O bond. The shortening of apical Ti-O bond induces stiffening of A{sub 1g} mode in the framework of the bond-order-length-strength correlation mechanism.

  19. Adsorption and stability of malonic acid on rutile TiO2 (110), studied by near edge X-ray absorption fine structure and photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Syres, Karen L.; Thomas, Andrew G.; Graham, Darren M.; Spencer, Ben F.; Flavell, Wendy R.; Jackman, Mark J.; Dhanak, Vinod R.

    2014-08-01

    The adsorption of malonic acid on rutile TiO2 (110) has been studied using photoelectron spectroscopy and C K-edge, near edge X-ray fine structure spectroscopy (NEXAFS). Analysis of the O 1s and Ti 2p spectra suggest that the molecule adsorbs dissociatively in a doubly-bidentate adsorption geometry as malonate. The data are unable to distinguish between a chelating bonding mode with the backbone of the molecule lying along the [001] azimuth or a bridging geometry along the direction. Work carried out on a wiggler beamline suggests that the molecule is unstable under irradiation by high-flux synchrotron radiation from this type of insertion device.

  20. Effect of 79 MeV Br ion irradiation on the surface features of rutile TiO{sub 2} thin film

    SciTech Connect

    Rath, H.; Dash, P.; Som, T.; Dash, B. N.; Singh, U. P.; Kanjilal, D.; Mishra, N. C.

    2012-07-23

    In this study, rutile titanium dioxide thin films deposited on Si (100) substrates by DC magnetron sputtering are irradiated by 79 MeV Br ions. Though each Br ion is expected to amorphize the medium along its path, the film remains crystalline even at the highest fluence of irradiation. The evolution of surface of the films with Br ion fluence is studied using atomicforce microscopy. The films were found to smoothen under dense electronic excitation of Br ions. The irregular shape grain of the pristine films convert to circular shape at a fluence of 1 Multiplication-Sign 10{sup 13} Br ions cm{sup -2}. Power spectral density (PSD) analysis of the AFM images indicates that irradiation induced smoothing of the surfaces is governed by the surface diffusion process.

  1. Controllable hydrothermal synthesis of rutile TiO{sub 2} hollow nanorod arrays on TiCl{sub 4} pretreated Ti foil for DSSC application

    SciTech Connect

    Xi, Min; Zhang, Yulan; Long, Lizhen; Li, Xinjun

    2014-11-15

    Rutile TiO{sub 2} nanorod arrays (TNRs) were achieved by hydrothermal process on TiCl{sub 4} pretreated Ti foil. Subsequently, TNRs were hydrothermally etched in HCl solution to form hollow TiO{sub 2} nanorod arrays (H-TNRs). The TiCl{sub 4} pretreatment plays key roles in enhancement of Ti foil corrosion resistance ability and crystal nucleation introduction for TNRs growth. TNRs with desired morphology can be obtained by controlling TiCl{sub 4} concentration and the amount of tetrabutyl titanate (TTB) accordingly. TNRs with the length of ∼1.5 μm and diameter of ∼200 nm, obtained on 0.15 M TiCl{sub 4} pretreated Ti foil with 0.6 mL TTB, exhibits relatively higher photocurrent. The increased pore volume of the H-TNRs has contributed to the increased surface area which is benefit for Dye-Sensitized Solar Cells (DSSC) application. And the 180 °C-H-TNRs photoanode obtained from the 0.15-TiCl{sub 4}-TNRs sample demonstrated 128.9% enhancement of photoelectric efficiency of DSSC compared to that of the original TNR photoanode. - Graphical abstract: Rutile hollow TiO{sub 2} nanorod array photoanode obtained from original TiO{sub 2} nanorod array photoanode by hydrothermal etching demonstrates enhanced photoelectric efficiency of DSSC. - Highlights: • TiO{sub 2} nanorods are prepared via hydrothermal process on TiCl{sub 4}-pretreated Ti foil. • Hollow TiO{sub 2} nanorods are obtained by hydrothermal etching of TiO{sub 2} nanorods. • TiCl{sub 4} pretreatment plays a key role in protecting Ti foil from chemical corrosion. • Hollow TiO{sub 2} nanorods photoanode shows enhanced photoelectric efficiency for DSSC.

  2. The growth and structure of titanium dioxide films on a Re(1 0 -1 0) surface: Rutile(0 1 1)-(2 × 1)

    NASA Astrophysics Data System (ADS)

    Rosenthal, D.; Zizak, I.; Darowski, N.; Magkoev, T. T.; Christmann, K.

    2006-07-01

    Titanium dioxide films were grown on Re(1 0 -1 0) by Ti vapor deposition in oxygen at T = 830 K and studied by means of low-energy electron diffraction (LEED), X-ray photoelectron spectroscopy (XPS), low-energy ion scattering (LEIS) and X-ray diffraction (XRD). The Ti oxide stoichiometry was determined by XPS as Ti:O = 1:2, with the Ti oxidation state (4+). The TiO 2 growth was monitored by means of LEED as a function of film thickness. Extending the coverage from the submonolayer into the multilayer regime gives rise to a p(2 × 2) pattern, a (poorly ordered) (1 × 1), and, finally, a stable (2 × 2) structure, the latter being associated with a homogeneous TiO 2 phase. For normal electron incidence, the (2 × 2) LEED pattern exhibits systematically extinguished beams at ( n ± 1/2, 0) positions, indicating a glide mirror plane. The pg(2 × 2) structure could be explained by both a rutile(0 1 1)-(2 × 1) reconstructed surface and a bulk truncated brookite(0 0 1) surface. Faceting phenomena, i.e. running LEED spots, observed with thin TiO 2 films point to the formation of a rutile(0 1 1)-(2 × 1) surface with two domains and {0 1 1}-(2 × 1) facets and rule out the brookite alternative. Confirmation of this assignment was obtained by an XRD analysis performed at the Berlin synchrotron facility BESSY.

  3. Improved assessment of P-T paths from combined Zr-in-rutile thermometry and major phase element zoning: An example from UHT granulites of the Gruf Complex, Central Alps

    NASA Astrophysics Data System (ADS)

    Oalmann, J.; Moeller, A.; Bousquet, R.

    2012-12-01

    Combining major element compositions of major minerals with accessory phase thermometry can provide robust constraints on the P-T evolution of polymetamorphic rocks. The Gruf Complex in the Lepontine Alps has experienced UHT metamorphism and an upper amphibolite to lower granulite facies overprint. Migmatitic orthogneisses are the volumetrically dominant rock type in the Gruf Complex, but charnockites and rare sapphirine-bearing granulites preserve UHT mineral assemblages. Distinct types of granulites include: 1) massive, Al- and Mg-rich granulites; 2) foliated, stromatic granulites; 3) foliated, leucocratic granulites; 4) massive to foliated retrogressed granulites. X-ray compositional maps were obtained by electron microprobe to characterize porphyroblasts in the different granulite types. Trace element compositions of rutile inclusions and matrix grains were determined by LA-ICP-MS, and Zr-in-rutile temperatures were calculated. Large (up to 2 cm) garnet porphyroblasts within residual granulites contain inclusion-rich inner zones and inclusion-poor outer zones. In the inner zones, Fe and Ca contents increase toward the outer zones, whereas Mg content decreases. The outer zones are characterized by concave-up Fe profiles and concave-down Mg profiles. These complex profiles possibly indicate at least two stages of garnet growth, with modification of inner zone growth zoning by diffusion during the second growth stage. Rutile inclusions in garnet record temperatures from 600-900°C, potentially spanning the full temperature range of garnet growth. In the stromatic granulites, garnet porphyroblasts exhibit concentric zoning characterized by increasing Mg and decreasing Fe, Ca, and Mn contents from core to rim. Rutile inclusions in garnet crystallized from 500-700°C, whereas rutile grains in symplectites around garnet porphyroblasts record UHT conditions. Leucocratic granulites are characterized by semi-atoll garnet porphyroblasts in which garnet is partly consumed

  4. Comparing Quasiparticle H2O Level Alignment on Anatase and Rutile TiO2

    SciTech Connect

    Sun, Huijuan; Mowbray, Duncan J.; Migani, Annapaola; Zhao, Jin; Petek, Hrvoje; Rubio, Angel

    2015-07-02

    Knowledge of the alignment of molecular frontier levels in the ground state can be used to predict the photocatalytic activity of an interface. The position of the adsorbate’s highest occupied molecular orbital (HOMO) levels relative to the substrate’s valence band maximum (VBM) in the interface describes the favorability of photogenerated hole transfer from the VBM to the adsorbed molecule. This is a key quantity for assessing and comparing H2O photooxidation activities on two prototypical photocatalytic TiO2 surfaces: anatase (A)-TiO2(101) and rutile (R)-TiO2(110). Using the projected density of states (DOS) from state-of-the-art quasiparticle (QP) G0W0 calculations, we assess the relative photocatalytic activity of intact and dissociated H2O on coordinately unsaturated (Ticus) sites of idealized stoichiometric A-TiO2(101)/R-TiO2(110) and bridging O vacancies (Obrvac) of defective A-TiO2-x(101)/R-TiO2-x(110) surfaces (x = 1/4, 1/8) for various coverages. Such a many-body treatment is necessary to correctly describe the anisotropic screening of electron-electron interactions at a photocatalytic interface and, hence, obtain accurate interfacial level alignments. The more favorable ground state HOMO level alignment for A-TiO2(101) may explain why the anatase polymorph shows higher photocatalytic activities than the rutile polymorph. Our results indicate that (1) hole trapping is more favored on A-TiO2(101) than RTiO2(110) and (2) HO@Ticus is more photocatalytically active than intact H2O@Ticus.

  5. Atomic layer deposition of rutile and TiO2-II from TiCl4 and O3 on sapphire: Influence of substrate orientation on thin film structure

    NASA Astrophysics Data System (ADS)

    Möldre, Kristel; Aarik, Lauri; Mändar, Hugo; Niilisk, Ahti; Rammula, Raul; Tarre, Aivar; Aarik, Jaan

    2015-10-01

    Atomic layer deposition of TiO2 from TiCl4 and ozone on single crystal α-Al2O3 substrates was investigated and the possibility to control the phase composition by the substrate orientation was demonstrated. Epitaxial growth of rutile and high-pressure TiO2-II on α-Al2O3(0 0 0 1) and rutile on α-Al2O3(0 1 1¯ 2) were obtained at 400-600 °C. On α-Al2O3(0 0 0 1), the epitaxial relationships were determined to be [0 1 0]R // [2 1¯ 1¯ 0]S and [0 0 1]R // [0 1 1¯ 0]S for rutile and sapphire, and [0 0 1]II // [2 1¯ 1¯ 0]S and [0 1¯ 0]II // [0 1 1¯ 0]S for TiO2-II and sapphire. The TiO2-II concentration up to 50% was obtained in the films deposited at 425-500 °C. On α-Al2O3(0 1 1¯ 2), the epitaxial relationship of rutile was [0 1 0]R // [2 1¯ 1¯ 0]S and [0 0 1]R // [0 1 1¯ 0]S. The densities of epitaxial films reached 4.2-4.3 g/cm3 on substrates with both orientations but the epitaxial quality was markedly higher on α-Al2O3(0 0 0 1).

  6. Phonon quarticity induced by changes in phonon-tracked hybridization during lattice expansion and its stabilization of rutile TiO2

    SciTech Connect

    Lan, Tian; Li, Chen W.; Hellman, O.; Kim, D. S.; Muñoz, Jorge A.; Smith, Hillary; Abernathy, Douglas L.; Fultz, B.

    2015-08-11

    Although the rutile structure of TiO2 is stable at high temperatures, the conventional quasiharmonic approximation predicts that several acoustic phonons decrease anomalously to zero frequency with thermal expansion, incorrectly predicting a structural collapse at temperatures well below 1000 K. In this paper, inelastic neutron scattering was used to measure the temperature dependence of the phonon density of states (DOS) of rutile TiO2 from 300 to 1373 K. Surprisingly, these anomalous acoustic phonons were found to increase in frequency with temperature. First-principles calculations showed that with lattice expansion, the potentials for the anomalous acoustic phonons transform from quadratic to quartic, stabilizing the rutile phase at high temperatures. In these modes, the vibrational displacements of adjacent Ti and O atoms cause variations in hybridization of 3d electrons of Ti and 2p electrons of O atoms. Finally, with thermal expansion, the energy variation in this “phonon-tracked hybridization” flattens the bottom of the interatomic potential well between Ti and O atoms, and induces a quarticity in the phonon potential.

  7. Spontaneous formation of suboxidic coordination around Co in ferromagnetic rutile Ti0.95Co0.5O2 film

    SciTech Connect

    Hu, Wen; Hayaski, Kouichi; Fukumura, Tomoteru; Akagi, Kazuto; Tsukada, Masaru; Happo, Naohisa; Hosokawa, Shinya; Ohwada, Kenji; Takahasi, Masamitu; Suzuki, Motohiro

    2015-06-02

    To evaluate local atomic structures around Co in high temperature diluted ferromagnetic semiconductor Co-doped TiO2, x-ray fluorescence holography and x-ray absorption fine structure experiments were carried out on rutile paramagnetic Ti0.99Co0.01O2 and ferromagnetic Ti0.95Co0.05O2 films. The Co atoms in the Ti0.99Co0.01O2 simply substituted for Ti sites in the rutile structure, whereas a suboxidic arrangement of CoO2Ti4 formed around Co in the Ti0.95Co0.05O2 films. A theoretical investigation based on a series of first-principles calculations indicated the stability of the aggregated suboxidic clusters in the rutile TiO2, supporting our hypothesis for the formation of suboxidic coordination in the highly Co-doped sample. As a result, the suboxidic coordination may be the source of strong exchange interaction, resulting in the high Curie temperature in Co-doped TiO2.

  8. Water adsorption on rutile TiO2(110) for applications in solar hydrogen production: A systematic hybrid-exchange density functional study

    NASA Astrophysics Data System (ADS)

    Patel, M.; Mallia, G.; Liborio, L.; Harrison, N. M.

    2012-07-01

    Periodic hybrid-exchange density functional theory calculations are used to predict the structure of water on the rutile TiO2(110) surface (Θ⩽ 1 ML), which is an important first step towards understanding the photocatalytic processes that occur in solar water splitting. A detailed model describing the water-water and water-surface interactions is developed by exploring thoroughly the adsorption energetics. The possible adsorption mode—molecular, dissociative, or mixed—and the binding energy are studied as a function of coverage and arrangement, thus separation, of adsorbed species. These dependencies (coverage and arrangement) have a significant influence on the nature of the interactions involved in the H2O-TiO2 system. The importance of both direct intermolecular and surface-mediated interactions between surface species is emphasized. Finally, to gain insight into the photooxidation of adsorbed species at the surface, the electronic structure of the predicted adsorbate-substrate geometries is analyzed in terms of total and projected density of states.

  9. Molecular mechanics of the cooperative adsorption of a Pro-Hyp-Gly tripeptide on a hydroxylated rutile TiO2(110) surface mediated by calcium ions.

    PubMed

    Zheng, Ting; Wu, Chunya; Chen, Mingjun; Zhang, Yu; Cummings, Peter T

    2016-07-20

    The interaction of amino acids with inorganic materials at interfaces plays an important role in enhancing the biocompatibility of titanium-based alloys. The adsorption of a tripeptide, i.e. Pro-Hyp-Gly, on the hydroxylated rutile TiO2(110) surface was investigated by the MD simulations. The changes in free energy during the adsorption of both the tripeptide and calcium ions were calculated by using the PMF method in order to obtain the adsorption strength. The results suggested that the adsorption of the tripeptide on the TiO2 surface through the carboxyl groups in glycine residues can be more stable compared with other binding conformations. Special attention was focused on the cooperative adsorption of the tripeptide with the assistance of calcium ions. Calcium ions preferred to absorb at the tetradentate or monodentate sites on the negatively charged TiO2 surface. As a result of the strong attraction between the carboxyl group and calcium ions, the tripeptide can be pulled down to the surface by following the trajectory of the calcium ions, forming an indirect interaction with a sandwich structure of peptide-cation-TiO2. However, this indirect interaction could eventually transform to the direct adsorption of the tripeptide on the TiO2 surface with higher binding energy. The results may help to interpret the adsorption of peptides on inorganic materials in aqueous solution with ions. PMID:27383367

  10. Adsorption geometry, molecular interaction, and charge transfer of triphenylamine-based dye on rutile TiO{sub 2}(110)

    SciTech Connect

    Yu Shun; Ahmadi, Sareh; Weissenrieder, Jonas; Goethelid, Mats; Zuleta, Marcelo; Tian Haining; Yang Xichuan; Schulte, Karina; Pietzsch, Annette; Hennies, Franz

    2010-12-14

    The fast development of new organic sensitizers leads to the need for a better understanding of the complexity and significance of their adsorption processes on TiO{sub 2} surfaces. We have investigated a prototype of the triphenylamine-cyanoacrylic acid (donor-acceptor) on rutile TiO{sub 2} (110) surface with special attention on the monolayer region. This molecule belongs to the type of dye, some of which so far has delivered the record efficiency of 10%-10.3% for pure organic sensitizers [W. Zeng, Y. Cao, Y. Bai, Y. Wang, Y. Shi, M. Zhang, F. Wang, C. Pan, and P. Wang, Chem. Mater. 22, 1915 (2010)]. The molecular configuration of this dye on the TiO{sub 2} surface was found to vary with coverage and adopt gradually an upright geometry, as determined from near edge x-ray absorption fine structure spectroscopy. Due to the molecular interaction within the increasingly dense packed layer, the molecular electronic structure changes systematically: all energy levels shift to higher binding energies, as shown by photoelectron spectroscopy. Furthermore, the investigation of charge delocalization within the molecule was carried out by means of resonant photoelectron spectroscopy. A fast delocalization ({approx}1.8 fs) occurs at the donor part while a competing process between delocalization and localization takes place at the acceptor part. This depicts the ''push-pull'' concept in donor-acceptor molecular system in time scale.

  11. Insights into Acetone Photochemistry on Rutile TiO2(110). 1. Off-Normal CH3 Ejection from Acetone Diolate.

    SciTech Connect

    Petrik, Nikolay G.; Henderson, Michael A.; Kimmel, Gregory A.

    2015-06-04

    Thermal- and photon-stimulated reactions of acetone co-adsorbed with oxygen on rutile TiO2(110) surface are studied with infrared reflection-adsorption spectroscopy (IRAS) combined with temperature programmed desorption and angle-resolved photon stimulated desorption. IRAS results show that n2-acetone diolate ((CH3)2COO) is produced via thermally-activated reactions between the chemisorbed oxygen with co-adsorbed acetone. Formation of acetone diolate is also consistent with 18O / 16O isotopic exchange experiments. During UV irradiation at 30 K, CH3 radicals are ejected from the acetone diolate with a distribution that is peaked at .-. +- 66 degrees from the surface normal along the azimuth (i.e. perpendicular to the rows of bridging oxygen and Ti5c ions). This distribution is also consistent with the orientation of the C–CH3 bonds in the n2-acetone diolate on TiO2(110). The acetone diolate peaks disappear from the IRAS spectra after UV irradiation and new peaks are observed and associated with n2-acetate. The data presented here demonstrate direct signatures of the proposed earlier 2-step mechanism for acetone photooxidation on TiO2(110)

  12. Interaction of carboxylic acids with rutile TiO2(110): IR-investigations of terephthalic and benzoic acid adsorbed on a single crystal substrate

    NASA Astrophysics Data System (ADS)

    Buchholz, Maria; Xu, Mingchun; Noei, Heshmat; Weidler, Peter; Nefedov, Alexei; Fink, Karin; Wang, Yuemin; Wöll, Christof

    2016-01-01

    The adsorption of two carboxylic acids, benzoic acid (BA) and terephthalic acid (TPA), on a single crystal rutile TiO2(110) substrate was studied using infrared reflection-absorption spectroscopy (IRRAS) in conjunction with DFT calculations. On the basis of the high-quality IR data (in particular for the OH bands), various adsorbate species with different geometries could be identified. The adsorption of both, BA and TPA, on TiO2(110) leads to deprotonation of carboxylic acids and protonation of substrate O-atoms. At low coverage, the deprotonated BA molecule adsorbs on TiO2(110) in an upright, bidentate configuration, while the TPA molecule adopts a flat-lying geometry with both carboxylates bound to the surface in a monodentate geometry. At higher coverages, a transition from flat-lying to upright-oriented TPA molecules occurs. At saturation coverage, both BA and TPA molecules undergo dimerization indicating the presence of pronounced attractive intermolecular interactions. We propose that the BA dimers are stabilized by the interaction between adjacent phenyl rings, while the TPA dimerization is attributed to the formation of double hydrogen bonds between adjacent apical carboxylic groups.

  13. H2O2-assisted photocatalysis on flower-like rutile TiO2 nanostructures: Rapid dye degradation and inactivation of bacteria

    NASA Astrophysics Data System (ADS)

    Kőrösi, László; Prato, Mirko; Scarpellini, Alice; Kovács, János; Dömötör, Dóra; Kovács, Tamás; Papp, Szilvia

    2016-03-01

    Hierarchically assembled flower-like rutile TiO2 (FLH-R-TiO2) nanostructures were successfully synthesized from TiCl4 at room temperature without the use of surfactants or templates. An initial sol-gel synthesis at room temperature allowed long-term hydrolysis and condensation of the precursors. The resulting FLH-R-TiO2 possessed relatively high crystallinity (85 wt%) and consisted of rod-shaped subunits assembling into cauliflower-like nanostructures. Hydrothermal evolution of FLH-R-TiO2 at different temperatures (150, 200 and 250 °C) was followed by means of X-ray diffraction, transmission and scanning electron microscopy. These FLH-R-TiO2 nanostructures were tested as photocatalysts under simulated daylight (full-spectrum lighting) in the degradation of methyl orange and in the inactivation of a multiresistant bacterium, Klebsiella pneumoniae. The effects of hydrothermal treatment on the structure, photocatalytic behavior and antibacterial activity of FLH-R-TiO2 are discussed.

  14. Growth and characterization of well-aligned densely-packed rutile TiO(2) nanocrystals on sapphire substrates via metal-organic chemical vapor deposition.

    PubMed

    Chen, C A; Chen, Y M; Korotcov, A; Huang, Y S; Tsai, D S; Tiong, K K

    2008-02-20

    Well-aligned densely-packed rutile TiO(2) nanocrystals (NCs) have been grown on sapphire (SA) (100) and (012) substrates via metal-organic chemical vapor deposition (MOCVD), using titanium-tetraisopropoxide (TTIP, Ti(OC(3)H(7))(4)) as a source reagent. The surface morphology as well as structural and spectroscopic properties of the as-deposited NCs were characterized using field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), selected-area electron diffractometry (SAED), x-ray diffraction (XRD) and micro-Raman spectroscopy. FESEM micrographs reveal that vertically aligned NCs were grown on SA(100), whereas the NCs on the SA(012) were grown with a tilt angle of ∼33° from the normal to substrates. TEM and SAED measurements showed that the TiO(2) NCs on SA(100) with square cross section have their long axis directed along the [001] direction. The XRD results reveal TiO(2) NCs with either (002) orientation on SA(100) substrate or (101) orientation on SA(012) substrate. A strong substrate effect on the alignment of the growth of TiO(2) NCs has been demonstrated and the probable mechanism for the formation of these NCs has been discussed. PMID:21817648

  15. Growth and characterization of well-aligned densely-packed rutile TiO2 nanocrystals on sapphire substrates via metal organic chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Chen, C. A.; Chen, Y. M.; Korotcov, A.; Huang, Y. S.; Tsai, D. S.; Tiong, K. K.

    2008-02-01

    Well-aligned densely-packed rutile TiO2 nanocrystals (NCs) have been grown on sapphire (SA) (100) and (012) substrates via metal-organic chemical vapor deposition (MOCVD), using titanium-tetraisopropoxide (TTIP, Ti(OC3H7)4) as a source reagent. The surface morphology as well as structural and spectroscopic properties of the as-deposited NCs were characterized using field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), selected-area electron diffractometry (SAED), x-ray diffraction (XRD) and micro-Raman spectroscopy. FESEM micrographs reveal that vertically aligned NCs were grown on SA(100), whereas the NCs on the SA(012) were grown with a tilt angle of ~33° from the normal to substrates. TEM and SAED measurements showed that the TiO2 NCs on SA(100) with square cross section have their long axis directed along the [001] direction. The XRD results reveal TiO2 NCs with either (002) orientation on SA(100) substrate or (101) orientation on SA(012) substrate. A strong substrate effect on the alignment of the growth of TiO2 NCs has been demonstrated and the probable mechanism for the formation of these NCs has been discussed.

  16. Growth of aligned single-crystalline rutile TiO2 nanowires on arbitrary substrates and their application in dye-sensitized solar cells

    SciTech Connect

    Kumar, Akshay; Madaria, Anuj R.; Zhou, Chongwu

    2010-05-06

    TiO{sub 2} is a wide band gap semiconductor with important applications in photovoltaic cells and photocatalysis. In this paper, we report synthesis of single-crystalline rutile phase TiO{sub 2} nanowires on arbitrary substrates, including fluorine-doped tin oxide (FTO), glass slides, tin-doped indium oxide (ITO), Si/SiO{sub 2}, Si(100), Si(111), and glass rods. By controlling the growth parameters such as growth temperature, precursor concentrations, and so forth, we demonstrate that anisotropic growth of TiO{sub 2} is possible leading to various morphologies of nanowires. Optimization of the growth recipe leads to well-aligned vertical array of TiO{sub 2} nanowires on both FTO and glass substrates. Effects of various titanium precursors on the growth kinetics, especially on the growth rate of nanowires, are also studied. Finally, application of vertical array of TiO{sub 2} nanowires on FTO as the photoanode is demonstrated in dye-sensitized solar cell with an efficiency of 2.9 ± 0.2%.

  17. Improved crystalline properties of laser molecular beam epitaxy grown SrTiO{sub 3} by rutile TiO{sub 2} layer on hexagonal GaN

    SciTech Connect

    Luo, W. B.; Zhu, J.; Chen, H.; Wang, X. P.; Zhang, Y.; Li, Y. R.

    2009-11-15

    Epitaxial SrTiO{sub 3} films were fabricated by laser molecular beam epitaxy on bare and TiO{sub 2} buffered GaN(0002), respectively. The whole deposition processes were in situ monitored by reflection high energy electron diffraction (RHEED). X-ray diffraction (XRD) was carried out to study the growth orientation and crystalline quality of STO films. The interfacial characters and epitaxial relationships were also investigated by high revolution transition electron microscope and selected area electron diffraction (SAED). According to the RHEED observation, the lowest epitaxy temperature of STO on TiO{sub 2} buffered GaN was decreased compared with the direct deposited one. The epitaxial relationship was (111)[110]STO//(0002)[1120]GaN in both cases as confirmed by RHEED, XRD, and SAED. The full width at half maximum of omega-scan and PHI-scan of STO on TiO{sub 2} buffered GaN was reduced compared with that deposited on bare GaN, indicating that epitaxial quality of STO film is improved by inserting TiO{sub 2} layer. In summary, the lattice mismatch was reduced by inserting rutile TiO{sub 2}. As a result, the crystalline temperature was reduced and enhanced epitaxial quality of STO thin film was obtained.

  18. The mechanism of emerging catalytic activity of gold nano-clusters on rutile TiO{sub 2}(110) in CO oxidation reaction

    SciTech Connect

    Mitsuhara, K.; Tagami, M.; Matsuda, T.; Visikovskiy, A.; Kido, Y.; Takizawa, M.

    2012-03-28

    This paper reveals the fact that the O adatoms (O{sub ad}) adsorbed on the 5-fold Ti rows of rutile TiO{sub 2}(110) react with CO to form CO{sub 2} at room temperature and the oxidation reaction is pronouncedly enhanced by Au nano-clusters deposited on the above O-rich TiO{sub 2}(110) surfaces. The optimum activity is obtained for 2D clusters with a lateral size of {approx}1.5 nm and two-atomic layer height corresponding to {approx}50 Au atoms/cluster. This strong activity emerging is attributed to an electronic charge transfer from Au clusters to O-rich TiO{sub 2}(110) supports observed clearly by work function measurement, which results in an interface dipole. The interface dipoles lower the potential barrier for dissociative O{sub 2} adsorption on the surface and also enhance the reaction of CO with the O{sub ad} atoms to form CO{sub 2} owing to the electric field of the interface dipoles, which generate an attractive force upon polar CO molecules and thus prolong the duration time on the Au nano-clusters. This electric field is screened by the valence electrons of Au clusters except near the perimeter interfaces, thereby the activity is diminished for three-dimensional clusters with a larger size.

  19. Thermally-Driven Processes on Rutile TiO2(110)-(1x1): A Direct View at the Atomic Scale

    SciTech Connect

    Dohnalek, Zdenek; Lyubinetsky, Igor; Rousseau, Roger J.

    2010-05-01

    The technological importance of TiO2 has led to a broad effort aimed at understanding the elementary steps that underlie catalytic and photocatalytic reactions. The most stable surface, rutile TiO2(110), in particular, has became a prototypical model for fundamental studies of TiO2. In this critical review we have selected oxygen, water, and alcohols to evaluate recent progress relevant for applications in the areas of water splitting and oxidation of organic contaminants. We first focus on the characterization of defects and the distribution of excess charge that results from their formation. The subsequent section demonstrates the role of individual surface sites and the effect of available charge in the adsorption processes. The discussion of adsorbate dynamics follows, providing models for intrinsic and extrinsic diffusion processes as well as rotational dynamics of anchored alkoxy species. The final section summarizes our current understanding of TiO2(110) catalyzed reactions between water, oxygen, and their dissociation products.

  20. Formation of a thermally stable bilayer of coadsorbed intact and deprotonated thymine exploiting the surface corrugation of rutile TiO2(110).

    PubMed

    Duncan, D A; Pfisterer, J H K; Deimel, P S; Acres, R G; Fritton, M; Feulner, P; Barth, J V; Allegretti, F

    2016-07-27

    The adsorption of thymine, a pyrimidine based nucleobase, was studied on the (110) termination of rutile titanium dioxide in order to understand the thermal stability and gross structural parameters of the interaction between a strongly polar adsorbate and a highly corrugated transition metal oxide surface. Near-edge X-ray absorption fine structure (NEXAFS), X-ray photoelectron spectroscopy (XPS), temperature programmed XPS and temperature programmed desorption indicated the growth of a room temperature stable bilayer, which could only be removed by annealing to 450 K. The remaining first layer was remarkably robust, surviving annealing up to 550 K before undergoing N-H bond scission. The comparison to XPS of a sub-monolayer exposure of 1-methyluracil shows that the origin of the room temperature stable bilayer is not intermolecular interactions. This discovery, alongside the deprotonation of one of the first layer's pyrimidinic nitrogen atoms at room temperature, suggests that the thymine molecules in the first layer bind to the undercoordinated surface Ti atoms, and the second layer thymine molecules coordinate with the bridging oxygen atoms which protrude above the Ti surface plane on the (110) surface. The NEXAFS results indicate an almost upright orientation of the molecules in both layers, with a 30 ± 10° tilt away from the surface normal.

  1. Low-Temperature Desorption of N2O from NO on Rutile TiO2(110)-1x1

    SciTech Connect

    Kim, Boseong; Li, Zhenjun; Kay, Bruce D.; Dohnalek, Zdenek; Kim, Yu Kwon

    2014-05-08

    We find that NO dosed on rutile TiO2(110)-1×1 at substrate temperatures as low as 50 K readily reacts to produce N2O which desorbs promptly from the surface leaving an oxygen adatom behind. The desorption rate of N2O reaches a maximum value after 1 – 2 sec at an NO flux of 1.2 ×1014 NO/cm2∙sec and then decreases rapidly as the initially clean, reduced TiO2(110) surface with ~5% oxygen vacancies (VO’s) becomes covered with oxygen adatoms and unreacted NO. The maximum desorption rate is also found to increase as the substrate temperature is raised up to about 100 K. Interestingly, the N2O desorption during the low-temperature (LT) NO dose is strongly suppressed when molecular oxygen is predosed, whereas it persists on the surface with VO’s passivated by surface hydroxyls. Our results show that the surface charge, not the VO sites, plays a dominant role in the LT N2O desorption induced by a facile NO reduction at such low temperatures.

  2. Manipulating the charge state of Au clusters on rutile TiO2(110) single crystal surfaces through molecular reactions probed by infrared spectroscopy.

    PubMed

    Cao, Yunjun; Hu, Shujun; Yu, Min; Wang, Tingting; Huang, Shiming; Yan, Shishen; Xu, Mingchun

    2016-07-14

    The charge state of Au clusters deposited on rutile TiO2(110) single crystal surfaces was studied by UHV-FTIRS using CO as a probe. The as-deposited Au clusters on oxidized TiO2(110) surfaces are electrically neutral and are identified by the 2105-2112 cm(-1) vibrational frequency of adsorbed CO depending on Au coverage. Annealing Au/TiO2(110) in a moderate O2 atmosphere at 400 K blue shifts the CO vibrational frequency by only 2-3 cm(-1) both on bare TiO2(110) surfaces and on Au clusters. However, NO exposure blue shifts the CO vibrational frequency by 16-26 cm(-1) for CO adsorbed on Au atoms near the interface and by 3-4 cm(-1) for CO adsorbed on top of Au clusters. As the acceptors of the intense charge transfer from Au, the Oa atoms generated through (NO)2→ N2O + Oa reactions on the small fraction of the bare TiO2(110) surface reside around the Au/TiO2(110) interface perimeter, causing the neutral Au(0) to be cationic Au(δ+) states. This is a new approach to manipulate the charge state of Au clusters on oxide surfaces, which may be helpful in regulating the catalytic redox reactions on oxide supported metal systems.

  3. Ambient rutile VO2(R) hollow hierarchitectures with rich grain boundaries from new-state nsutite-type VO2, displaying enhanced hydrogen adsorption behavior.

    PubMed

    Xie, Junfeng; Wu, Changzheng; Hu, Shuanglin; Dai, Jun; Zhang, Ning; Feng, Jun; Yang, Jinlong; Xie, Yi

    2012-04-14

    Modulating the interaction between small gas molecules and solid host materials is becoming increasingly important for the future society due to the alternative energy resources especially for the hydrogen energy. As is known, two catalogues of materials such as two-dimensional (2D) lamellar cavity structures and three-dimensional (3D) infinite tunnel structures have received intensive considerations during the past decades. Herein, we put forward a new alternative that the solid materials with synergic effects of grain-boundary-rich (GBR) structure and 3D hierarchical hollow structure would also be a promising candidate for modulating the gas molecules in solid adsorbents. As expected, our constructed novel 3D hollow hierarchitectures with GBR shells standing on the hollow spherical cavity indeed resulted in the enhanced hydrogen adsorption behavior. The as-prepared 3D hollow hierarchitectures were very uniform in large scale, and the very simple reaction process offers high convenience, short reaction time, and no need for any complex manipulations or equipments. The hollow outlook of the rutile VO(2)(R) 3D hierarchitectures is the reminiscence of the hollow cavity of nsutite-type VO(2), while the formation of the VO(2)(R) GBR structure is attributed to volume shrink from a unique intergrowth structure of nsutite-type VO(2). The novel gas modulation model with the synergic effect of GBR structure and hierarchical hollow structure may pave a new way for developing materials in energy and environmental fields in the near future.

  4. Colossal dielectric permittivity in (Al + Nb) co-doped rutile SnO2 ceramics with low loss at room temperature

    NASA Astrophysics Data System (ADS)

    Song, Yongli; Wang, Xianjie; Zhang, Xingquan; Qi, Xudong; Liu, Zhiguo; Zhang, Lingli; Zhang, Yu; Wang, Yang; Sui, Yu; Song, Bo

    2016-10-01

    The exploration of colossal dielectric permittivity (CP) materials with low dielectric loss in a wide range of frequencies/temperatures continues to attract considerable interest. In this paper, we report CP in (Al + Nb) co-doped rutile SnO2 ceramics with a low dielectric loss at room temperature. Al0.02Nb0.05Sn0.93O2 and Al0.03Nb0.05Sn0.92O2 ceramics exhibit high relative dielectric permittivities (above 103) and low dielectric losses (0.015 < tan δ < 0.1) in a wide range of frequencies and at temperatures from 140 to 400 K. Al doping can effectively modulate the dielectric behavior by increasing the grain and grain boundary resistances. The large differences in the resistance and conductive activation energy of the grains and grain boundaries suggest that the CP in co-doped SnO2 ceramics can be attributed to the internal barrier layer capacitor effect.

  5. Orientation-Dependent Oxygen Evolution Activities of Rutile IrO2 and RuO2.

    PubMed

    Stoerzinger, Kelsey A; Qiao, Liang; Biegalski, Michael D; Shao-Horn, Yang

    2014-05-15

    The activities of the oxygen evolution reaction (OER) on IrO2 and RuO2 catalysts are among the highest known to date. However, the intrinsic OER activities of surfaces with defined crystallographic orientations are not well-established experimentally. Here we report that the (100) surface of IrO2 and RuO2 is more active in alkaline environments (pH 13) than the most thermodynamically stable (110) surface. The OER activity was correlated with the density of coordinatively undersaturated metal sites of each crystallographic facet. The surface-orientation-dependent activities can guide the design of nanoscale catalysts with increased activity for electrolyzers, metal-air batteries, and photoelectrochemical water splitting applications. PMID:26270358

  6. Experimental calibration of a Ti-in-quartz thermobarometer: an overview for applications to mylonites

    NASA Astrophysics Data System (ADS)

    Thomas, Jay

    2013-04-01

    During the last decade several trace element thermometers (Ti-in-quartz, Ti-in-zircon, Zr-in-rutile and Zr-in-sphene) were developed at RPI by determining the solubilities of trace elements in minerals as a function of pressure and temperature. The Ti-in-quartz thermometer is of particular interest for potentially estimating the P-T conditions of ductile deformation in crustal rocks because quartz fabric development and microstructural formation has been extensively studied. In this presentation I will discuss the experimental approach and thermodynamic basis used to calibrate trace element solubilities for usage as trace element thermometers, and overview some fundamental considerations necessary to 'take the temperature of ductile deformation'. In our experiments quartz and rutile were crystallized at equilibrium from SiO2- and TiO2-saturated fluids (aqueous solutions, hydrous melts) so that TiO2 activity was unity during quartz crystallization. During growth, Ti4+ substituted for Si4+ on the tetrahedral site in quartz so that the quartz contained the equilibrium concentration of Ti for each P-T condition. In static sub-solidus quartzose systems metamorphosed at high temperature conditions, Ti solubility equilibrium in quartz crystals must be attained by Ti diffusion from a Ti-bearing source (e.g. rutile, garnet, ilmenite, etc.). Due to the low diffusivity of Ti and the timescales of thermal events, Ti solubility equilibrium may not be attained in some systems. There are few studies that have investigated the role of dynamic recrystallization in attaining solubility equilibrium (e.g. Behr and Platt 2011; Grujic et al. 2011; Kidder et al. 2013). Constraining TiO2 activity during deformation is particularly important. The presence of rutile during deformation does not necessarily guarantee unity TiO2 activity unless it crystallized during the deformation event of interest. Behr WM, Platt JP (2011) A naturally constrained stress profile through the middle crust in

  7. LASS U-Th-Pb monazite and rutile geochronology of felsic high-pressure granulites (Rhodope, N Greece): Effects of fluid, deformation and metamorphic reactions in local subsystems

    NASA Astrophysics Data System (ADS)

    Wawrzenitz, Nicole; Krohe, Alexander; Baziotis, Ioannis; Mposkos, Evripidis; Kylander-Clark, Andrew R. C.; Romer, Rolf L.

    2015-09-01

    The specific chemical composition of monazite in shear zones is controlled by the syndeformation dissolution-precipitation reactions of the rock-forming minerals. This relation can be used for dating deformation, even when microfabric characteristics like shape preferred orientation or intracrystalline deformation of monazite itself are missing. Monazite contemporaneously formed in and around the shear zones may have different compositions. These depend on the local chemical context rather than reflecting successive crystallization episodes of monazite. This is demonstrated in polymetamorphic, mylonitic high-pressure (HP) garnet-kyanite granulites of the Alpine Sidironero Complex (Rhodope UHP terrain, Northern Greece). The studied mylonitic rocks escaped from regional migmatization at 40-36 Ma and from subsequent shearing through cooling until 36 Ma. In-situ laser-ablation split-stream inductively-coupled plasma mass spectrometry (LASS) analyses have been carried out on monazite from micro-scale shear zones, from pre-mylonitic microlithons as well as of monazite inclusions in relictic minerals complimented by U-Pb data on rutile and Rb-Sr data of biotite. Two major metamorphic episodes, Mesozoic and Cenozoic, are constrained. Chemical compositions, isotopic characteristics and apparent ages systematically vary among monazite of four different microfabric domains (I-IV). Within three pre-mylonitic domains (inclusions in (I) pre-mylonitic kyanite and (II) garnet porphyroclasts, and (III) in pre-mylonitic microlithons) monazite yields ages of ca. 130-150 Ma for HP-granulite metamorphism, in line with previous geochronological results in the area. Patchy alteration of the pre-mylonitic monazite by intra-grain dissolution-precipitation processes variably increased negative Eu anomaly and reduced the HREE contents. The apparent age of this altered monazite is reduced. Monazite in the syn-mylonitic shear bands (IV) differs in chemical composition from unaltered and

  8. Dynamics and structure of hydration water on rutile and cassiterite nano-powders studied by quasielastic neutron scattering and molecular dynamics simulations

    SciTech Connect

    Mamontov, Eugene

    2007-01-01

    Quasielastic neutron scattering (QENS) experiments carried out using time-of-flight and backscattering neutron spectrometers with widely different energy resolution and dynamic range revealed the diffusion dynamics of hydration water in nano-powder rutile (TiO2) and cassiterite (SnO2) that possess the rutile crystal structure with the (110) crystal face predominant on the surface. These isostructural oxides differ in their bulk dielectric constants, metal atom electronegativities, and lattice spacings, which may all contribute to differences in the structure and dynamics of sorbed water. When hydrated under ambient conditions, the nano-powders had similar levels of hydration: about 3.5 (OH/H2O) molecules per Ti2O4 surface structural unit of TiO2 and about 4.0 (OH/H2O) molecules per Sn2O4 surface unit of SnO2. Ab initio-optimized classical molecular dynamics (MD) simulations of the (110) surfaces in contact with SPC/E water at these levels of hydration indicate three structurally-distinct sorbed water layers L1, L2, and L3, where the L1 species are either associated water molecules or dissociated hydroxyl groups in direct contact with the surface, L2 water molecules are hydrogen bonded to L1 and structural oxygen atoms at the surface, and L3 water molecules are more weakly bound. At the hydration levels studied, L3 is incomplete compared with axial oxygen density profiles of bulk SPC/E water in contact with these surfaces, but the structure and dynamics of L1 "L3 species are remarkably similar at full and reduced water coverage. Three hydration water diffusion components, on the time scale of a picosecond, tens of picoseconds, and a nanosecond could be extracted from the QENS spectra of both oxides. However, the spectral weight of the faster components was significantly lower for SnO2 compared to TiO2. In TiO2 hydration water, the more strongly bound L2 water molecules exhibited slow (on the time scale of a nanosecond) dynamics characterized by super

  9. The effect of oxygen vacancies on the binding interactions of NH3 with rutile TiO2(110) -1×1

    SciTech Connect

    Kim, Boseong; Li, Zhenjun; Kay, Bruce D.; Dohnalek, Zdenek; Kim, Yu Kwon

    2012-11-21

    A series of NH3 temperature-programmed desorption (TPD) spectra was taken after the NH3 dose at 70 K on rutile TiO2(110)-1×1 surfaces with the oxygen vacancy (VO) concentrations of ~0% (p-TiO2) and 5% (r-TiO2), respectively, to study the effect of VO’s on the desorption energy of NH3 as a function of the coverage, θ. Our results show that at zero coverage limit, the desorption energy of NH3 on r-TiO2 is 115 kJ/mol, which is 10 kJ/mol less than that on p-TiO2. The desorption energy from the Ti4+ sites decreases with increasing θ due to the repulsive NH3 - NH3 interactions and approaches ~ 55 kJ/mol upon the saturation of Ti4+ sites (θ = 1 monolayer, ML) on both p- and r-TiO2. The absolute saturation coverage is determined to be about 10% smaller on r-TiO2 than that on p-TiO2. Further, the trailing edges of the NH3 TPD spectra on the hydroxylated TiO2(110) (h-TiO2) appear to be the same as that on r-TiO2 while those on oxidized TiO2(110) (o-TiO2) shift to higher temperatures. We present the detailed analysis of the results and reconcile the observed differences based on the repulsive adsorbate-adsorbate interactions between neighboring NH3 molecules and the surface charge associated with the presence of VO’s. Besides NH3, no other reaction products are observed in the TPD spectra.

  10. Enhanced photocatalytic activity of Cl-residual rutile TiO2 nanorods after targeted co-modification with phosphoric and boric acids.

    PubMed

    Wu, Jing; Cui, Haiqin; Zhang, Xuliang; Luan, Yunbo; Jing, Liqiang

    2015-06-28

    The promotion of O2 adsorption on semiconductor surfaces for effectively capturing photogenerated electrons in the photocatalytic degradation of pollutants is highly desired. In this study, the targeted co-modification of residual chlorine rutile TiO2 nanorods with phosphoric and boric acids has been accomplished for the first time by simple wet chemical processes. The key to targeted co-modification is to connect -P-OH and -B-OH to the Cl-residual TiO2 surfaces by -Ti-OH and -Ti-Cl, respectively, consequently forming -Ti-O-P-OH and -Ti-Cl:B-OH ends. By means of the atmosphere-controlled surface photovoltage spectroscopy, the degrees for capturing photogenerated electrons by the adsorbed O2 as receptors on the resulting TiO2 nanorods are quantitatively analyzed. It is confirmed that the targeted co-modification could greatly promote the capture of the photogenerated electrons compared to the phosphate and borate modification alone. This is attributed to increased amounts of adsorbed O2 based on electrochemical O2 reduction and O2 temperature-programmed desorption measurements, further leading to the enhanced separation of photogenerated charges, characterized by an increase in the amount of produced hydroxyl radicals. This is responsible for the obviously enhanced photocatalytic activity of TiO2 nanorods towards the degradation of colorless gas-phase acetaldehyde and liquid-phase phenol. This work would provide us a feasible route for the co-modification with inorganic acids to synthesize efficient nanosized TiO2-based photocatalysts.

  11. Characterization of the Active Surface Species Responsible for UV-Induced Desorption of O2 from the Rutile TiO2(110) Surface

    SciTech Connect

    Henderson, Michael A.; Shen, Mingmin; Wang, Zhitao; Lyubinetsky, Igor

    2013-03-21

    We have examined the chemical and photochemical properties of molecular oxygen on the (110) surface of rutile TiO2 at 100 K using electron energy loss spectroscopy (EELS), photon stimulated desorption (PSD) and scanning tunneling microscopy (STM). Oxygen chemisorbs on the TiO2(110) surface at 100 K through charge transfer from surface Ti3+ sites. The charge transfer process is evident in EELS by a decrease in the intensity of the Ti3+ d-to-d transition in EELS at ~0.9 eV and formation of a new loss ~2.8 eV. Based on comparisons with the available homogeneous and heterogeneous literature for complexed/adsorbed O2, the species responsible for the 2.8 eV peak can be assigned to a surface peroxo (O2 2-) state of O2. This species was identified as the active form of adsorbed O2 on TiO2(110) for PSD. The adsorption site of this peroxo species was assigned to that of a regular five-cooridinated Ti4+ (Ti5c) site based on comparisons between the UV exposure dependent behavior of O2 in STM, PSD and EELS data. Assignment of the active form of adsorbed O2 to a peroxo species at normal Ti5c sites necessitates reevaluation of the simple mechanism in which a single valence band hole neutralizes a singly charged O2 species (superoxo or O2-) leading to desorption of O2 from a physisorbed potential energy surface. This work was supported by the U.S. Department of Energy (DOE), Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences, and the Chemical Imaging Initiative at Pacific Northwest National Laboratory (PNNL), and was performed in the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOE's Office of Biological and Environmental Research and located at PNNL.

  12. Discovery of deep and shallow trap states from step structures of rutile TiO{sub 2} vicinal surfaces by second harmonic and sum frequency generation spectroscopy

    SciTech Connect

    Takahashi, Hiroaki; Watanabe, Ryosuke; Miyauchi, Yoshihiro; Mizutani, Goro

    2011-04-21

    In this report, local electronic structures of steps and terraces on rutile TiO{sub 2} single crystal faces were studied by second harmonic and sum frequency generation (SHG/SFG) spectroscopy. We attained selective measurement of the local electronic states of the step bunches formed on the vicinal (17 18 1) and (15 13 0) surfaces using a recently developed step-selective probing technique. The electronic structures of the flat (110)-(1x1) (the terrace face of the vicinal surfaces) and (011)-(2x1) surfaces were also discussed. The SHG/SFG spectra showed that step structures are mainly responsible for the formation of trap states, since significant resonances from the trap states were observed only from the vicinal surfaces. We detected deep hole trap (DHT) states and shallow electron trap (SET) states selectively from the step bunches on the vicinal surfaces. Detailed analysis of the SHG/SFG spectra showed that the DHT and SET states are more likely to be induced at the top edges of the step bunches than on their hillsides. Unlike the SET states, the DHT states were observed only at the step bunches parallel to [1 1 1][equivalent to the step bunches formed on the (17 18 1) surface]. Photocatalytic activity for each TiO{sub 2} sample was also measured through methylene blue photodegradation reactions and was found to follow the sequence: (110) < (17 18 1) < (15 13 0) < (011), indicating that steps along [0 0 1] are more reactive than steps along [1 1 1]. This result implies that the presence of the DHT states observed from the step bunches parallel to [1 1 1] did not effectively contribute to the methylene blue photodegradation reactions.

  13. A nano-patterned self assembled monolayer (SAM) rutile titania cancer chip for rapid, low cost, highly sensitive, direct cancer analysis in MALDI-MS.

    PubMed

    Manikandan, M; Gopal, Judy; Hasan, Nazim; Wu, Hui-Fen

    2014-12-01

    We developed a cancer chip by nano-patterning a highly sensitive SAM titanium surface capable of capturing and sensing concentrations as low as 10 cancer cells/mL from the environment by Matrix Assisted Laser Desorption and Ionization Time of Flight Mass Spectrometry (MALDI-TOF MS). The current approach evades any form of pretreatment and sample preparation processes; it is time saving and does not require the (expensive) conventional MALDI target plate. The home made aluminium (Al) target holder cost, on which we loaded the cancer chips for MALDI-TOF MS analysis, is about 60 USD. While the conventional stainless steel MALDI target plate is more than 700 USD. The SAM surface was an effective platform leading to on-chip direct MALDI-MS detection of cancer cells. We compared the functionality of this chip with the unmodified titanium surfaces and thermally oxidized (TO) titanium surfaces. The lowest detectable concentration of the TO chip was 10(3) cells/mL, while the lowest detectable concentration of the control or unmodified titanium chips was 10(6) cells/mL. Compared to the control surface, the SAM cancer chip showed 100,000 times of enhanced sensitivity and compared with the TO chip, 1000 times of increased sensitivity. The high sensitivity of the SAM surfaces is attributed to the presence of the rutile SAM, surface roughness and surface wettability as confirmed by AFM, XRD, contact angle microscope and FE-SEM. This study opens a new avenue for the potent application of the SAM cancer chip for direct cancer diagnosis by MALDI-TOF MS in the near future.

  14. First-principles study of electronic structure and magnetic properties of doped SnO 2 (rutile) with single and double impurities

    NASA Astrophysics Data System (ADS)

    Fakhim Lamrani, A.; Belaiche, M.; Benyoussef, A.; El Kenz, A.; Saidi, E. H.

    2011-12-01

    Using the augmented spherical wave method, the electronic structure and magnetic properties of the rutile SnO2 doped with single and double impurities: Sn1-xMnxO2, Sn1-xWxO2, and Sn1-2xMnxWxO2 with x=0.0625, have been studied. The scalar-relativistic implementation with a generalized gradient approximation functional has been used for treating the effects of exchange and correlation. The ground state of Mn-, and W-doped SnO2 systems have a total magnetic moments of 3 and 2 μB, respectively. The half-metallic nature appears in Sn1-2xMnxWxO2, which makes them suitable as spintronic systems with total magnetic moment of 5 μB. The advantages of doping SnO2 with double impurities are investigated in this work. The total moment of the system, the local magnetic moments of the impurities, and their oxidation states are also discussed. Since there are two possible couplings between the impurities, we studied both configurations (ferromagnetic and antiferromagnetic) for double-impurities-doped SnO2. Magnetic properties and interatomic exchange have been computed for various distances between Mn and W. The indirect exchange between double impurities has similarities with the Zener mechanism in transition metal oxides. Based on the interaction between localized moments, via hybridization between impurities orbitals with the host oxygen, a double exchange mechanism is proposed to explain the ferromagnetism of our system.

  15. Experimental Pi.

    ERIC Educational Resources Information Center

    Corris, G.

    1990-01-01

    Discusses the calculation of pi by means of experimental methods. Polygon circle ratios, Archimedes' method, Buffon's needles, a Monte Carlo method, and prime number approaches are used. Presents three BASIC programs for the calculations. (YP)

  16. Reaction Kinetics of Water Molecules with Oxygen Vacancies on Rutile TiO2(110)

    SciTech Connect

    Petrik, Nikolay G.; Kimmel, Gregory A.

    2015-09-16

    The formation of bridging hydroxyls (OHb) via reactions of water molecules with oxygen vacancies (VO) on reduced TiO2(110) surfaces is studied using infrared reflection-absorption spectroscopy (IRAS), electron-stimulated desorption (ESD), and photon-stimulated desorption (PSD). Narrow IRAS peaks at 2737 cm-1 and 3711 cm-1 are observed for stretching vibrations of ODb and OHb on TiO2(110), respectively. IRAS measurements with s- and p-polarized light demonstrate that the bridging hydroxyls are oriented normal to the (110) surface. The IR peaks disappear after the sample is exposed to O2 or annealed in the temperature range of 400 – 600 K (correlating with the temperature at which pairs of OHb’s reform water and then desorb), which is consistent with their identification as bridging hydroxyls. We have studied the kinetics of water reacting with the vacancies by monitoring the formation of bridging hydroxyls (using IRAS) as a function of the annealing temperature for a small amount of water initially dosed on the TiO2(110) at low temperature. Separate experiments have also monitored the loss of water molecules (using water ESD) and vacancies (using the CO photooxidation reaction) due to the reactions of water molecules with the vacancies. All three techniques show that the reaction rate becomes appreciable for T > 150 K and that the reactions largely complete for T > 250 K. The temperature-dependent water-VO reaction kinetics are consistent with a Gaussian distribution of activation energies with Ea = 0.545 eV, ΔEa(FWHM) = 0.125 eV, and a “normal” prefactor, v = 1012 s-1. In contrast, a single activation energy with a physically reasonable prefactor does not fit the data well. Our experimental activation energy is close to theoretical estimates for the diffusion of water molecules along the Ti5c rows on the reduced TiO2

  17. Convenience experimentation.

    PubMed

    Krohs, Ulrich

    2012-03-01

    Systems biology aims at explaining life processes by means of detailed models of molecular networks, mainly on the whole-cell scale. The whole cell perspective distinguishes the new field of systems biology from earlier approaches within molecular cell biology. The shift was made possible by the high throughput methods that were developed for gathering 'omic' (genomic, proteomic, etc.) data. These new techniques are made commercially available as semi-automatic analytic equipment, ready-made analytic kits and probe arrays. There is a whole industry of supplies for what may be called convenience experimentation. My paper inquires some epistemic consequences of strong reliance on convenience experimentation in systems biology. In times when experimentation was automated to a lesser degree, modeling and in part even experimentation could be understood fairly well as either being driven by hypotheses, and thus proceed by the testing of hypothesis, or as being performed in an exploratory mode, intended to sharpen concepts or initially vague phenomena. In systems biology, the situation is dramatically different. Data collection became so easy (though not cheap) that experimentation is, to a high degree, driven by convenience equipment, and model building is driven by the vast amount of data that is produced by convenience experimentation. This results in a shift in the mode of science. The paper shows that convenience driven science is not primarily hypothesis-testing, nor is it in an exploratory mode. It rather proceeds in a gathering mode. This shift demands another shift in the mode of evaluation, which now becomes an exploratory endeavor, in response to the superabundance of gathered data.

  18. Experimental errors?

    NASA Astrophysics Data System (ADS)

    Downie, Neil; Turner, Jez

    2014-07-01

    In reply to Matin Durrani's article “Experimental mistake” (May p15, see also http://ow.ly/vDYlM) criticizing plans to base A-level science exams in England entirely on written tests, with practical skills noted as a separate grade.

  19. CO2 gas detection properties of a TIO2/Al2O3 heterostructure under UV light irradiation

    NASA Astrophysics Data System (ADS)

    Karaduman, Irmak; Demir, Mehmet; Yıldız, Dilber Esra; Acar, Selim

    2015-05-01

    Al/TiO2/p-Si and Al/TİO2/Al2O3/p-Si samples were prepared using the atomic layer deposition method (ALD) and their gas sensing properties were investigated. The electrical properties of the samples were studied using a two probe method in the temperature range 25-230 °C and at room temperature UV conditions. The TiO2/Al2O3 heterojunction sample exhibited an excellent gas sensing response to CO2 gas at room temperature and improved the effect of UV light irradiation. The results showed that heterostructures helped to improve the gas sensor properties, affected the sensing at room temperature and thus guided the design of photocatalysts. The TiO2/Al2O3 heterojunction prepared using this method can be used as a material for semiconductor gas sensors detecting poisonous gases like CO2 at room temperature with high sensitivity and selectivity.

  20. Modification mechanism of praseodymium doping for the photocatalytic performance of TiO2: a combined experimental and theoretical study.

    PubMed

    Duan, Zhi-Gang; Zhao, Zong-Yan; Shi, Qing-Nan

    2015-07-15

    Impurity doping is a simple and efficient modification method to improve the photocatalytic performance of wide band gap photocatalysts. However, some basic and important issues about the mechanism of impurity doping modification still need to be further confirmed and explained. In the present work, Pr-doped TiO2 with a mono-phase crystal structure was prepared by a sol-gel method. Then, the crystal structure, binding information, optical absorption, and photocatalytic activity were systematically investigated. The experimental results show that Pr doping could significantly enhance the photocatalytic activity of TiO2, and the effects of modification on rutile TiO2 are more obvious than for anatase TiO2. In order to understand the underlying mechanism, density functional theory was utilized to calculate the crystal structure and electronic structure of pure and Pr-doped TiO2. The differences in electronic structure between anatase and rutile phases lead to the above photocatalytic performance. The experimental measurements and theoretical calculations mutually support each other in the present work. Two points are confirmed: the position of the band edge determines the redox activity of the photocatalyst, and the shallow energy bands induced by impurity doping could improve the photocatalytic performance.

  1. Modification mechanism of praseodymium doping for the photocatalytic performance of TiO2: a combined experimental and theoretical study.

    PubMed

    Duan, Zhi-Gang; Zhao, Zong-Yan; Shi, Qing-Nan

    2015-07-15

    Impurity doping is a simple and efficient modification method to improve the photocatalytic performance of wide band gap photocatalysts. However, some basic and important issues about the mechanism of impurity doping modification still need to be further confirmed and explained. In the present work, Pr-doped TiO2 with a mono-phase crystal structure was prepared by a sol-gel method. Then, the crystal structure, binding information, optical absorption, and photocatalytic activity were systematically investigated. The experimental results show that Pr doping could significantly enhance the photocatalytic activity of TiO2, and the effects of modification on rutile TiO2 are more obvious than for anatase TiO2. In order to understand the underlying mechanism, density functional theory was utilized to calculate the crystal structure and electronic structure of pure and Pr-doped TiO2. The differences in electronic structure between anatase and rutile phases lead to the above photocatalytic performance. The experimental measurements and theoretical calculations mutually support each other in the present work. Two points are confirmed: the position of the band edge determines the redox activity of the photocatalyst, and the shallow energy bands induced by impurity doping could improve the photocatalytic performance. PMID:26130404

  2. Comparison of the Photodesorption Activities of cis-Butene, trans-Butene and Isobutene on the Rutile TiO2(110) Surface

    SciTech Connect

    Henderson, Michael A.

    2013-10-17

    The chemical and photochemical properties of three butene molecules (cis-butene, trans-butene and isobutene) were explored on the clean rutile TiO2(110) surface using temperature programmed desorption (TPD) and photon simulated desorption (PSD). At the low coverage limit, trans-butene was the most strongly bound butene on the TiO2(110) surface, desorbing at ~ 210 K, however increased intermolecular repulsions between trans-butene molecules at higher coverage diminished its binding. Both cis-butene and isobutene saturated the first layer on TiO2(110) at a coverage of ~0.50 ML in a single TPD feature at 184 and 192 K, respectively. In contrast, the maximum coverage that trans-butene could achieve in its 210 K peak was ~1/3 ML, with higher coverages resulting a low temperature desorption at ~137 K. Coverages of these molecules above 0.50 ML resulted in population of second layer and multilayer states. The instability of trans-butene at a coverage of 0.5 ML on the surface was linked to the inversion center in its symmetry. In the absence of coadsorbed oxygen, the primary photochemical pathway of each butene molecule on TiO2(110) was photodesorption. The photoactivities of these molecules on TiO2(110) at an initial coverage of 0.50 ML followed the trend: isobutene > cis-butene > trans-butene. In contrast, the photoactivities of low coverages of cis-butene and trans-butene exceeded those measured at 0.50 ML. These data suggest that intermolecular interactions (repulsions) play a significant role in diminishing the photoactivities of weakly bound molecules on TiO2 photocatalysts. Work reported here was supported by the U.S. Department of Energy, Office of Basic Energy Science, Division of Chemical Sciences, Geosciences, and Biosciences, and performed in the Williams R. Wiley Environmental Molecular Science Laboratory (EMSL), a Department of Energy user facility funded by the Office of Biological and

  3. Impact of nonadiabatic charge transfer on the rate of redox chemistry of carbon oxides on rutile TiO2 (110) surface

    SciTech Connect

    Yoon, Yeohoon; Wang, Yanggang; Rousseau, Roger J.; Glezakou, Vassiliki Alexandra

    2015-03-06

    We present the results of a density functional theory (DFT) within the LDA+U approximation on large models of partially reduced TiO2 (110) rutile surface to investigate the nature of charge transfer and the role of non-adiabatic effects on three prototypical redox reactions: (i) O2 adsorption (ii) CO oxidation and (iii) CO2 reduction. Charge-constrained DFT (cDFT) is used to estimate kinetic parameters for a Marcus theory rate law that accounts for adiabatic coupling effects on reaction rates. We find that for O2 adsorption, the coupling between adiabatic states is strong, leading to fast charge transfer rates. The lowest energy structures at high coverage consist of two chemisorbed O2-, one adsorbed at a VO site and the other adsorbed at an adjacent Ti5C site. For CO oxidation, however, all reactions are kinetically hindered on the ground state due to the weak adiabatic coupling at the state crossing, such that one has to overcome two kinetically unfavorable charge transfer events to drive the process (non-adiabatically) on the thermal ground state. The process can be driven by photochemical means but would result in an adsorbed radical [OCOO-] intermediate species. Similarly, CO2 reduction also proceeds via a non-adiabatic charge transfer to form an adsorbed CO2- species followed by a second non-adiabatic charge transfer to produce CO. Our analysis provides important computational guidelines for modeling these types of processes. We thank Z. Dohnalek, M. Hendersen, G. Kimmel, H. Metieu, and N. Petrik for invaluable discussions. This work was supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences and performed at the Pacific Northwest National Laboratory (PNNL). PNNL is a multi-program national laboratory operated for DOE by Battelle. Computational resources were provided at W. R. Wiley Environmental Molecular Science Laboratory (EMSL), a national scientific user facility sponsored by the

  4. Experimental colitis.

    PubMed

    MacPherson, B; Pfeiffer, C J

    1976-01-01

    Ulcerative colitis and Crohn's disease are complex, problematic diseases of unknown etiology in man, and appropriate experimental models would be useful in elucidating their pathogenesis and treatment. Although there have been numerous attempts to produce inflammatory ulcerative colonic disease in laboratory animals resembling those human disease forms, none has been entirely successful. Investigators have conducted experiments involving almost every etiological factor suggested for initiation of these diseases. The methods reviewed in this paper include production of experimental colitis by vascular impairment, and immunological methods such as bacterial infection, allergic reactions, direct and indirect hypersensitivity reactions, as well as autoimmune mechanisms. The results of carrageenan-induced colitis, irradiation, dietary, and drug-induced techniques are also discussed and the frequency and nature of spontaneous colonic lesions in animals is summarized.

  5. Animal experimentation.

    PubMed

    Kolar, Roman

    2006-01-01

    Millions of animals are used every year in often times extremely painful and distressing scientific procedures. Legislation of animal experimentation in modern societies is based on the supposition that this is ethically acceptable when certain more or less defined formal (e.g. logistical, technical) demands and ethical principles are met. The main parameters in this context correspond to the "3Rs" concept as defined by Russel and Burch in 1959, i.e. that all efforts to replace, reduce and refine experiments must be undertaken. The licensing of animal experiments normally requires an ethical evaluation process, often times undertaken by ethics committees. The serious problems in putting this idea into practice include inter alia unclear conditions and standards for ethical decisions, insufficient management of experiments undertaken for specific (e.g. regulatory) purposes, and conflicts of interest of ethics committees' members. There is an ongoing societal debate about ethical issues of animal use in science. Existing EU legislation on animal experimentation for cosmetics testing is an example of both the public will for setting clear limits to animal experiments and the need to further critically examine other fields and aspects of animal experimentation.

  6. Calculations of Photoemission from Rutile

    NASA Astrophysics Data System (ADS)

    Hjalmarson, Harold; Schultz, Peter; Moore, Chris

    2015-03-01

    Photoemission is a well-known mechanism for release of electrons from a surface during electrical breakdown of a gas such as air. During air breakdown, UV photons, which are emitted from the highly excited gas molecules, are absorbed in the surfaces such as the cathode and the anode. These absorbed photons create energetic electrons, and a small portion of these electrons reach the surface. Those that overcome the potential energy barrier at the surface tend to be emitted. In this talk, the Boltzmann equation that describes these phenomena is formulated. A Monte Carlo probabilistic method is used to obtain the rate of electron emission as a function of photon energy. The role of bandstructure effects will be discussed. This bandstructure information is obtained by using a density-functional theory (DFT) method. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

  7. The influence of surface structure on H4SiO4 oligomerization on rutile and amorphous TiO2 surfaces: an ATR-IR and synchrotron XPS study.

    PubMed

    Song, Yantao; Swedlund, Peter J; McIntosh, Grant J; Cowie, Bruce C C; Waterhouse, Geoffrey I N; Metson, James B

    2012-12-11

    Silicic acid (H(4)SiO(4)) is ubiquitous in natural aquatic systems. Applications of TiO(2) in these systems will be influenced by H(4)SiO(4) sorption and oligomerization reactions on the TiO(2) surface, and this can affect many aspects of TiO(2) reactivity. The spatial arrangement of sorption sites on a metal oxide surface can promote specific lateral interactions, such as oligomerization, between sorbed species. In this work we explore the relationship between surface structure and interfacial H(4)SiO(4) oligomerization by quantifying the extent of H(4)SiO(4) sorption and oligomerization on three TiO(2) phases; a rutile phase having well-developed (110) faces (R180), a rutile phase with poorly developed (110) faces (R60), and an amorphous TiO(2) (TiO(2(am))). The in situ ATR-IR spectra measured over time as 0.2 mM H(4)SiO(4) reacted with TiO(2) were quite different on the three TiO(2) phases. The percentage of the surface H(4)SiO(4) that was present as oligomers increased over time on all phases, but after 20 h almost all H(4)SiO(4) on the R180 surface was oligomeric, while the H(4)SiO(4) on TiO(2(am)) was predominantly monomeric. The extent of H(4)SiO(4) oligomerization on R60 was intermediate. When the TiO(2) phases reacted with 1.5 mM H(4)SiO(4) the ATR-IR spectra showed oligomeric silicates dominating the surface of all three TiO(2) phases; however, after 20 h the percentage of the surface H(4)SiO(4) present as three-dimensional polymers was ∼30, 10, and 0% on R180, R60, and TiO(2(am)) respectively. The Si 2s photoelectron peak binding energy (BE) and the H(4)SiO(4) surface coverage (Γ(Si)) were measured by XPS over a range of Γ(Si). For any given Γ(Si) the Si 2s BE's were in the order R180 > R60 > TiO(2(am)). A higher Si 2s BE indicates a greater degree of silicate polymerization. The ATR-IR and XPS results support the existing model for interfacial H(4)SiO(4) oligomerization where linear trimeric silicates are formed by insertion of a solution H(4)SiO(4

  8. Experimental macroevolution†

    PubMed Central

    Bell, Graham

    2016-01-01

    The convergence of several disparate research programmes raises the possibility that the long-term evolutionary processes of innovation and radiation may become amenable to laboratory experimentation. Ancestors might be resurrected directly from naturally stored propagules or tissues, or indirectly from the expression of ancestral genes in contemporary genomes. New kinds of organisms might be evolved through artificial selection of major developmental genes. Adaptive radiation can be studied by mimicking major ecological transitions in the laboratory. All of these possibilities are subject to severe quantitative and qualitative limitations. In some cases, however, laboratory experiments may be capable of illuminating the processes responsible for the evolution of new kinds of organisms. PMID:26763705

  9. Experimental macroevolution.

    PubMed

    Bell, Graham

    2016-01-13

    The convergence of several disparate research programmes raises the possibility that the long-term evolutionary processes of innovation and radiation may become amenable to laboratory experimentation. Ancestors might be resurrected directly from naturally stored propagules or tissues, or indirectly from the expression of ancestral genes in contemporary genomes. New kinds of organisms might be evolved through artificial selection of major developmental genes. Adaptive radiation can be studied by mimicking major ecological transitions in the laboratory. All of these possibilities are subject to severe quantitative and qualitative limitations. In some cases, however, laboratory experiments may be capable of illuminating the processes responsible for the evolution of new kinds of organisms. PMID:26763705

  10. EXPERIMENTAL THYROIDISM

    PubMed Central

    Cunningham, R. H.

    1898-01-01

    From the results of the various experiments already detailed I feel justified in drawing the following conclusions: (1) Absolutely fresh thyroid gland is not poisonous, in the usual sense of the term, when absorbed through the alimentary canal. (2) The symptoms of induced thyroidism are manifestations of an intoxication resulting from the ingestion of decomposed thyroid material, a conclusion that agrees in part with the previously related observations of Lanz. (3) The so-called experimental thyroidism is not specific for the thyroid only, for the ingestion of many substances derived from animal tissues other than the thyroid gland may produce an intoxication strikingly similar in every respect to that of experimental thyroidism. (4) Most, if not all, animal tissues yield substances which, if injected in large quantities directly into the circulation or beneath the skin, will produce an intoxication often very similar to that produced by injections of various substances derived from the fresh thyroid tissue. (5) The effects resulting from the intravascular or subcutaneous injections of aqueous extracts, decoctions and the concentrated extractives of the thyroid tissue, of the thymus, of muscle, etc., are by no means necessarily indicative of the function and the action of the hypothetical internal secretions of the same tissues during life. (6) The utilization of the fact that ingestion of decomposed thyroid material produces on certain occasions an intoxication with certain symptoms similar to some of those of G-raves' disease is not justifiable for the furtherance of the theory that the symptoms of exophthalmic goitre result from an over-production of the thyroid secretion. (7) Our results lead us to conclude with Drechsel that the fresh thyroid tissue yields at least probably two substances that are capable of palliating the symptoms of the acute cachexia in totally thyroidless dogs. (8) The thymus tissue also yields one and probably two substances that are as

  11. Constrained Surface Complexation Modeling: Rutile in RbCl, NaCl, and NaCF3SO3 Media to 250 °C

    SciTech Connect

    Machesky, Michael L.; Předota, Milan; Ridley, Moira K.; Wesolowski, David J.

    2015-06-01

    In this paper, a comprehensive set of molecular-level results, primarily from classical molecular dynamics (CMD) simulations, are used to constrain CD-MUSIC surface complexation model (SCM) parameters describing rutile powder titrations conducted in RbCl, NaCl, and NaTr (Tr = triflate, CF3SO3) electrolyte media from 25 to 250 °C. Rb+ primarily occupies the innermost tetradentate binding site on the rutile (110) surface at all temperatures (25, 150, 250 °C) and negative charge conditions (-0.1 and -0.2 C/m2) probed via CMD simulations, reflecting the small hydration energy of this large, monovalent cation. Consequently, variable SCM parameters (Stern-layer capacitance values and intrinsic Rb+ binding constants) were adjusted relatively easily to satisfactorily match the CMD and titration data. The larger hydration energy of Na+ results in a more complex inner-sphere distribution, which shifts from bidentate to tetradentate binding with increasing negative charge and temperature, and this distribution was not matched well for both negative charge conditions, which may reflect limitations in the CMD and/or SCM approaches. Finally, in particular, the CMD axial density profiles for Rb+ and Na+ reveal that peak binding distances shift toward the surface with increasing negative charge, suggesting that the CD-MUSIC framework may be improved by incorporating CD or Stern-layer capacitance values that vary with charge.

  12. Experimental radioimmunotherapy.

    PubMed

    Buchsbaum, D J; Langmuir, V K; Wessels, B W

    1993-01-01

    Radiolabeled monoclonal antibodies have been used for radioimmunotherapy studies with human tumor spheroids and murine and human tumor xenografts in experimental animals. This paper reviews the work that has been performed in these models with different types of cancer, and highlights those papers that have presented dosimetry estimates and attempts to correlate the findings. Radioimmunotherapy studies in multicell spheroids, as a model for micrometastases, have been performed in human neuroblastoma, colon cancer, and melanoma cell lines using 131I-, 125I-, 186Re-, and 212Bi-labeled antibodies. The uniform geometry of the spheroid has allowed radiation dose estimates to be made. Up to three logs of cell kill have been achieved with 131I- and 186Re-specific antibody with minimal toxicity from labeled nonspecific antibody, but 212Bi-antibody had little effect because of its short half-life as shown by Langmuir. It appears that the two most important factors for therapeutic efficacy in this model are good penetration of the radiolabeled antibody and an adequate radionuclide half-life to allow penetration of the immunoconjugate prior to significant radionuclide decay. Radioimmunotherapy studies in animals bearing transplants of colon cancer, leukemia, lymphoma, hepatoma, renal cell carcinoma, neuroblastoma, glioma, mammary carcinoma, small cell lung carcinoma, cervical carcinoma, ovarian carcinoma, and bladder cancer have been performed with 131I, 90Y, 186Re, 153Sm, and 177Lu beta emitting, and 212Bi alpha emitting radionuclides conjugated to monoclonal antibodies. A few studies compared different radionuclides in the same model system. The approaches that have been used in these studies to estimate tumor dosimetry include the MIRD approach, thermoluminescent dosimetry, autoradiography, and comparison to external irradiation. The majority of investigators have estimated the dose to tumor and normal organs using MIRD-based calculations (time-activity curve and

  13. O2 evolution on a clean partially reduced rutile TiO2(110) surface and on the same surface precovered with Au1 and Au2: the importance of spin conservation.

    PubMed

    Chrétien, Steeve; Metiu, Horia

    2008-08-21

    We have used spin-polarized density functional theory (DFT) to study O(2) evolution on a clean partially reduced rutile TiO(2)(110) surface (i.e., a surface having oxygen vacancies) and its interaction with Au(1) or Au(2) cluster adsorbed on it. We assume that the total spin of the electronic wave function is related to the number of unpaired spins (N(s)) and calculate the binding and the activation energies involved in O(2) evolution for fixed values of N(s). In addition to keeping N(s) constant, we assume that reactions in which the N(s) of the reactants differs from that of the products are very slow. The potential energy surfaces obtained in this way depend strongly on N(s). For example, O(2) dissociation at the vacancy site on a clean partially reduced TiO(2)(110) surface is exothermic by 0.85 eV in the triplet state and the highest activation energy in the chain of reactions leading to the O(2) dissociation is 0.67 eV. In the singlet state, O(2) dissociation is endothermic by 0.11 eV and the activation energy leading to dissociation is 1.30 eV. These observations are in qualitative agreement with scanning tunneling microscopy experiment in which O(2) dissociation on a partially reduced rutile TiO(2)(110) surface is observed at temperature as low as 120 K. In contrast, O(2) dissociation is predicted to be endothermic and is prevented by an activation barrier larger than 1 eV in all the previous DFT calculations, in which the DFT program varies N(s) to get the lowest energy state. We find that on a partially reduced rutile TiO(2)(110) with Au(1) and Au(2) preadsorbed on its surface, O(2) dissociates at the vacancy site: One oxygen atom fills the oxygen vacancy and the other becomes available for oxidation chemistry. This means that Au(1) and Au(2) supported on a partially reduced TiO(2)(110) surface is not an oxidation catalyst since the presence of oxygen turns it into a stoichiometric Au(n)/TiO(2)(110) surface. Finally, we find that the evolution of oxygen on

  14. Experimental Summary and Outlook

    SciTech Connect

    Peter Bosted

    2005-02-01

    A brief experimental overview of the workshop is given, with emphasis on polarized targets from the experimental equipment perspective, and kinematic coverage, precision, and newly investigated channels from the experimental results perspective.

  15. First-principles prediction of new photocatalyst materials with visible-light absorption and improved charge separation: surface modification of rutile TiO₂ with nanoclusters of MgO and Ga₂O₃.

    PubMed

    Nolan, Michael

    2012-11-01

    Titanium dioxide is an important and widely studied photocatalytic material, but to achieve photocatalytic activity under visible-light absorption, it needs to have a narrower band gap and reduced charge carrier recombination. First-principles simulations are presented in this paper to show that heterostructures of rutil TiO₂ modified with nanoclusters of MgO and Ga₂O₃ will be new photocatalytically active materials in the UV (MgO-TiO₂) and visible (Ga₂O₃-TiO₂) regions of the solar spectrum. In particular, our investigations of a model of the excited state of the heterostructures demonstrate that upon light excitation electrons and holes can be separated onto the TiO₂ surface and the metal oxide nanocluster, which will reduce charge recombination and improve photocatalytic activity. For MgO-modified TiO₂, no significant band gap change is predicted, but for Ga₂O₃-modified TiO₂ we predict a band gap change of up to 0.6 eV, which is sufficient to induce visible light absorption. Comparisons with unmodified TiO₂ and other TiO₂-based photocatalyst structures are presented.

  16. Spectral restoration in high resolution electron energy loss spectroscopy based on iterative semi-blind Lucy-Richardson algorithm applied to rutile surfaces

    SciTech Connect

    Lazzari, Rémi Li, Jingfeng Jupille, Jacques

    2015-01-15

    A new spectral restoration algorithm of reflection electron energy loss spectra is proposed. It is based on the maximum likelihood principle as implemented in the iterative Lucy-Richardson approach. Resolution is enhanced and point spread function recovered in a semi-blind way by forcing cyclically the zero loss to converge towards a Dirac peak. Synthetic phonon spectra of TiO{sub 2} are used as a test bed to discuss resolution enhancement, convergence benefit, stability towards noise, and apparatus function recovery. Attention is focused on the interplay between spectral restoration and quasi-elastic broadening due to free carriers. A resolution enhancement by a factor up to 6 on the elastic peak width can be obtained on experimental spectra of TiO{sub 2}(110) and helps revealing mixed phonon/plasmon excitations.

  17. Investigations of defect structures and g factors for octahedral (CrO6)7‑ and (VO6)8‑ clusters in rutile-type crystals

    NASA Astrophysics Data System (ADS)

    Zhu, Lianxuan; Wang, Minjie

    2016-05-01

    The electron paramagnetic resonance (EPR) g factor formulas for Cr5+ and V4+ ions in Al2O3, TiO2 and VO2 crystals are deduced from Jahn-Teller effect and contributions of the charge transfer (CT) levels. The tetragonal distortions. ΔR(R∥‑ R⊥) = ‑0.0184,‑0.0045 and ‑0.0124 nm, and Δ𝜃 = 0∘, ‑ 0.001∘ and 0∘, for Al2O3:Cr5+, TiO2:V4+ and VO2, respectively. The calculations of the g factors agree well with the experimental values. The contributions of the CT levels to g factors increase with the increasing valence state. It must be taken into account in the precise calculations of g factors for the high valence state d1 ions in crystals.

  18. Structure of Hydrated Zn2+ at the Rutile TiO2 (110)-Aqueous Solution Interface: Comparison of X-ray Standing Wave, X-ray Absorption Spectroscopy, and Density Functional Theory Results

    SciTech Connect

    Zhang, Zhan; Fenter, Paul; Kelly, Shelly D; Catalano, Jeffery G.; Bandura, Andrei V.; Kubicki, James D.; Sofo, Jorge O.; Wesolowski, David J; Machesky, Michael L.; Sturchio, N. C.; Bedzyk, Michael J.

    2006-01-01

    Adsorption of Zn{sup 2+} at the rutile TiO{sub 2} (110)-aqueous interface was studied with Bragg-reflection X-ray standing waves (XSW), polarization-dependent surface extended X-ray absorption fine structure (EXAFS) spectroscopy, and density functional theory (DFT) calculations to understand the interrelated issues of adsorption site, its occupancy, ion-oxygen coordination and hydrolysis. At pH 8, Zn{sup 2+} was found to adsorb as an inner-sphere complex at two different sites, i.e., monodentate above the bridging O site and bidentate between two neighboring terminal O sites. EXAFS results directly revealed a four or fivefold first shell coordination environment for adsorbed Zn{sup 2+} instead of the sixfold coordination found for aqueous species at this pH. DFT calculations confirmed the energetic stability of a lower coordination environment for the adsorbed species and revealed that the change to this coordination environment is correlated with the hydrolysis of adsorbed Zn{sup 2+}. In addition, the derived adsorption locations and the occupancy factors of both sites from three methods agree well, with some quantitative discrepancies in the minor site location among the XSW, EXAFS, and DFT methods. Additional XSW measurements showed that the adsorption sites of Zn{sup 2+} were unchanged at pH 6. However, the Zn{sup 2+} partitioning between the two sites changed substantially, with an almost equal distribution between the two types of sites at pH 6 compared to predominantly monodentate occupation at pH 8.

  19. A novel cesium hydroxygallophosphate with a layered structure built up of rutile ribbons: CsGa{sub 2}(OH){sub 2}[(PO{sub 4})H(PO{sub 4})

    SciTech Connect

    Lesage, J.; Guesdon, A. . E-mail: anne.guesdon@ensicaen.fr; Raveau, B.

    2006-12-15

    A new cesium gallophosphate, CsGa{sub 2}(OH){sub 2}[(PO{sub 4})H(PO{sub 4})], with an original layer structure has been synthesized by hydrothermal route characterized by single-crystal X-ray diffraction (R=0.0344, R{sub w}=0.0319). Its structure crystallizes in the monoclinic space group P2{sub 1}/a with cell parameters a=16.079(6)A, b=5.9873(12)A, c=4.5033(15)A, {beta}=93.36(4){sup o} and Z=2. It consists of [Ga(OH)PO{sub 4}]{sub {approx}} layers built up of rutile ribbons interconnected through PO{sub 4} tetrahedra. The structure of CsGa{sub 2}(OH){sub 2}[(PO{sub 4})H(PO{sub 4})] is closely related to those of (NH{sub 4})Ga(OH)PO{sub 4} and (en)Ga{sub 2}(OH){sub 2}(PO{sub 4}){sub 2} (en=ethylenediamine [H{sub 3}N(CH{sub 2}){sub 2}NH{sub 3}]{sup 2+}). The three structures differ mainly from each other by the relative positions and the spacing of the successive layers, which are governed by different hydrogen bonding modes between [Ga(OH)PO{sub 4}]{sub {approx}} layers and the interleaved species. The title compound presents strong symmetric hydrogen bonds O-H-O which bridge two PO{sub 4} tetrahedra of two successive layers. As a consequence, the distance between the layers is significantly shorter than in the two other amine compounds.

  20. A new LA-ICP-MS method for Ti-in-Quartz: Implications and application to HP rutile-quartz veins from the Czech Erzgebirge

    NASA Astrophysics Data System (ADS)

    Cruz-Uribe, A. M.; Mertz-Kraus, R.; Zack, T.; Feineman, M. D.; Woods, G.

    2014-12-01

    Experimental determination of the pressure and temperature controls on Ti solubility in quartz provide a calibration of the Ti-in-quartz (TitaniQ) geothermometer applicable to geologic conditions up to ~20 kbar (Thomas et al. (2010) Contrib Mineral Petrol 160, 743-759). One of the greatest limitations to analyzing Ti in metamorphic quartz by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is the lack of a suitable matrix-matched reference material. Typically LA-ICP-MS analyses of Ti in minerals use 49Ti as a normalizing mass because of an isobaric interference from 48Ca, which is present in most well characterized reference glasses, on 48Ti. The benefit of using a matrix-matched reference material to analyze Ti in quartz is the opportunity to use 48Ti (73.8 % abundance) as a normalizing mass, which results in an order of magnitude increase in signal strength compared to the less abundant isotope 49Ti (5.5 % abundance), thereby increasing the analytical precision. Here we characterize Ti-bearing SiO2 glasses from Heraeus Quarzglas and natural quartz grains from the Bishop Tuff by cathodoluminescence (CL) imaging, electron probe microanalysis (EPMA), and LA-ICP-MS, in order to determine their viability as reference materials for Ti in quartz. Titanium contents in low-CL rims in the Bishop Tuff quartz grains were determined to be homogenous by EPMA (41 ± 2 µg/g Ti, 2σ), and are a potential natural reference material. We present a new method for determining 48Ti concentrations in quartz by LA-ICP-MS at the 1 µg/g level, relevant to quartz in HP-LT terranes. We suggest that natural quartz such as the homogeneous low-CL rims of the Bishop Tuff quartz are more suitable than NIST reference glasses as an in-house reference material for low Ti concentrations because matrix effects are limited and Ca isobaric interferences are avoided, thus allowing for the use of 48Ti as a normalizing mass. Titanium concentration from 33 analyses of low

  1. Microexperiencia Educativa (Microeducational Experimentation).

    ERIC Educational Resources Information Center

    Burton Meis, Roberto

    1970-01-01

    Experimentation for educational reform in Argentina is limited to specifically designated schools which are to be in a permanent state of experimentation. This article presents the official statements designating the experimental schools and includes remarks covering administration, evaluation, and supervision. (VM)

  2. The Experimental Hydrology Wiki

    NASA Astrophysics Data System (ADS)

    Blume, T.; Tromp-van Meerveld, I.

    2009-04-01

    The „Experimental Hydrology Wiki" is a forum for experimental hydrologists, which allows us to learn about, recommend, question and discuss methods and equipment of experimental hydrology. As a database of "lessons learned" it does not only contain short descriptions of specific experimental equipment but also information on encountered errors and problems and recommendations on how to deal with them. This makes valuable personal field experience accessible to a wider audience and thus helps us in not making the same mistakes others have made before us. The general idea and layout of the Experimental Hydrology Wiki is presented here along with an invitation to all experimental hydrologists to contribute with their knowledge and experience! http://www.experimental-hydrology.net/

  3. Is animal experimentation fundamental?

    PubMed

    d'Acampora, Armando José; Rossi, Lucas Félix; Ely, Jorge Bins; de Vasconcellos, Zulmar Acciolli

    2009-01-01

    The understanding about the utilization of experimental animals in scientific research and in teaching is many times a complex issue. Special attention needs to be paid to attain the understanding by the general public of the importance of animal experimentation in experimental research and in undergraduate medical teaching. Experimental teaching and research based on the availability of animals for experimentation is important and necessary for the personal and scientific development of the physician-to-be. The technological arsenal which intends to mimic experimentation animals and thus fully replace their use many times does not prove to be compatible with the reality of the living animal. The purpose of this paper is to discuss aspects concerning this topic, bringing up an issue which is complex and likely to arouse in-depth reflections.

  4. 7. VIEW WEST, FERNOW EXPERIMENTAL FOREST WELL HOUSE, FERNOW EXPERIMENTAL ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    7. VIEW WEST, FERNOW EXPERIMENTAL FOREST WELL HOUSE, FERNOW EXPERIMENTAL FOREST BUNKHOUSE, FERNOW EXPERIMENTAL FOREST GARAGE, AND FERNOW EXPERIMENTAL FOREST RESIDENCE. - Parsons Nursery, South side of U.S. Route 219, Parsons, Tucker County, WV

  5. The Experimental Hydrology Wiki

    NASA Astrophysics Data System (ADS)

    Blume, Theresa; van Meerveld, Ilja; Graeff, Thomas

    2013-04-01

    The "Experimental Hydrology Wiki" is a forum for hydrologists to learn about, recommend, question and discuss new and established, basic and advanced methods and equipment for hydrological research. As a database of "lessons learned" it does not only contain short descriptions of specific experimental equipment but also information on encountered errors and problems and recommendations on how to deal with them. This makes valuable personal field experience accessible to a wider audience. The Wiki allows experimentalists to share and find solutions for common problems and thus helps us in not making the same mistakes others have made before us. At the same time modellers can use this platform to find information on sources of error and uncertainty in the data they use for model validation and calibration. The general idea and layout of the Experimental Hydrology Wiki is presented here along with an invitation to all experimental hydrologists to contribute their knowledge and experiences! http://www.experimental- hydrology.net/

  6. Experimental Semiotics: A Review

    PubMed Central

    Galantucci, Bruno; Garrod, Simon

    2010-01-01

    In the last few years a new line of research has appeared in the literature. This line of research, which may be referred to as experimental semiotics (ES; Galantucci, 2009; Galantucci and Garrod, 2010), focuses on the experimental investigation of novel forms of human communication. In this review we will (a) situate ES in its conceptual context, (b) illustrate the main varieties of studies thus far conducted by experimental semioticians, (c) illustrate three main themes of investigation which have emerged within this line of research, and (d) consider implications of this work for cognitive neuroscience. PMID:21369364

  7. Experimental semiotics: a review.

    PubMed

    Galantucci, Bruno; Garrod, Simon

    2011-01-01

    In the last few years a new line of research has appeared in the literature. This line of research, which may be referred to as experimental semiotics (ES; Galantucci, 2009; Galantucci and Garrod, 2010), focuses on the experimental investigation of novel forms of human communication. In this review we will (a) situate ES in its conceptual context, (b) illustrate the main varieties of studies thus far conducted by experimental semioticians, (c) illustrate three main themes of investigation which have emerged within this line of research, and (d) consider implications of this work for cognitive neuroscience.

  8. Designing an Experimental "Accident"

    ERIC Educational Resources Information Center

    Picker, Lester

    1974-01-01

    Describes an experimental "accident" that resulted in much student learning, seeks help in the identification of nematodes, and suggests biology teachers introduce similar accidents into their teaching to stimulate student interest. (PEB)

  9. Nuclear test experimental science

    SciTech Connect

    Struble, G.L.; Middleton, C.; Bucciarelli, G.; Carter, J.; Cherniak, J.; Donohue, M.L.; Kirvel, R.D.; MacGregor, P.; Reid, S.

    1989-01-01

    This report discusses research being conducted at Lawrence Livermore Laboratory under the following topics: prompt diagnostics; experimental modeling, design, and analysis; detector development; streak-camera data systems; weapons supporting research.

  10. Summary of experimental talks

    SciTech Connect

    Derrick, M.

    1999-12-08

    This final talk of the meeting briefly discussed a number of experimental topics that the author found particularly interesting in the area of High Energy Physics. It also includes some critical comments about the future direction of their discipline.

  11. Mechanical properties of one-dimensional nanostructures, experimental measurement and numerical simulation

    NASA Astrophysics Data System (ADS)

    Wu, Xiaoxia

    nanoindentation of 1D nanostructures, resulting in unreliable data on mechanical properties of 1D nanostructures. In this work, factors which could affect measured nanostructure-on-substrate system modulus such as the selection of a substrate to support the nanostructure, the cross section of a nanostructure, the width-to-thickness ratio (or diameter) of a nanostructure, and the nanostructure-substrate contact mechanism were first subjected to a systematic experimental investigation. A Finite Element Modeling (FEM)-based data inverse analysis process was then proposed to extract the intrinsic modulus of nanostructures from measured system modulus. This data inverse process solved the intrinsic modulus of nanostructures by equalizing the simulated nanostructure-on-substrate modulus with the experimentally measured system modulus. In finite element simulation, another important aspect: the experimental indenter area function in addition to aforementioned other factors was carefully considered. Based on systematic experimental and numerical investigations, the Young's modulus of rutile TiO2 nanoribbons, CaB6 nanostructures, SrB6 nanostructures and BaB6 nanostructures was determined to be 360, 175--365, 300--425 and 270--475 GPa, respectively. These numbers are the first reported mechanical properties for these nanomaterials. Besides the finite element simulation, an "analytical" solution to obtain a nanostructure-on-substrate system modulus is also presented. Compared to the finite element simulation, the solution could significantly reduce processing time for the data inverse method. It is applicable to a nanostructure with a width to thickness ratio larger than 4. This part of dissertation work clearly demonstrates that both experimental and numerical investigations are needed for studying of mechanical properties of 1D nanostructures by nanoindentation.

  12. Saturation curve of SiO{sub 2} component in rutile-type GeO{sub 2}: A recoverable high-temperature pressure standard from 3 GPa to 10 GPa

    SciTech Connect

    Leinenweber, Kurt; Gullikson, Amber L.; Stoyanov, Emil; Malik, Abds-Sami

    2015-09-15

    The accuracy and precision of pressure measurements and the pursuit of reliable and readily available pressure scales at simultaneous high temperatures and pressures are still topics in development in high pressure research despite many years of work. In situ pressure scales based on x-ray diffraction are widely used but require x-ray access, which is lacking outside of x-ray beam lines. Other methods such as fixed points require several experiments to bracket a pressure calibration point. In this study, a recoverable high-temperature pressure gauge for pressures ranging from 3 GPa to 10 GPa is presented. The gauge is based on the pressure-dependent solubility of an SiO{sub 2} component in the rutile-structured phase of GeO{sub 2} (argutite), and is valid when the argutite solid solution coexists with coesite. The solid solution varies strongly in composition, mainly in pressure but also somewhat in temperature, and the compositional variations are easily detected by x-ray diffraction of the recovered products because of significant changes in the lattice parameters. The solid solution is measured here on two isotherms, one at 1200 °C and the other at 1500 °C, and is developed as a pressure gauge by calibrating it against three fixed points for each temperature and against the lattice parameter of MgO measured in situ at a total of three additional points. A somewhat detailed thermodynamic analysis is then presented that allows the pressure gauge to be used at other temperatures. This provides a way to accurately and reproducibly evaluate the pressure in high pressure experiments and applications in this pressure-temperature range, and could potentially be used as a benchmark to compare various other pressure scales under high temperature conditions. - Graphical abstract: The saturation curve of SiO{sub 2} in TiO{sub 2} shows a strong pressure dependence and a strong dependence of unit cell volume on composition. This provides an opportunity to use this

  13. Integrated Bayesian Experimental Design

    NASA Astrophysics Data System (ADS)

    Fischer, R.; Dreier, H.; Dinklage, A.; Kurzan, B.; Pasch, E.

    2005-11-01

    Any scientist planning experiments wants to optimize the design of a future experiment with respect to best performance within the scheduled experimental scenarios. Bayesian Experimental Design (BED) aims in finding optimal experimental settings based on an information theoretic utility function. Optimal design parameters are found by maximizing an expected utility function where the future data and the parameters of physical scenarios of interest are marginalized. The goal of the Integrated Bayesian Experimental Design (IBED) concept is to combine experiments as early as on the design phase to mutually exploit the benefits of the other experiments. The Bayesian Integrated Data Analysis (IDA) concept of linking interdependent measurements to provide a validated data base and to exploit synergetic effects will be used to design meta-diagnostics. An example is given by the Thomson scattering (TS) and the interferometry (IF) diagnostics individually, and a set of both. In finding the optimal experimental design for the meta-diagnostic, TS and IF, the strengths of both experiments can be combined to synergistically increase the reliability of results.

  14. Experimental scattershot boson sampling

    PubMed Central

    Bentivegna, Marco; Spagnolo, Nicolò; Vitelli, Chiara; Flamini, Fulvio; Viggianiello, Niko; Latmiral, Ludovico; Mataloni, Paolo; Brod, Daniel J.; Galvão, Ernesto F.; Crespi, Andrea; Ramponi, Roberta; Osellame, Roberto; Sciarrino, Fabio

    2015-01-01

    Boson sampling is a computational task strongly believed to be hard for classical computers, but efficiently solvable by orchestrated bosonic interference in a specialized quantum computer. Current experimental schemes, however, are still insufficient for a convincing demonstration of the advantage of quantum over classical computation. A new variation of this task, scattershot boson sampling, leads to an exponential increase in speed of the quantum device, using a larger number of photon sources based on parametric down-conversion. This is achieved by having multiple heralded single photons being sent, shot by shot, into different random input ports of the interferometer. We report the first scattershot boson sampling experiments, where six different photon-pair sources are coupled to integrated photonic circuits. We use recently proposed statistical tools to analyze our experimental data, providing strong evidence that our photonic quantum simulator works as expected. This approach represents an important leap toward a convincing experimental demonstration of the quantum computational supremacy. PMID:26601164

  15. Experimental scattershot boson sampling.

    PubMed

    Bentivegna, Marco; Spagnolo, Nicolò; Vitelli, Chiara; Flamini, Fulvio; Viggianiello, Niko; Latmiral, Ludovico; Mataloni, Paolo; Brod, Daniel J; Galvão, Ernesto F; Crespi, Andrea; Ramponi, Roberta; Osellame, Roberto; Sciarrino, Fabio

    2015-04-01

    Boson sampling is a computational task strongly believed to be hard for classical computers, but efficiently solvable by orchestrated bosonic interference in a specialized quantum computer. Current experimental schemes, however, are still insufficient for a convincing demonstration of the advantage of quantum over classical computation. A new variation of this task, scattershot boson sampling, leads to an exponential increase in speed of the quantum device, using a larger number of photon sources based on parametric down-conversion. This is achieved by having multiple heralded single photons being sent, shot by shot, into different random input ports of the interferometer. We report the first scattershot boson sampling experiments, where six different photon-pair sources are coupled to integrated photonic circuits. We use recently proposed statistical tools to analyze our experimental data, providing strong evidence that our photonic quantum simulator works as expected. This approach represents an important leap toward a convincing experimental demonstration of the quantum computational supremacy.

  16. SPHINX experimenters information package

    SciTech Connect

    Zarick, T.A.

    1996-08-01

    This information package was prepared for both new and experienced users of the SPHINX (Short Pulse High Intensity Nanosecond X-radiator) flash X-Ray facility. It was compiled to help facilitate experiment design and preparation for both the experimenter(s) and the SPHINX operational staff. The major areas covered include: Recording Systems Capabilities,Recording System Cable Plant, Physical Dimensions of SPHINX and the SPHINX Test cell, SPHINX Operating Parameters and Modes, Dose Rate Map, Experiment Safety Approval Form, and a Feedback Questionnaire. This package will be updated as the SPHINX facilities and capabilities are enhanced.

  17. Experimental probes of axions

    SciTech Connect

    Chou, Aaron S.; /Fermilab

    2009-10-01

    Experimental searches for axions or axion-like particles rely on semiclassical phenomena resulting from the postulated coupling of the axion to two photons. Sensitive probes of the extremely small coupling constant can be made by exploiting familiar, coherent electromagnetic laboratory techniques, including resonant enhancement of transitions using microwave and optical cavities, Bragg scattering, and coherent photon-axion oscillations. The axion beam may either be astrophysical in origin as in the case of dark matter axion searches and solar axion searches, or created in the laboratory from laser interactions with magnetic fields. This note is meant to be a sampling of recent experimental results.

  18. Experimentation: the next step

    PubMed Central

    Marinker, Marshall

    1987-01-01

    General practice has entered a period of accelerating change, and those responsible for planning its development now put forward a variety of promising proposals. Unless provision is made for large scale experimentation and scientific evaluation, the direction of future change will be determined not by evidence but by rhetoric. A framework for creating and evaluating a substantial programme of experimentation is suggested. The programme is the logical next step in the process of change which was given impetus by the publication of the government green paper. It should be seen as a professional, moral and political priority. PMID:3681850

  19. EXPERIMENTAL ANIMAL MAINTENANCE

    DOEpatents

    Finkel, M.P.

    1962-01-22

    A method of housing experimental animals such as mice in individual tube- like plastic enclosures is described. Contrary to experience, when this was tried with metal the mice did not become panicky. Group housing, with its attendant difficulties, may thus be dispensed with. (AEC)

  20. Communicating Uncertain Experimental Evidence

    ERIC Educational Resources Information Center

    Davis, Alexander L.; Fischhoff, Baruch

    2014-01-01

    Four experiments examined when laypeople attribute unexpected experimental outcomes to error, in foresight and in hindsight, along with their judgments of whether the data should be published. Participants read vignettes describing hypothetical experiments, along with the result of the initial observation, considered as either a possibility…

  1. Experimental Trends in Videoprogramming.

    ERIC Educational Resources Information Center

    Kalba, Kas

    A review of experimental activities in educational broadcasting shows that mass television and instructional television, as we think of them today, are likely to constitute two points on a greatly expanded spectrum of television concepts in the future. Television will become much more like the publishing industry, with its mix of pamphlets, art…

  2. Experimental fluvial geomorphology

    SciTech Connect

    Schumm, S.A.; Mosley, M.P.; Weaver, W.

    1987-01-01

    The authors bring together the results of several years of experimental work in drainage basin evolution, hydrology, river-channel morphology, and sedimentology. These investigations are related to real-world applications, particularly geological exploration and mapping. This text shows how awareness of natural phenomena can improve management of the natural environment, such as the control of rivers and eroding gullies.

  3. Administrative Aspects of Human Experimentation.

    ERIC Educational Resources Information Center

    Irvine, George W.

    1992-01-01

    The following administrative aspects of scientific experimentation with human subjects are discussed: the definition of human experimentation; the distinction between experimentation and treatment; investigator responsibility; documentation; the elements and principles of informed consent; and the administrator's role in establishing and…

  4. Teaching experimental design.

    PubMed

    Fry, Derek J

    2014-01-01

    Awareness of poor design and published concerns over study quality stimulated the development of courses on experimental design intended to improve matters. This article describes some of the thinking behind these courses and how the topics can be presented in a variety of formats. The premises are that education in experimental design should be undertaken with an awareness of educational principles, of how adults learn, and of the particular topics in the subject that need emphasis. For those using laboratory animals, it should include ethical considerations, particularly severity issues, and accommodate learners not confident with mathematics. Basic principles, explanation of fully randomized, randomized block, and factorial designs, and discussion of how to size an experiment form the minimum set of topics. A problem-solving approach can help develop the skills of deciding what are correct experimental units and suitable controls in different experimental scenarios, identifying when an experiment has not been properly randomized or blinded, and selecting the most efficient design for particular experimental situations. Content, pace, and presentation should suit the audience and time available, and variety both within a presentation and in ways of interacting with those being taught is likely to be effective. Details are given of a three-day course based on these ideas, which has been rated informative, educational, and enjoyable, and can form a postgraduate module. It has oral presentations reinforced by group exercises and discussions based on realistic problems, and computer exercises which include some analysis. Other case studies consider a half-day format and a module for animal technicians. PMID:25541547

  5. Teaching experimental design.

    PubMed

    Fry, Derek J

    2014-01-01

    Awareness of poor design and published concerns over study quality stimulated the development of courses on experimental design intended to improve matters. This article describes some of the thinking behind these courses and how the topics can be presented in a variety of formats. The premises are that education in experimental design should be undertaken with an awareness of educational principles, of how adults learn, and of the particular topics in the subject that need emphasis. For those using laboratory animals, it should include ethical considerations, particularly severity issues, and accommodate learners not confident with mathematics. Basic principles, explanation of fully randomized, randomized block, and factorial designs, and discussion of how to size an experiment form the minimum set of topics. A problem-solving approach can help develop the skills of deciding what are correct experimental units and suitable controls in different experimental scenarios, identifying when an experiment has not been properly randomized or blinded, and selecting the most efficient design for particular experimental situations. Content, pace, and presentation should suit the audience and time available, and variety both within a presentation and in ways of interacting with those being taught is likely to be effective. Details are given of a three-day course based on these ideas, which has been rated informative, educational, and enjoyable, and can form a postgraduate module. It has oral presentations reinforced by group exercises and discussions based on realistic problems, and computer exercises which include some analysis. Other case studies consider a half-day format and a module for animal technicians.

  6. Two Challenges for Experimenters

    NASA Astrophysics Data System (ADS)

    Berry, R. Stephen

    2013-10-01

    In recent years, several theoretical studies have indicated potentially interesting, even perhaps surprising phenomena that could be observed by experiment-but have not yet been studied in the laboratory. Here we give the background and motivation for two of these, with the admitted goal of stimulating those experimental studies. The two topics: (1) the production and study of amorphous alkali metal halide clusters; (2) Penning detachment, the analogue of the well-studied Penning ionization, but in which an electron is detached from a negative ion, rather than from a neutral atom, by energy transfer in collision with an excited atom. The latter phenomenon could be particularly relevant for stellar atmospheres where negative ions are abundant. In each case, we indicate the implications and potential of having substantive experimental information about each, in effect explaining the motivation to carry out the experiments.

  7. Geoengineering as Collective Experimentation.

    PubMed

    Stilgoe, Jack

    2016-06-01

    Geoengineering is defined as the 'deliberate and large-scale intervention in the Earth's climatic system with the aim of reducing global warming'. The technological proposals for doing this are highly speculative. Research is at an early stage, but there is a strong consensus that technologies would, if realisable, have profound and surprising ramifications. Geoengineering would seem to be an archetype of technology as social experiment, blurring lines that separate research from deployment and scientific knowledge from technological artefacts. Looking into the experimental systems of geoengineering, we can see the negotiation of what is known and unknown. The paper argues that, in renegotiating such systems, we can approach a new mode of governance-collective experimentation. This has important ramifications not just for how we imagine future geoengineering technologies, but also for how we govern geoengineering experiments currently under discussion.

  8. Geoengineering as Collective Experimentation.

    PubMed

    Stilgoe, Jack

    2016-06-01

    Geoengineering is defined as the 'deliberate and large-scale intervention in the Earth's climatic system with the aim of reducing global warming'. The technological proposals for doing this are highly speculative. Research is at an early stage, but there is a strong consensus that technologies would, if realisable, have profound and surprising ramifications. Geoengineering would seem to be an archetype of technology as social experiment, blurring lines that separate research from deployment and scientific knowledge from technological artefacts. Looking into the experimental systems of geoengineering, we can see the negotiation of what is known and unknown. The paper argues that, in renegotiating such systems, we can approach a new mode of governance-collective experimentation. This has important ramifications not just for how we imagine future geoengineering technologies, but also for how we govern geoengineering experiments currently under discussion. PMID:25862639

  9. Experimental adaptive Bayesian tomography

    NASA Astrophysics Data System (ADS)

    Kravtsov, K. S.; Straupe, S. S.; Radchenko, I. V.; Houlsby, N. M. T.; Huszár, F.; Kulik, S. P.

    2013-06-01

    We report an experimental realization of an adaptive quantum state tomography protocol. Our method takes advantage of a Bayesian approach to statistical inference and is naturally tailored for adaptive strategies. For pure states, we observe close to N-1 scaling of infidelity with overall number of registered events, while the best nonadaptive protocols allow for N-1/2 scaling only. Experiments are performed for polarization qubits, but the approach is readily adapted to any dimension.

  10. Experimental Neutrino Physics

    ScienceCinema

    Walter, Chris [Duke University, Durham, North Carolina, United States

    2016-07-12

    In this talk, I will review how a set of experiments in the last decade has given us our current understanding of neutrino properties.  I will show how experiments in the last year or two have clarified this picture, and will discuss how new experiments about to start will address remaining questions.  I will particularly emphasize the relationship between various experimental techniques.

  11. Blois V: Experimental summary

    SciTech Connect

    Albrow, M.G.

    1993-09-01

    The author gives a summary talk of the best experimental data given at the Vth Blois Workshop on Elastic and Diffractive Scattering. He addresses the following eight areas in his talk: total and elastic cross sections; single diffractive excitation; electron-proton scattering; di-jets and rapidity gaps; areas of future study; spins and asymmetries; high-transverse momentum and masses at the Tevatron; and disoriented chiral condensates and cosmic radiation.

  12. Experimental Models of Cryptococcosis

    PubMed Central

    Sabiiti, Wilber; May, Robin C.; Pursall, E. Rhiannon

    2012-01-01

    Cryptococcosis is a life-threatening fungal disease that infects around one million people each year. Establishment and progression of disease involves a complex interplay between the fungus and a diverse range of host cell types. Over recent years, numerous cellular, tissue, and animal models have been exploited to probe this host-pathogen interaction. Here we review the range of experimental models that are available for cryptococcosis research and compare the relative advantages and limitations of the different systems. PMID:22007224

  13. MSFC Skylab experimenter's reference

    NASA Technical Reports Server (NTRS)

    1974-01-01

    The methods and techniques for experiment development and integration that evolved during the Skylab Program are described to facilitate transferring this experience to experimenters in future manned space programs. Management responsibilities and the sequential process of experiment evolution from initial concept through definition, development, integration, operation and postflight analysis are outlined in the main text and amplified, as appropriate, in appendixes. Emphasis is placed on specific lessons learned on Skylab that are worthy of consideration by future programs.

  14. Modeling and experimental studies of oxide covered metal surfaces: TiO sub 2 /Ti a model system

    SciTech Connect

    Smyrl, W.H.

    1991-01-01

    Prior work in our laboratories at the Corrosion Research Center has shown that thin, anodic TiO{sub 2} films formed by the Slow Growth Mode (SGM) on polycrystalline titanium and microcrystalline with a texture that varies from one metal grain to another. Furthermore, the underlying metal grains are mapped by the photoelectrochemical response of the oxide. The same characteristics have also been demonstrated in our laboratory for ZnO grown on Zn. The TiO{sub 2}/Ti system has been chosen for study both because of its importance in energy systems, and because it can serve as a model system for other metal-metal oxide couples. The investigations of anodic TiO{sub 2} films on Ti have shown that the properties of thin films are consistent with the rutile form of the oxide. Both experimental data and theoretical calculations show the close resemblance to results on single crystal TiO{sub 2}. Furthermore, the modeling studies reveal that the optical transitions near the bandedge arise from the bulk band structure. The photoelectrochemical properties of anodic TiO{sub 2} films have now been shown to obey the simple Gaertner-Butler model for the semiconductor-electrolyte interface, with a few modifications. The most important deviation has now been shown to be a result of multiple internal reflections in the oxide film.

  15. Modeling and experimental studies of oxide covered metal surfaces: TiO{sub 2}/Ti a model system. Progress report

    SciTech Connect

    Smyrl, W.H.

    1991-12-31

    Prior work in our laboratories at the Corrosion Research Center has shown that thin, anodic TiO{sub 2} films formed by the Slow Growth Mode (SGM) on polycrystalline titanium and microcrystalline with a texture that varies from one metal grain to another. Furthermore, the underlying metal grains are mapped by the photoelectrochemical response of the oxide. The same characteristics have also been demonstrated in our laboratory for ZnO grown on Zn. The TiO{sub 2}/Ti system has been chosen for study both because of its importance in energy systems, and because it can serve as a model system for other metal-metal oxide couples. The investigations of anodic TiO{sub 2} films on Ti have shown that the properties of thin films are consistent with the rutile form of the oxide. Both experimental data and theoretical calculations show the close resemblance to results on single crystal TiO{sub 2}. Furthermore, the modeling studies reveal that the optical transitions near the bandedge arise from the bulk band structure. The photoelectrochemical properties of anodic TiO{sub 2} films have now been shown to obey the simple Gaertner-Butler model for the semiconductor-electrolyte interface, with a few modifications. The most important deviation has now been shown to be a result of multiple internal reflections in the oxide film.

  16. MODELING THE INTERACTION OF AGROCHEMICALS WITH ENVIRONMENTAL SURFACES: PESTICIDES ON RUTILE AND ORGANO-RUTILE SURFACES

    EPA Science Inventory

    Non-bonded interactions between model pesticides and organo-mineral surfaces have been studied using molecular mechanical conformational calculations and molecular dynamics simulations. The minimum energy conformations and relative binding energies for the interaction of atrazine...

  17. EXPERIMENTAL ANIMAL WATERING DEVICE

    DOEpatents

    Finkel, M.P.

    1964-04-01

    A device for watering experimental animals confined in a battery of individual plastic enclosures is described. It consists of a rectangular plastic enclosure having a plurality of fluid-tight compartments, each with a drinking hole near the bottom and a filling hole on the top. The enclosure is immersed in water until filled, its drinking holes sealed with a strip of tape, and it is then placed in the battery. The tape sealing prevents the flow of water from the device, but permits animals to drink by licking the drinking holes. (AEC)

  18. Electrodeless Experimental Thruster

    SciTech Connect

    Brainerd, Jerome J.; Reisz, Al

    2009-03-16

    An electrodeless experimental electric thruster has been built and tested at the NASA Marshall Space Flight Center (MSFC). The plasma is formed by Electron-Cyclotron Resonance (ECR) absorption of RF waves (microwaves). The RF source operates in the 1 to 2 kW range. The plasma is overdense and is confined radially by an applied axial dc magnetic field. The field is shaped by a strong magnetic mirror on the upstream end and a magnetic nozzle on the downstream end. Argon is used as the propellant. The velocity profile in the exhaust plume has been measured with Laser Induced Fluorescence (LIF). An unusual bimodal velocity profile has been measured.

  19. Outsourcing of experimental work.

    PubMed

    Nielsen, Henrik

    2011-01-01

    With the development of new technologies for simultaneous analysis of many genes, transcripts, or proteins (the "omics" revolution), it has become common to outsource parts of the experimental work. In order to maintain the integrity of the research projects, it is important that the interphase between the researcher and the service is further developed. This involves robust protocols for sample preparation, an informed choice of analytical tool, development of standards for individual technologies, and transparent data analysis. This chapter introduces some of the problems related to analysis of RNA samples in the "omics" context and gives a few hints and key references related to sample preparation for the non-specialist.

  20. [Animal experimentation in Israel].

    PubMed

    Epstein, Yoram; Leshem, Micah

    2002-04-01

    In 1994 the Israeli parliament (Knesset) amended the Cruelty to Animals Act to regulate the use of experimental animals. Accordingly, animal experiments can only be carried out for the purposes of promoting health and medical science, reducing suffering, advancing scientific research, testing or production of materials and products (excluding cosmetics and cleaning products) and education. Animal experiments are only permitted if alternative methods are not possible. The National Board for Animal Experimentation was established to implement the law. Its members are drawn from government ministries, representatives of doctors, veterinarians, and industry organizations, animal rights groups, and academia. In order to carry out an animal experiment, the institution, researchers involved, and the specific experiment, all require approval by the Board. To date the Board has approved some 35 institutions, about half are public institutions (universities, hospitals and colleges) and the rest industrial firms in biotechnology and pharmaceutics. In 2000, 250,000 animals were used in research, 85% were rodents, 11% fowls, 1,000 other farm animals, 350 dogs and cats, and 39 monkeys. Academic institutions used 74% of the animals and industry the remainder. We also present summarized data on the use of animals in research in other countries.

  1. Experimental Quantum Coin Tossing

    NASA Astrophysics Data System (ADS)

    Molina-Terriza, G.; Vaziri, A.; Ursin, R.; Zeilinger, A.

    2005-01-01

    In this Letter we present the first implementation of a quantum coin-tossing protocol. This protocol belongs to a class of “two-party” cryptographic problems, where the communication partners distrust each other. As with a number of such two-party protocols, the best implementation of the quantum coin tossing requires qutrits, resulting in a higher security than using qubits. In this way, we have also performed the first complete quantum communication protocol with qutrits. In our experiment the two partners succeeded to remotely toss a row of coins using photons entangled in the orbital angular momentum. We also show the experimental bounds of a possible cheater and the ways of detecting him.

  2. Experimental traumatic brain injury

    PubMed Central

    2010-01-01

    Traumatic brain injury, a leading cause of death and disability, is a result of an outside force causing mechanical disruption of brain tissue and delayed pathogenic events which collectively exacerbate the injury. These pathogenic injury processes are poorly understood and accordingly no effective neuroprotective treatment is available so far. Experimental models are essential for further clarification of the highly complex pathology of traumatic brain injury towards the development of novel treatments. Among the rodent models of traumatic brain injury the most commonly used are the weight-drop, the fluid percussion, and the cortical contusion injury models. As the entire spectrum of events that might occur in traumatic brain injury cannot be covered by one single rodent model, the design and choice of a specific model represents a major challenge for neuroscientists. This review summarizes and evaluates the strengths and weaknesses of the currently available rodent models for traumatic brain injury. PMID:20707892

  3. Experimental evolution gone wild.

    PubMed

    Scheinin, M; Riebesell, U; Rynearson, T A; Lohbeck, K T; Collins, S

    2015-05-01

    Because of their large population sizes and rapid cell division rates, marine microbes have, or can generate, ample variation to fuel evolution over a few weeks or months, and subsequently have the potential to evolve in response to global change. Here we measure evolution in the marine diatom Skeletonema marinoi evolved in a natural plankton community in CO2-enriched mesocosms deployed in situ. Mesocosm enclosures are typically used to study how the species composition and biogeochemistry of marine communities respond to environmental shifts, but have not been used for experimental evolution to date. Using this approach, we detect a large evolutionary response to CO2 enrichment in a focal marine diatom, where population growth rate increased by 1.3-fold in high CO2-evolved lineages. This study opens an exciting new possibility of carrying out in situ evolution experiments to understand how marine microbial communities evolve in response to environmental change.

  4. [Experimental stab wound].

    PubMed

    Hirt, Miroslav; Vorel, František; Zelený, Michal

    2015-01-01

    Stab wounds caused by knives and daggers are usually of different appearances. The knife wound has one edge sharp while the second one is blunt. The wound caused by blow of dagger has both edges sharp. The forensic expert must very often decide whether the knife or dagger was used. The aim of this experimental work was to show how a single-edged knife penetrates the skin and causes the wound typical for the double-edged dagger. The fact was verified. The wound typical for dagger can be found if the knife is used only according to the scheme. The forensic expert can say that a one cutting edge knife was used if the one edge of wound is squared and the other one is sharp. If the both of them are sharp, forensic expert must be very careful in his decision.Key words: stab wounds - knife - dagger - forensic expertise. PMID:25671417

  5. Experimental Quantum Error Detection

    PubMed Central

    Jin, Xian-Min; Yi, Zhen-Huan; Yang, Bin; Zhou, Fei; Yang, Tao; Peng, Cheng-Zhi

    2012-01-01

    Faithful transmission of quantum information is a crucial ingredient in quantum communication networks. To overcome the unavoidable decoherence in a noisy channel, to date, many efforts have been made to transmit one state by consuming large numbers of time-synchronized ancilla states. However, such huge demands of quantum resources are hard to meet with current technology and this restricts practical applications. Here we experimentally demonstrate quantum error detection, an economical approach to reliably protecting a qubit against bit-flip errors. Arbitrary unknown polarization states of single photons and entangled photons are converted into time bins deterministically via a modified Franson interferometer. Noise arising in both 10 m and 0.8 km fiber, which induces associated errors on the reference frame of time bins, is filtered when photons are detected. The demonstrated resource efficiency and state independence make this protocol a promising candidate for implementing a real-world quantum communication network. PMID:22953047

  6. Experimental Economics in the Classroom.

    ERIC Educational Resources Information Center

    Walker, Joe

    1987-01-01

    Discusses and describes several studies regarding experimental economics. Recommends that economics teachers and textbook authors incorporate more of these projects into their work. Presents a consumer demand exercise that incorporates experimental economics into the classroom. (RKM)

  7. Antecedents and analogues - Experimental aircraft

    NASA Technical Reports Server (NTRS)

    Smith, R. H.

    1978-01-01

    The paper reviews the development of experimental aircraft from 1953 to the present. Consideration is given to the X-series experimental aircraft, to X-15 (the first aerospace plane), to the transition of experimental aircraft to high-speed flight, to XB-70 research, to lifting body research aircraft, and to current high-speed flight research.

  8. Experimental Particle Physics

    SciTech Connect

    Rosenfeld, Carl; Mishra, Sanjib R.; Petti, Roberto; Purohit, Milind V.

    2014-08-31

    The high energy physics group at the University of South Carolina, under the leadership of Profs. S.R. Mishra, R. Petti, M.V. Purohit, J.R. Wilson (co-PI's), and C. Rosenfeld (PI), engaged in studies in "Experimental Particle Physics." The group collaborated with similar groups at other universities and at national laboratories to conduct experimental studies of elementary particle properties. We utilized the particle accelerators at the Fermi National Accelerator Laboratory (Fermilab) in Illinois, the Stanford Linear Accelerator Center (SLAC) in California, and the European Center for Nuclear Research (CERN) in Switzerland. Mishra, Rosenfeld, and Petti worked predominantly on neutrino experiments. Experiments conducted in the last fifteen years that used cosmic rays and the core of the sun as a source of neutrinos showed conclusively that, contrary to the former conventional wisdom, the "flavor" of a neutrino is not immutable. A neutrino of flavor "e," "mu," or "tau," as determined from its provenance, may swap its identity with one of the other flavors -- in our jargon, they "oscillate." The oscillation phenomenon is extraordinarily difficult to study because neutrino interactions with our instruments are exceedingly rare -- they travel through the earth mostly unimpeded -- and because they must travel great distances before a substantial proportion have made the identity swap. Three of the experiments that we worked on, MINOS, NOvA, and LBNE utilize a beam of neutrinos from an accelerator at Fermilab to determine the parameters governing the oscillation. Two other experiments that we worked on, NOMAD and MIPP, provide measurements supportive of the oscillation experiments. Good measurements of the neutrino oscillation parameters may constitute a "low energy window" on related phenomena that are otherwise unobservable because they would occur only at energies way above the reach of conceivable accelerators. Purohit and Wilson participated in the BaBar experiment

  9. Experimental quantum data locking

    NASA Astrophysics Data System (ADS)

    Liu, Yang; Cao, Zhu; Wu, Cheng; Fukuda, Daiji; You, Lixing; Zhong, Jiaqiang; Numata, Takayuki; Chen, Sijing; Zhang, Weijun; Shi, Sheng-Cai; Lu, Chao-Yang; Wang, Zhen; Ma, Xiongfeng; Fan, Jingyun; Zhang, Qiang; Pan, Jian-Wei

    2016-08-01

    Classical correlation can be locked via quantum means: quantum data locking. With a short secret key, one can lock an exponentially large amount of information in order to make it inaccessible to unauthorized users without the key. Quantum data locking presents a resource-efficient alternative to one-time pad encryption which requires a key no shorter than the message. We report experimental demonstrations of a quantum data locking scheme originally proposed by D. P. DiVincenzo et al. [Phys. Rev. Lett. 92, 067902 (2004), 10.1103/PhysRevLett.92.067902] and a loss-tolerant scheme developed by O. Fawzi et al. [J. ACM 60, 44 (2013), 10.1145/2518131]. We observe that the unlocked amount of information is larger than the key size in both experiments, exhibiting strong violation of the incremental proportionality property of classical information theory. As an application example, we show the successful transmission of a photo over a lossy channel with quantum data (un)locking and error correction.

  10. Experimental chloroquine retinopathy.

    PubMed

    Matsumura, M; Ohkuma, M; Tsukahara, I

    1986-01-01

    Chloroquine retinopathy was produced experimentally in the eye of the albino corydoras (one of the tropical fish) by daily administration of chloroquine (0.1 mg per os). The enucleated eyes were examined from the 14th day to 3 months after the beginning of drug administration under light and electron microscopy. The first change of retina was the appearance of membraneous cytoplasmic body (MCB) in the cytoplasm of ganglion, amacrine, bipolar and horizontal cells. MCB might be degenerated lysosome. They showed lamellar figures or crystalline lattice-like structures. Secondarily, these MCB appeared in the inner segments of photoreceptor cells. The outer segments of rod cells disappeared, and then those of cone cells. Although photoreceptor cells were diminished in number in advanced degeneration, the cells of inner nuclear layer and ganglion cells were maintained in number. The presence of MCB dose not mean death of cells. The retinal pigment epithelial cells contained MCB in its cytoplasm only in severe degenerative cases, and did not show other remarkable changes. MCB also appeared in the cytoplasm of pericytes of retinal vessels. Chloroquine is considered to damage directly photoreceptor cells most severely. PMID:3018650

  11. Thrombocytopenia in Experimental Trypanosomiasis

    PubMed Central

    Davis, Charles E.; Robbins, Robert S.; Weller, Richard D.; Braude, Abraham I.

    1974-01-01

    The effect of experimental trypanosomiasis on coagulation was studied because a patient in this hospital with Rhodesian trypanosomiasis developed thrombocytopenia with disseminated intravascular coagulation. Rats injected intraperitoneally with this strain of Trypanosoma rhodesiense consistently developed trypanosomiasis and severe thrombocytopenia without changes in hematocrit or concentration of fibrinogen or fibrin split products. At the time of 50% mortality (4-5 days) mean platelet counts per cubic millimeter of infected rats were 18,000±9,000 (±2 SEM) compared to 1,091,000±128,000 in uninfected controls. In vitro, concentrated trypanosomes and trypanosomefree supernates of disrupted organisms added to normal rat, rabbit, or human blood produced platelet aggregation within 30 min. This platelet aggregation was not blocked by inhibitors of ADP, kinins, or early or late components of complement. In vivo thrombocytopenia also occurred in infected rabbits congenitally deficient in C6 and in infected, splenectomized rats. Although the aggregating substance obtained from disrupted trypanosomes is heat-labile, it is active in the presence of complement inhibitors, suggesting that this trypanosomal product may be a protein enzyme or toxin. Since the phenomenon is independent of immune complexes, complement, ADP, and kinins, it appears to represent a new mechanism of microbial injury of platelets and the induction of thrombocytopenia. Images PMID:4207622

  12. Experimental optical diabolos.

    PubMed

    Egorov, Roman I; Soskin, Marat S; Freund, Isaac

    2006-07-01

    The canonical point singularity of elliptically polarized light is an isolated point of circular polarization, a C point. As one recedes from such a point the surrounding polarization figures evolve into ellipses characterized by a major axis of length a, a minor axis of length b, and an azimuthal orientational angle alpha: at the C point itself, alpha is singular (undefined) and a and b are degenerate. The profound effects of the singularity in alpha on the orientation of the ellipses surrounding the C point have been extensively studied both theoretically and experimentally for over two decades. The equally profound effects of the degeneracy of a and b on the evolving shapes of the surrounding ellipses have only been described theoretically. As one recedes from a C point, a and b generate a surface that locally takes the form of a double cone (i.e., a diabolo). Contour lines of constant a and b are the classic conic sections, ellipses or hyperbolas depending on the shape of the diabolo and its orientation relative to the direction of propagation. We present measured contour maps, surfaces, cones, and diabolos of a and b for a random ellipse field (speckle pattern).

  13. Particle physics---Experimental

    SciTech Connect

    Lord, J.J.; Boynton, P.E.; Burnett, T.H.; Wilkes, R.J.

    1991-08-21

    We are continuing a research program in particle astrophysics and high energy experimental particle physics. We have joined the DUMAND Collaboration, which is constructing a deep undersea astrophysical neutrino detector near Hawaii. Studies of high energy hadronic interactions using emulsion chamber techniques were also continued, using balloon flight exposures to ultra-high cosmic ray nuclei (JACEE) and accelerator beams. As members of the DUMAND Collaboration, we have responsibility for development a construction of critical components for the deep undersea neutrino detector facility. We have designed and developed the acoustical positioning system required to permit reconstruction of muon tracks with sufficient precision to meet the astrophysical goals of the experiment. In addition, we are making significant contributions to the design of the database and triggering system to be used. Work has been continuing in other aspects of the study of multiparticle production processes in nuclei. We are participants in a joint US/Japan program to study nuclear interactions at energies two orders of magnitude greater than those of existing accelerators, using balloon-borne emulsion chambers. On one of the flights we found two nuclear interactions of multiplicity over 1000 -- one with a multiplicity of over 2000 and pseudorapidity density {approximately} 800 in the central region. At the statistical level of the JACEE experiment, the frequency of occurrence of such events is orders of magnitude too large. We have continued our ongoing program to study hadronic interactions in emulsions exposed to high energy accelerator beams.

  14. X-38 Experimental Aerothermodynamics

    NASA Technical Reports Server (NTRS)

    Horvath, Thomas J.; Berry, Scott A.; Merski, N. Ronald; Fitzgerald, Steve M.

    2000-01-01

    The X-38 program seeks to demonstrate an autonomously returned orbital test flight vehicle to support the development of an operational Crew Return Vehicle for the International Space Station. The test flight, anticipated in 2002, is intended to demonstrate the entire mission profile of returning Space Station crew members safely back to earth in the event of medical or mechanical emergency. Integral to the formulation of the X-38 flight data book and the design of the thermal protection system, the aerothermodynamic environment is being defined through a synergistic combination of ground based testing and computational fluid dynamics. This report provides an overview of the hypersonic aerothermodynamic wind tunnel program conducted at the NASA Langley Research Center in support of the X-38 development. Global and discrete surface heat transfer force and moment, surface streamline patterns, and shock shapes were measured on scaled models of the proposed X-38 configuration in different test gases at Mach 6, 10 and 20. The test parametrics include angle of attack from 0 to 50 degs, unit Reynolds numbers from 0.3 x 10 (exp 6) to 16 x 10 (exp 6)/ ft, rudder deflections of 0, 2, and 5 deg. and body flap deflections from 0 to 30 deg. Results from hypersonic aerodynamic screening studies that were conducted as the configuration evolved to the present shape at, presented. Heavy gas simulation tests have indicated that the primary real gas effects on X-38 aerodynamics at trim conditions are expected to favorably influence flap effectiveness. Comparisons of the experimental heating and force and moment data to prediction and the current aerodynamic data book are highlighted. The effects of discrete roughness elements on boundary layer transition were investigated at Mach 6 and the development of a transition correlation for the X-38 vehicle is described. Extrapolation of ground based heating measurements to flight radiation equilibrium wall temperatures at Mach 6 and 10 were

  15. Experimental Volcanology: 2010 and 2020

    NASA Astrophysics Data System (ADS)

    Dingwell, D. B.

    2010-12-01

    The advent of an experimental approach to volcanology has its roots in decades-old laboratory based approaches to characterising the properties of magmas and analog materials, together with the attempts at simulating volcanic processes in the lab. A little over ten years ago many new thrusts of experimental advance led to a new dawn for experimental science applied to volcanic eruptions. Along with that, new expectations, new goals and new strategies emerged about ten years ago. Ten years later, in 2010, many fruits have been born of this labour, and new frontiers are being unfolded as we meet here. Here are some of the youngest captivating themes being explored in experimental programs today: 1) interfacing volcanic monitoring systems to experimentally generated eruptions. 2) elucidating the physicochemical behavior of experimentally generated volcanic ash as an agent in the earth system. 3) blending experimental rock deformation and magmatology studies to understand the strength and stability of volcanic materials and volcanic structures 4) exploiting the kinematics of experimentally-generated versus natural volcanic products to understand flow style and strain history. The past ten years of experimental developments in volcanology have prepared us for great advances in the future, most of which were not perceived as likely avenues of investigation as little as ten years ago! The situation is likely to repeat itself in 2020.

  16. Experimental Design and Some Threats to Experimental Validity: A Primer

    ERIC Educational Resources Information Center

    Skidmore, Susan

    2008-01-01

    Experimental designs are distinguished as the best method to respond to questions involving causality. The purpose of the present paper is to explicate the logic of experimental design and why it is so vital to questions that demand causal conclusions. In addition, types of internal and external validity threats are discussed. To emphasize the…

  17. Assessing Pupils' Skills in Experimentation

    ERIC Educational Resources Information Center

    Hammann, Marcus; Phan, Thi Thanh Hoi; Ehmer, Maike; Grimm, Tobias

    2008-01-01

    This study is concerned with different forms of assessment of pupils' skills in experimentation. The findings of three studies are reported. Study 1 investigates whether it is possible to develop reliable multiple-choice tests for the skills of forming hypotheses, designing experiments and analysing experimental data. Study 2 compares scores from…

  18. MEASUREMENT AND PRECISION, EXPERIMENTAL VERSION.

    ERIC Educational Resources Information Center

    Harvard Univ., Cambridge, MA. Harvard Project Physics.

    THIS DOCUMENT IS AN EXPERIMENTAL VERSION OF A PROGRAMED TEXT ON MEASUREMENT AND PRECISION. PART I CONTAINS 24 FRAMES DEALING WITH PRECISION AND SIGNIFICANT FIGURES ENCOUNTERED IN VARIOUS MATHEMATICAL COMPUTATIONS AND MEASUREMENTS. PART II BEGINS WITH A BRIEF SECTION ON EXPERIMENTAL DATA, COVERING SUCH POINTS AS (1) ESTABLISHING THE ZERO POINT, (2)…

  19. Majorana Thermosyphon Prototype Experimental Setup

    SciTech Connect

    Reid, Douglas J.; Guzman, Anthony D.; Munley, John T.

    2011-08-01

    This report presents the experimental setup of Pacific Northwest National Laboratory’s MAJORANA DEMONSTRATOR thermosyphon prototype cooling system. A nitrogen thermosyphon prototype of such a system has been built and tested at PNNL. This document presents the experimental setup of the prototype that successfully demonstrated the heat transfer performance of the system.

  20. Experimental Mathematics and Computational Statistics

    SciTech Connect

    Bailey, David H.; Borwein, Jonathan M.

    2009-04-30

    The field of statistics has long been noted for techniques to detect patterns and regularities in numerical data. In this article we explore connections between statistics and the emerging field of 'experimental mathematics'. These includes both applications of experimental mathematics in statistics, as well as statistical methods applied to computational mathematics.

  1. Preclinical electrogastrography in experimental pigs

    PubMed Central

    Květina, Jaroslav; Varayil, Jithinraj Edakkanambeth; Ali, Shahzad Marghoob; Kuneš, Martin; Bureš, Jan; Tachecí, Ilja; Rejchrt, Stanislav; Kopáčová, Marcela

    2010-01-01

    Surface electrogastrography (EGG) is a non-invasive means of recording gastric myoelectric activity or slow waves from cutaneous leads placed over the stomach. This paper provides a comprehensive review of preclinical EGG. Our group recently set up and worked out the methods for EGG in experimental pigs. We gained our initial experience in the use of EGG in assessment of porcine gastric myoelectric activity after volume challenge and after intragastric administration of itopride and erythromycin. The mean dominant frequency in pigs is comparable with that found in humans. EGG in experimental pigs is feasible. Experimental EGG is an important basis for further preclinical projects in pharmacology and toxicology. PMID:21217873

  2. {alpha}- and {beta}-La{sub 4}Ti{sub 9}Si{sub 4}O{sub 30}. Synthesis and structure of the second member (m = 2) of novel layered oxosilicates containing (110) rutile sheets. Electrical property and band structure characterization of the mixed-valence titanium(III/IV) oxosilicate series, La{sub 4}Ti(Si{sub 2}O{sub 7}){sub 2}(TiO{sub 2}){sub 4m} (m = 1, 2)

    SciTech Connect

    Wang, S.; Hwu, S.J.; Paradis, J.A.; Whangbo, M.H.

    1995-05-24

    Detailed description is presented of molten salt synthesis, single crystal structures, and a comparison is offered of the {alpha}- and {beta}-La{sub 4}Ti{sub 9}Si{sub 4}O{sub 30} phases. The electrical property and band struture of this mixed-valence titanium (III/IV) oxosilicate series, La{sub 4}Ti(Si{sub 2}O{sub 7}){sub 2}(TiO{sub 2}){sub 4m} (m = 1,2), are discussed in terms of electronic interactions in a confined space with respect to the (110) rutile sheets. The results from the extended Hueckel tight binding calculations and the bond valence sum analysis are contrasted with regard to charge distribution. 33 refs., 9 figs., 3 tabs.

  3. The Beginnings of Experimental Petrology

    ERIC Educational Resources Information Center

    Eugster, Hans P.

    1971-01-01

    An account of Van't Hoff's change from theoretical chemistry to petrology provides data on the European intellectual climate of the early 1900's and shows how his work laid the foundation for experimental petrology of hard rocks." (AL)

  4. Animal Experimentation in High Schools

    ERIC Educational Resources Information Center

    Ansevin, Kystyna D.

    1970-01-01

    Recommends that teacher and student be provided with the broadest possible spectrum of meaningful and feasible experiments in which the comfort of the experimental animal is protected by the design of the experiment. (BR)

  5. [Experimental studies of micromotor headpieces].

    PubMed

    Kanaev, V F; Repin, V A

    1982-01-01

    Experimental studies of handpieces for micromotors have been performed to make more precise their operating parameters. The special stand has been used for the measurements of the following data: head temperature, power losses in handpieces at no-load, and operating power required for machining by means of spherical burrs. The experimental results made it possible to specify more exactly the range of handpiece rotational speeds and to select optimum loads under reliability testing. PMID:7050601

  6. The experimental status of |Vub|

    NASA Astrophysics Data System (ADS)

    Won, Eunil

    2009-12-01

    In this presentation, we review the current experimental status in the measurements of |Vcb| from semileptonic B??? decays to DX ℓv???. Over 10 years of impressive progress in both theoretical and experimental approaches, now less than 2% precision is achieved. In order to further improve these measurements to test standard model, one expects to have better understanding of theoretical uncertainties and to have much more data from future higher luminosity B-factories and LHCb experiment.

  7. [The ethics of animal experimentation].

    PubMed

    Goffi, Jean-Yves

    2013-01-01

    The paper starts with a short definition of animal experimentation, then three main approaches to the practice are considered: unconditional approval (as advocated by Claude Bernard), conditional and restricted approval (as advocated by Peter Singer) and strict prohibition (as advocated by Tom Regan and Gary Francione). It is argued that what is actually approved or condemned in animal experimentation is the value of the scientific enterprise.

  8. Experimental Models for Neurotrauma Research.

    PubMed

    Davidsson, Johan; Risling, Mårten

    2016-01-01

    Physical trauma in the central nervous system (CNS) is usually the result of a number of forces in different directions and dimensions. A large number of experimental models have been developed to improve the possibilities to understand the outcome of CNS trauma. In this chapter, we will describe the need for a variety of experimental models for research on traumatic brain injury (TBI) and spinal cord injury (SCI). Models can serve different needs, such as: to test new treatments for injuries, to reveal thresholds for injuries, to provide a better understanding of injury mechanisms, or to test tools and methods for translation between experiments and clinical data. In this chapter, we will discuss on the validation of models and translation between experimental and clinical studies. PMID:27604724

  9. Experimental verification of quantum computation

    NASA Astrophysics Data System (ADS)

    Barz, Stefanie; Fitzsimons, Joseph F.; Kashefi, Elham; Walther, Philip

    2013-11-01

    Quantum computers are expected to offer substantial speed-ups over their classical counterparts and to solve problems intractable for classical computers. Beyond such practical significance, the concept of quantum computation opens up fundamental questions, among them the issue of whether quantum computations can be certified by entities that are inherently unable to compute the results themselves. Here we present the first experimental verification of quantum computation. We show, in theory and experiment, how a verifier with minimal quantum resources can test a significantly more powerful quantum computer. The new verification protocol introduced here uses the framework of blind quantum computing and is independent of the experimental quantum-computation platform used. In our scheme, the verifier is required only to generate single qubits and transmit them to the quantum computer. We experimentally demonstrate this protocol using four photonic qubits and show how the verifier can test the computer's ability to perform quantum computation.

  10. Experimentation on humans and nonhumans.

    PubMed

    Pluhar, Evelyn B

    2006-01-01

    In this article, I argue that it is wrong to conduct any experiment on a nonhuman which we would regard as immoral were it to be conducted on a human, because such experimentation violates the basic moral rights of sentient beings. After distinguishing the rights approach from the utilitarian approach, I delineate basic concepts. I then raise the classic "argument from marginal cases" against those who support experimentation on nonhumans but not on humans. After next replying to six important objections against that argument, I contend that moral agents are logically required to accord basic moral rights to every sentient being. I conclude by providing criteria for distinguishing ethical from unethical experimentation. PMID:16988895

  11. Animal experimentation ethics from an experimenter's point of view.

    PubMed

    Ehinger, B E

    1986-01-01

    The experimental biologist faces two kinds of ethical problems: practical and philosophical. The practical problems comprise increased costs of experimental animals, and the risk of being harassed or even raided by animal activists. There is also today a growing bureaucratic ethics overhead that has to be paid for, one way or another. The philosophical problems are the true ethical problems. Most laws and regulations emphasize that pain and agony should be minimized, but it is shown that this is neither always necessary nor always adequate. Scientists expect logical reasoning and opinions based on facts, but it is easy to find examples that the public opinion is quite illogical concerning pain and agony. For instance, you may under certain circumstances very well torture and kill animals just for pleasure. Our present legislation should be amended so as to concur better with current public views on how animals should be treated. The Swedish Committees on Animal Experimentation Ethics were intended to help scientists understand the demands of the public opinion. It is doubtful if they have been successful. The ethics of animal experimentation are perforce centered on the experimenter. He alone, at the final moment, makes the decision whether or not to use and, eventually, to kill the animal. When he kills, he obviously has a reason for doing so, and has decided that the purpose justifies the action. With the very large increase in the number of animal experiments in the last few decades, society has justifiably become increasingly concerned about the ethical considerations involved.(ABSTRACT TRUNCATED AT 250 WORDS)

  12. Experimental Approach to Teaching Fluids

    NASA Astrophysics Data System (ADS)

    Stern, Catalina

    2015-11-01

    For the last 15 years we have promoted experimental work even in the theoretical courses. Fluids appear in the Physics curriculum of the National University of Mexico in two courses: Collective Phenomena in their sophomore year and Continuum Mechanics in their senior year. In both, students are asked for a final project. Surprisingly, at least 85% choose an experimental subject even though this means working extra hours every week. Some of the experiments were shown in this congress two years ago. This time we present some new results and the methodology we use in the classroom. I acknowledge support from the Physics Department, Facultad de Ciencias, UNAM.

  13. Graphical Models for Quasi-Experimental Designs

    ERIC Educational Resources Information Center

    Kim, Yongnam; Steiner, Peter M.; Hall, Courtney E.; Su, Dan

    2016-01-01

    Experimental and quasi-experimental designs play a central role in estimating cause-effect relationships in education, psychology, and many other fields of the social and behavioral sciences. This paper presents and discusses the causal graphs of experimental and quasi-experimental designs. For quasi-experimental designs the authors demonstrate…

  14. Big Explosives Experimental Facility - BEEF

    SciTech Connect

    2014-10-31

    The Big Explosives Experimental Facility or BEEF is a ten acre fenced high explosive testing facility that provides data to support stockpile stewardship and other national security programs. At BEEF conventional high explosives experiments are safely conducted providing sophisticated diagnostics such as high speed optics and x-ray radiography.

  15. Experimental investigations of ICRF effects

    SciTech Connect

    Not Available

    1991-01-01

    The goal of the Phaedrus program is to establish the relative efficiency of helicity and momentum current drive for rf near and below omega{sub ci} and compare to theory. This paper discusses major accomplishments in the rf program; extension of operating parameters; facility improvements; and additional experimental activities. (LSP)

  16. Experimental medicine 1000 years ago

    PubMed Central

    Abdel-Halim, Rabie E.

    2011-01-01

    Little is known about the state of experimentation in the field of medicine during the Medieval Islamic era. With few exceptions, most of the contemporary sources on history of medicine propagate the idea that the roots of experimental medicine in its modern form, including clinical trials and drug-potency studies, first started during the European Renaissance in the 16th to the 18th centuries. This study is part of an ongoing multidisciplinary primary-source investigation of the original Arabic works of 11 Islamic medical scholars who lived and practiced between the 9th and the 13th centuries. The study critically evaluated and documented their contributions to the development of the scientific method and experimental medicine during that medieval Islamic era in several areas including critical appraisal of previous knowledge, clinical observations and case reports, clinical therapeutic trials, drug potency trials, experimentation on animals, dissection and dissection experiments as well as postmortem examinations. In each of the above-mentioned areas, significant contributions were made during the Medieval Islamic era from as early as the ninth century AD. PMID:21747591

  17. The drawing of experimental curves

    NASA Technical Reports Server (NTRS)

    Norton, F H

    1921-01-01

    This report presents a discussion of how to determine the location of a line or surface from experimental data. What we desire to know practically is the number of ordinates required to obtain a certain probable precision in drawing a line or surface.

  18. Experimental Neutrino Physics: Final Report

    SciTech Connect

    Lane, Charles E.; Maricic, Jelena

    2012-09-05

    Experimental studies of neutrino properties, with particular emphasis on neutrino oscillation, mass and mixing parameters. This research was pursued by means of underground detectors for reactor anti-neutrinos, measuring the flux and energy spectra of the neutrinos. More recent investigations have been aimed and developing detector technologies for a long-baseline neutrino experiment (LBNE) using a neutrino beam from Fermilab.

  19. Big Explosives Experimental Facility - BEEF

    ScienceCinema

    None

    2016-07-12

    The Big Explosives Experimental Facility or BEEF is a ten acre fenced high explosive testing facility that provides data to support stockpile stewardship and other national security programs. At BEEF conventional high explosives experiments are safely conducted providing sophisticated diagnostics such as high speed optics and x-ray radiography.

  20. Evaluating E-Labs' Experimentation

    ERIC Educational Resources Information Center

    Plaisent, Michel; Maguiraga, Lassana; Bernard, Prosper; Larhrib, Samir

    2004-01-01

    This communication discusses preliminary results on an experimentation of e-Learning with MIS students, mainly in order to cope with the logistics of lab organization. A learning management software was installed which changed completely the learning process, from content to logistics. Students have expressed their satisfaction with the e-Learning…

  1. An experimenter and his methodology

    NASA Astrophysics Data System (ADS)

    Filonovich, S. R.

    1990-12-01

    A review of experimental works by Ernst Mach has been given. The works reffer to optics and acoustics. The author is representing Ernst Mach as a physicist rather than a phylosopher, which contradicts the point of view obviously accepted in Soviet history of sciences and philosophy.

  2. Experimental and molecular dynamics study of the growth of crystalline TiO{sub 2}

    SciTech Connect

    Houska, J.; Mraz, S.; Schneider, J. M.

    2012-10-01

    Thin films of crystalline TiO{sub 2} are of high interest due to their photoactivity and photoinduced hydrophilicity. Previously, preparation of TiO{sub 2} has been described in terms of extrinsic process parameters, such as total pressure, oxygen partial pressure, or substrate bias potential. We study the growth of TiO{sub 2} phases, rutile and anatase, by atom-by-atom molecular dynamics simulations. We focus on the effect of intrinsic process parameters including particle energy, growth temperature, and growth template. While experiments indicate that the deposition of rutile requires higher temperatures and/or energies compared to anatase, we show that the growth of previously nucleated rutile can take place in a wider range of temperatures and energies compared to anatase. In parallel, we show relationships between crystal growth and the lateral size of a crystal. The results facilitate defining new synthesis pathways for TiO{sub 2}, and constitute phenomena which may be relevant for other ceramics.

  3. Interpreting physicochemical experimental data sets.

    PubMed

    Colclough, Nicola; Wenlock, Mark C

    2015-09-01

    With the wealth of experimental physicochemical data available to chemoinformaticians from the literature, commercial, and company databases an increasing challenge is the interpretation of such datasets. Subtle differences in experimental methodology used to generate these datasets can give rise to variations in physicochemical property values. Such methodology nuances will be apparent to an expert experimentalist but not necessarily to the data analyst and modeller. This paper describes the differences between common methodologies for measuring the four most important physicochemical properties namely aqueous solubility, octan-1-ol/water distribution coefficient, pK(a) and plasma protein binding highlighting key factors that can lead to systematic differences. Insight is given into how to identify datasets suitable for combining. PMID:26054297

  4. Experimental multiparty sequential state discrimination

    NASA Astrophysics Data System (ADS)

    Solís-Prosser, M. A.; González, P.; Fuenzalida, J.; Gómez, S.; Xavier, G. B.; Delgado, A.; Lima, G.

    2016-10-01

    Recently, a protocol for quantum state discrimination (QSD) in a multiparty scenario has been introduced [Phys. Rev. Lett. 111, 100501 (2013), 10.1103/PhysRevLett.111.100501]. In this protocol, Alice generates a quantum system in one of two predefined nonorthogonal qubit states, and the goal is to send the generated state information to different parties without classical communication exchanged between them during the protocol's session. The interesting feature is that, by resorting to sequential generalized measurements onto this single system, there is a nonvanishing probability that all observers identify the state prepared by Alice. Here, we present the experimental implementation of this protocol based on polarization single-photon states. Our scheme works over an optical network, and since QSD lies in the core of many protocols, it represents a step towards experimental multiparty quantum information processing.

  5. Experimental research on air propellers

    NASA Technical Reports Server (NTRS)

    Durand, William F

    1918-01-01

    The purposes of the experimental investigation on the performance of air propellers described in this report are as follows: (1) the development of a series of design factors and coefficients drawn from model forms distributed with some regularity over the field of air-propeller design and intended to furnish a basis of check with similar work done in other aerodynamic laboratories, and as a point of departure for the further study of special or individual types and forms; (2) the establishment of a series of experimental values derived from models and intended for later use as a basis for comparison with similar results drawn from certain selected full-sized forms and tested in free flight.

  6. Experimental lithium system. Final report

    SciTech Connect

    Kolowith, R.; Berg, J.D.; Miller, W.C.

    1985-04-01

    A full-scale mockup of the Fusion Materials Irradiation Test (FMIT) Facility lithium system was built at the Hanford Engineering Development Laboratory (HEDL). This isothermal mockup, called the Experimental Lithium System (ELS), was prototypic of FMIT, excluding the accelerator and dump heat exchanger. This 3.8 m/sup 3/ lithium test loop achieved over 16,000 hours of safe and reliable operation. An extensive test program demonstrated satisfactory performance of the system components, including the HEDL-supplied electromagnetic lithium pump, the lithium jet target, the purification and characterization hardware, as well as the auxiliary argon and vacuum systems. Experience with the test loop provided important information on system operation, performance, and reliability. This report presents a complete overview of the entire Experimental Lithium System test program and also includes a summary of such areas as instrumentation, coolant chemistry, vapor/aerosol transport, and corrosion.

  7. Experimental unconditionally secure bit commitment.

    PubMed

    Liu, Yang; Cao, Yuan; Curty, Marcos; Liao, Sheng-Kai; Wang, Jian; Cui, Ke; Li, Yu-Huai; Lin, Ze-Hong; Sun, Qi-Chao; Li, Dong-Dong; Zhang, Hong-Fei; Zhao, Yong; Chen, Teng-Yun; Peng, Cheng-Zhi; Zhang, Qiang; Cabello, Adán; Pan, Jian-Wei

    2014-01-10

    Quantum physics allows for unconditionally secure communication between parties that trust each other. However, when the parties do not trust each other such as in the bit commitment scenario, quantum physics is not enough to guarantee security unless extra assumptions are made. Unconditionally secure bit commitment only becomes feasible when quantum physics is combined with relativistic causality constraints. Here we experimentally implement a quantum bit commitment protocol with relativistic constraints that offers unconditional security. The commitment is made through quantum measurements in two quantum key distribution systems in which the results are transmitted via free-space optical communication to two agents separated with more than 20 km. The security of the protocol relies on the properties of quantum information and relativity theory. In each run of the experiment, a bit is successfully committed with less than 5.68×10(-2) cheating probability. This demonstrates the experimental feasibility of quantum communication with relativistic constraints.

  8. Experimental Unconditionally Secure Bit Commitment

    NASA Astrophysics Data System (ADS)

    Liu, Yang; Cao, Yuan; Curty, Marcos; Liao, Sheng-Kai; Wang, Jian; Cui, Ke; Li, Yu-Huai; Lin, Ze-Hong; Sun, Qi-Chao; Li, Dong-Dong; Zhang, Hong-Fei; Zhao, Yong; Chen, Teng-Yun; Peng, Cheng-Zhi; Zhang, Qiang; Cabello, Adán; Pan, Jian-Wei

    2014-01-01

    Quantum physics allows for unconditionally secure communication between parties that trust each other. However, when the parties do not trust each other such as in the bit commitment scenario, quantum physics is not enough to guarantee security unless extra assumptions are made. Unconditionally secure bit commitment only becomes feasible when quantum physics is combined with relativistic causality constraints. Here we experimentally implement a quantum bit commitment protocol with relativistic constraints that offers unconditional security. The commitment is made through quantum measurements in two quantum key distribution systems in which the results are transmitted via free-space optical communication to two agents separated with more than 20 km. The security of the protocol relies on the properties of quantum information and relativity theory. In each run of the experiment, a bit is successfully committed with less than 5.68×10-2 cheating probability. This demonstrates the experimental feasibility of quantum communication with relativistic constraints.

  9. Experimental unconditionally secure bit commitment

    NASA Astrophysics Data System (ADS)

    Liu, Yang; Cao, Yuan; Curty, Marcos; Liao, Sheng-Kai; Wang, Jian; Cui, Ke; Li, Yu-Huai; Lin, Ze-Hong; Sun, Qi-Chao; Li, Dong-Dong; Zhang, Hong-Fei; Zhao, Yong; Chen, Teng-Yun; Peng, Cheng-Zhi; Zhang, Qiang; Cabello, Adan; Pan, Jian-Wei

    2014-03-01

    Quantum physics allows unconditionally secure communication between parties that trust each other. However, when they do not trust each other such as in the bit commitment, quantum physics is not enough to guarantee security. Only when relativistic causality constraints combined, the unconditional secure bit commitment becomes feasible. Here we experimentally implement a quantum bit commitment with relativistic constraints that offers unconditional security. The commitment is made through quantum measurements in two quantum key distribution systems in which the results are transmitted via free-space optical communication to two agents separated with more than 20 km. Bits are successfully committed with less than 5 . 68 ×10-2 cheating probability. This provides an experimental proof of unconditional secure bit commitment and demonstrates the feasibility of relativistic quantum communication.

  10. KRITZ-2 Experimental Benchmark Analysis

    SciTech Connect

    Pavlovichev, A.M.

    2001-09-28

    The KRITZ-2 experiment has been adopted by the OECD/NEA Task Force on Reactor-Based Plutonium Disposition for use as a benchmark exercise. The KRITZ-2 experiment consists of three different core configurations (one with near-weapons-grade MOX) with critical conditions a 20 C and 245 C. The KRITZ-2 experiment has calculated the MCU-REA code, which is a continuous energy Monte Carlo code system developed at the Russian Research Center--Kurchatov Institute and is used extensively in the Fissile Materials Disposition Program. The calculated results for k{sub eff} and fission rate distributions are compared with the experimental data and results of other codes. The results are in good agreement with the experimental values.

  11. Experimental unconditionally secure bit commitment.

    PubMed

    Liu, Yang; Cao, Yuan; Curty, Marcos; Liao, Sheng-Kai; Wang, Jian; Cui, Ke; Li, Yu-Huai; Lin, Ze-Hong; Sun, Qi-Chao; Li, Dong-Dong; Zhang, Hong-Fei; Zhao, Yong; Chen, Teng-Yun; Peng, Cheng-Zhi; Zhang, Qiang; Cabello, Adán; Pan, Jian-Wei

    2014-01-10

    Quantum physics allows for unconditionally secure communication between parties that trust each other. However, when the parties do not trust each other such as in the bit commitment scenario, quantum physics is not enough to guarantee security unless extra assumptions are made. Unconditionally secure bit commitment only becomes feasible when quantum physics is combined with relativistic causality constraints. Here we experimentally implement a quantum bit commitment protocol with relativistic constraints that offers unconditional security. The commitment is made through quantum measurements in two quantum key distribution systems in which the results are transmitted via free-space optical communication to two agents separated with more than 20 km. The security of the protocol relies on the properties of quantum information and relativity theory. In each run of the experiment, a bit is successfully committed with less than 5.68×10(-2) cheating probability. This demonstrates the experimental feasibility of quantum communication with relativistic constraints. PMID:24483878

  12. Does experimental research support psychoanalysis?

    PubMed

    Cohen, David

    2011-12-01

    The question of whether a psychodynamic view is compatible with experimental research is still a challenging issue-especially for child and adolescent psychopathology-despite the influence of psychoanalytic theory in this field until the 1980s. In this article, is explored the relationship between psychodynamic theory and experimental research using examples of evidence-based studies in the fields of (i) psychotherapeutic intervention assessment, (ii) placebo response in children and adolescents, (iii) unconscious lasting traumatic effects in children and adolescents, (iv) psychodynamic-oriented psychological testing. There are now a sufficient number of evidence-based studies to support the use of psychodynamic therapy in mental disorders, particularly in personality disorder and anxious/depressive disorder. In addition, placebo responses in children and adolescents with internalizing disorders are significantly higher in major depression compared to obsessive-compulsive disorder or other anxiety disorders, which highlights differential psychopathologies regarding the experience of loss. Also, using an experimental task, psychoanalysts are able to identify, without explicit knowledge and above the level of chance, healthy adults whose siblings had experienced cancer during childhood. This experiment suggests that implicit information regarding a participant's history is conveyed in interpersonal exchanges that can be intuitively perceived by judges experienced in listening to free associations from a psychodynamic perspective. Finally, psychodynamic-oriented psychological testing may predict the transition to schizophrenia in adolescents with a history of manic/mixed episodes. It can be concluded that there are no discrepancies between psychodynamic views and experimental data, whether one tests psychotherapeutic approaches, discusses data from other fields such as psychopharmacology, or designs experiments based on psychodynamic theory. PMID:21963530

  13. Elements of Bayesian experimental design

    SciTech Connect

    Sivia, D.S.

    1997-09-01

    We consider some elements of the Bayesian approach that are important for optimal experimental design. While the underlying principles used are very general, and are explained in detail in a recent tutorial text, they are applied here to the specific case of characterising the inferential value of different resolution peakshapes. This particular issue was considered earlier by Silver, Sivia and Pynn (1989, 1990a, 1990b), and the following presentation confirms and extends the conclusions of their analysis.

  14. Experimental tests of quantum chromodynamics

    SciTech Connect

    Dorfan, J.

    1987-04-01

    Experimental tests of quantum chromodynamics are discussed in the e/sup +/e/sup -/ continuum, in pp and anti p p collisions, in measurements of ..cap alpha../sub s/ from UPSILON decays, in deep inelastic lepton scattering, and in the measurement of the photon structure function. A large body of data relating to the testing of quantum chromodynamics is reviewed, showing qualitative agreement between the data from a wide range of processes and QCD. 66 refs., 79 figs. (LEW)

  15. Experimental observation of fractional echoes

    NASA Astrophysics Data System (ADS)

    Karras, G.; Hertz, E.; Billard, F.; Lavorel, B.; Siour, G.; Hartmann, J.-M.; Faucher, O.; Gershnabel, Erez; Prior, Yehiam; Averbukh, Ilya Sh.

    2016-09-01

    We report the observation of fractional echoes in a double-pulse excited nonlinear system. Unlike standard echoes, which appear periodically at delays which are integer multiples of the delay between the two exciting pulses, the fractional echoes appear at rational fractions of this delay. We discuss the mechanism leading to this phenomenon, and provide experimental demonstration of fractional echoes by measuring third harmonic generation in a thermal gas of CO2 molecules excited by a pair of femtosecond laser pulses.

  16. Experimental realization of invisibility cloaking

    NASA Astrophysics Data System (ADS)

    Shchelokova, A. V.; Melchakova, I. V.; Slobozhanyuk, A. P.; Yankovskaya, E. A.; Simovski, C. R.; Belov, P. A.

    2015-02-01

    Advances in the studies of metamaterials have pushed the development of invisibility cloaks, which suppress scattering by objects within certain frequency ranges. During recent years, there has been a transition from a purely theoretical consideration of the cloaking effect to its practical implementation. This paper is an overview of the current state of the art in the area of invisibility cloaks. Special emphasis is put on experimental realizations of such devices.

  17. Experimental data confronts nuclear structure

    SciTech Connect

    Garrett, J.D.

    1988-01-01

    The physical content of experimental data for a variety of excitation energies and angular momenta is summarized. The specific nuclear structure questions which these data address are considered. The specific regions discussed are: low-spin data near the particle separation thresholds; low-spin data at intermediate excitation energies; high-spin, near-yrast data and high-spin data at larger excitation energies. 63 refs., 14 figs., 1 tab.

  18. Experimental Crystallization of Yamato 980459

    NASA Technical Reports Server (NTRS)

    Jones, John H.; Galenas, M. G.; Danielson, L. R.

    2009-01-01

    Currently, only two martian meteorites QUE 94201 (QUE) and Yamato 980459 (Y98) have been experimentally shown to me true melt compositions. Most martian meteorites are instead, cumulates or partial cumulates. We have performed experiments on a Y98 composition to assess whether QUE could be related to Y98 by some fractionation process [1]. Y98 is a basaltic shergottite from the SNC (Shergotty, Nakhla, Chassigny) meteorite group. Y98 is composed of 26% olivine, 48% pyroxene, 25% mesostasis, and no plagioclase [2]. The large size of the olivine megacrysts and absence of plagioclase suggest that the parental melt which formed this meteorite had begun cooling slowly until some mechanism, such as magma ascent, caused rapid cooling [3]. Y98 s olivines have the highest Mg content of all the shergottites suggesting that it is the most primitive [4]. Y98 has been determined to be a melt composition by comparing the composition of experimental liquidus olivines with the composition of the cores of Y98 olivines [4]. The liquidus of Y98 is predicted by MELTS [5] and by experimentation [6] to be 1450 C. Analyses of Y98 show it to be very depleted in LREEs and it has similar depleted patterns as other shergottites such as QUE [7].

  19. National Ignition Facility: Experimental plan

    SciTech Connect

    Not Available

    1994-05-01

    As part of the Conceptual Design Report (CDR) for the National Ignition Facility (NIF), scientists from Lawrence Livermore National Laboratory (LLNL), Los Alamos National Laboratory (LANL), Sandia National Laboratory (SNL), the University of Rochester`s Laboratory for Laser Energetics (UR/LLE), and EG&G formed an NIF Target Diagnostics Working Group. The purpose of the Target Diagnostics Working Group is to prepare conceptual designs of target diagnostics for inclusion in the facility CDR and to determine how these specifications impact the CDR. To accomplish this, a subgroup has directed its efforts at constructing an approximate experimental plan for the ignition campaign of the NIF CDR. The results of this effort are contained in this document, the Experimental Plan for achieving fusion ignition in the NIF. This group initially concentrated on the flow-down requirements of the experimental campaign leading to ignition, which will dominate the initial efforts of the NIF. It is envisaged, however, that before ignition, there will be parallel campaigns supporting weapons physics, weapons effects, and other research. This plan was developed by analyzing the sequence of activities required to finally fire the laser at the level of power and precision necessary to achieve the conditions of an ignition hohlraum target, and to then use our experience in activating and running Nova experiments to estimate the rate of completing these activities.

  20. 47 CFR 73.1510 - Experimental authorizations.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... the degree required for the particular type of station. (3) The experimental operations may be... for the class and type of station must be met. AM stations also may conduct experimental operations... experimental transmissions. (d) The FCC may request a report of the research, experimentation and results...