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Sample records for rutile a-tio2 experimental

  1. 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

  2. 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

  3. Multiphoton Effects in Rutile.

    NASA Astrophysics Data System (ADS)

    Royce, Gerald A.

    Multiphoton effects are investigated in crystalline rutile TiO(,2) using Nd:YAG laser photons. The 1.06 micron laser is operated in Q-switched mode with intensities up to 1.4 x 10('6) watts/cm('2) on the rutile crystal. Photoconductivity measurements provide data indicating a mixture of modes for electrons to be photoionized. Assuming aluminum impurity as the contributing sites, the first order photionization cross section is found to be 1.5 x 10('-26) cm('2) and second order cross section is found to be 7.7 x 10('-51) cm('4)-s. No appreciable change in cross section is observed for circular versus linear polarization of the laser. Observations of the photo-emission of the laser illuminated crystal provide radiative relaxation times on the order of 100 nanoseconds with emission peaks at 4500 and 5000 angstroms plus a near infrared continuum out to 1 micron. The thermoluminescence of rutile shows a number of trapping levels between 0.4 and 0.8 eV below the conduction band. These are attributed to an aluminum impurity.

  4. U-Pb rutile thermochronology: a review and status report on a vexing conundrum (Invited)

    NASA Astrophysics Data System (ADS)

    Schmitz, M. D.; Dye, J. H.

    2009-12-01

    Among the available intermediate-temperature thermochronometers utilizing U-Pb isotopic measurements of accessory minerals, rutile stands out as among the least apparently understood in terms of diffusion kinetics and daughter-loss mechanisms. Discrepancies persist between a variety of empirical and experimental estimates of apparent closure temperature for the U-Pb rutile thermochronometer, ranging from as low as 400°C to greater than 600°C. This range in the temperature component of the thermochronometer is particularly vexing given the otherwise attractive chronologic and petrologic characteristics of rutile, and a new Zr-in-rutile thermometric calibration (Watson et al., 2006, Crystallization thermometers for zircon and rutile, Contrib. Mineral. Petrol. 151:413-433) that could complement U-Pb-based thermochronology. The crux of the U-Pb rutile conundrum lies in apparent discrepancy between nominal closure temperatures inferred on the basis of: a) empirical multiple mineral-isotope relative thermochronology for metamorphic terrains, versus b) the available experimental determination of Pb volume diffusion parameters in rutile (Cherniak et al., 2000, Pb diffusion in rutile, Contrib. Mineral. Petrol. 139:198-207). This contribution will review the state-of-the-art in U-Pb analytical measurements of rutile, and the constraints provided by empirical studies of the relative closure properties of rutile and a variety of other mineral-isotope thermochronometers. A thermochronological case study combining Rb-Sr mica and U-Pb zircon, monazite, titanite and rutile ages and trace element thermometry from Cretaceous-Paleogene amphibolite-facies gneisses of the northern U.S. Cordillera will highlight the problems and potential of this valuable thermochronometer.

  5. 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.

  6. 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

  7. 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).

  8. 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.

  9. Effect of Chemical Lithium Intercalation into Rutile TiO2 Nanorods

    SciTech Connect

    Vijayakumar, M.; Kerisit, Sebastien N.; Wang, Chong M.; Nie, Zimin; Rosso, Kevin M.; Yang, Zhenguo; Graff, Gordon L.; Liu, Jun; Hu, Jian Z.

    2009-08-13

    Rutile TiO2 nanorods were synthesized by hydrolysis of TiCl4 followed by a hydrothermal method. Lithium insertion into the rutile nanorods was achieved by a chemical lithium intercalation process. The structural evolution of nano-structured rutile upon lithium intercalation was characterized by several experimental techniques, namely, XRD, TEM and 6Li MAS NMR. The XRD and TEM studies indicate the formation of a new lithium titanate phase (LixTiO2) during lithium intercalation. Additionally, SAED patterns show that the lithium titanate phase has cubic symmetry. Finally, ultra-high magnetic field (21.1T) 6Li MAS NMR reveals that the lithium titanate phase adopts two different structures depending on lithium content. Taken together, the three techniques consistently show that the intercalation of lithium into rutile TiO2 nanorods causes two consecutive structural phase transformations to lithium titanate phases with spinel (Fd m) and rocksalt (Fm m) structures at x=0.46 and 0.88, respectively. In addition, the broad line widths in the 6Li MAS NMR spectrum of the rocksalt phase are indicative of a disordered structure. Density functional theory calculations of the rutile, spinel and rocksalt bulk phases as a function of lithium content corroborate the observed phase transformations. These phase transitions could account for the large irreversible capacity loss of nano-structured rutile anodes observed in electrochemical cycling experiments.

  10. 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

  11. 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.

  12. Fluid-inclusion microthermometry and the Zr-in-rutile thermometer for hydrothermal rutile

    NASA Astrophysics Data System (ADS)

    Cabral, Alexandre Raphael; Rios, Francisco Javier; de Oliveira, Lucilia Aparecida Ramos; de Abreu, Francisco Robério; Lehmann, Bernd; Zack, Thomas; Laufek, František

    2015-03-01

    The Zr-in-rutile thermometer is well established for the determination of metamorphic temperatures, particularly in high-grade metamorphic terrains, and for sedimentary provenance studies. The robustness of the rutile thermometry has not been tested on hydrothermal systems. Unlike quartz, a common hydrothermal mineral with abundant fluid inclusions, it is difficult to find fluid inclusions in rutile that are suitable for fluid-inclusion microthermometry. Here, we report fluid-inclusion microthermometric measurements in rutile from the auriferous quartz-kaolinite-hematite vein that typifies the gold deposit of Mil Oitavas in the southern Serra do Espinhaço, Minas Gerais, Brazil. Primary fluid inclusions in the rutile record moderately saline (10-12 wt% NaCl equivalent), aqueous-carbonic fluids with a total homogenization temperature of ~250 °C, which were likely trapped at about 300 °C and 2.0 kbar. This temperature is approximately 200 °C lower than that predicted by the Zr-in-rutile thermometer. For hydrothermal conditions of relatively low temperature, direct measurements of homogenization temperatures in rutile-hosted fluid inclusions should be preferred to the Zr-in-rutile thermometer.

  13. Catalytic reduction of CO with hydrogen sulfide. 4. Temperature-programmed desorption of methanethiol on anatase, rutile, and sulfided rutile

    SciTech Connect

    Beck, D.D.; White, J.M.; Ratcliffe, C.T.

    1986-07-03

    The interaction of methanethiol with anatase, rutile, and sulfided rutile was studied by temperature-programmed desorption. Dissociative adsorption occurs on rutile but is insignificant on anatase. Decomposition products are dominated by H/sub 2/ on rutile and by CH/sub 4/ on sulfided rutile. In both cases desorption occurs between 500 and 775 K. The 5- and 4-coordinate sites on the (110) face of rutile are proposed as the active sites for decomposition. The dominance of methane on a sulfided surface is attributed to the relatively large supply of highly mobile surface hydrogen atoms.

  14. Moessbauer spectroscopic studies of iron-doped rutile.

    NASA Technical Reports Server (NTRS)

    Stampfl, P. P.; Travis, J. C.; Bielefeld, M. J.

    1973-01-01

    Moessbauer spectra were obtained of single crystal and powdered samples of rutile (TiO2) doped to about one percent by weight in isotopically enriched iron. It is shown that the oxidation state may be reversibly altered in situ. After reduction, the oxygen neighbors of the dopant ion are apparently shifted to accomodate the larger ferrous ion. The agreement of calculated quadrupole splittings with experimental results suggests that impurities and oxygen vacancies are uniformly distributed in powdered samples, giving the dopant ions an 'ideal lattice' local environment. The differences between the single crystal and powder sample hyperfine parameters are attributed to variations in stoichiometry, charge compensation mechanisms, or other diffusion related parameters.

  15. Antiferromagnetism in Bulk Rutile RuO2

    NASA Astrophysics Data System (ADS)

    Berlijn, T.; Snijders, P. C.; Kent, P. R. C.; Maier, T. A.; Zhou, H.-D.; Cao, H.-B.; Delaire, O.; Wang, Y.; Koehler, M.; Weitering, H. H.

    While bulk rutile RuO2 has long been considered to be a Pauli paramagnet, we conclude it to host antiferromagnetism based on our combined theoretical and experimental study. This constitutes an important finding given the large amount of applications of RuO2 in the electrochemical and electronics industry. Furthermore the high onset temperature of the antiferromagnetism around 1000K together with the high electrical conductivity makes RuO2 unique among the ruthenates and among oxide materials in general. This work was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division.

  16. 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.

  17. 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.

  18. 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

  19. Differential Nb-Ta diffusion in rutile: disequilibrium formation of the continental crust

    NASA Astrophysics Data System (ADS)

    Marschall, H. R.; Dohmen, R.; Ludwig, T.

    2012-12-01

    Models for the differentiation of the crust-mantle system are guided by elemental abundances in these reservoirs. Elements are fractionated between coexisting phases during partial melting, and geochemical models have mostly been based on the assumption that trace-element equilibrium is established between the partial melts and the restitic minerals. Based on this assumption, experimentally determined mineral/melt element partition coefficients have been used to model the effects of crust-mantle differentiation. The element pair niobium and tantalum has been key for the distinction of different melting regimes involved in crustal differentiation, but equilibrium partition models have largely failed to reproduce the observed Nb/Ta patterns. Here we demonstrate that Nb and Ta are significantly fractionated kinetically by diffusion, and that Nb/Ta systematics of partial melts and restites will likely be influenced by kinetic factors. We employed two different experimental setups to determine diffusivities of Nb and Ta in rutile: (1) Thin film diffusion couples prepared by PLD [1] were annealed in gas mixing furnaces between 850 and \\unit{1150}{ȩlsius}. The resulting diffusion profiles were analysed by SIMS in depth profiling mode. (2) Rutile single crystals were placed in rutile-saturated Nb-Ta-doped basaltic melt at \\unit{1250}{ȩlsius} and lateral diffusion profiles were analysed by EPMA. Both sets of experiments demonstrate consistently and unequivocally that diffusion coefficients in rutile of Nb are 3 to 5 (!) times higher than those of Ta for the entire temperature range. The significantly higher mobility of Nb compared to Ta in rutile has direct consequences for their liquid-rock fractionation during partial melting events. We conclude that trace-element equilibrium cannot be expected for the natural range of grain sizes of rutile (the dominant mineral host of Nb and Ta in high-grade rocks) and the temperatures and time scales involved in partial melting of

  20. Rutile geochemistry and its potential use in quantitative provenance studies

    NASA Astrophysics Data System (ADS)

    Zack, T.; von Eynatten, H.; Kronz, A.

    2004-10-01

    Rutile is among the most stable detrital minerals in sedimentary systems. Information contained in rutile is therefore of prime importance, especially in the study of mature sediments, where most diagnostic minerals are no longer stable. In contrast to zircon, rutile provides information about the last metamorphic cycle as rutile is not stable at greenschist facies conditions. Several known geochemical characteristics of rutile can be used to retrace provenance. The lithology of source rocks can be determined using Nb and Cr contents in rutile, because the most important source rocks for rutile, metapelites and metabasites, imprint a distinct Nb and Cr signature in rutiles. Since Zr in rutile, coexisting with zircon and quartz, is extremely temperature dependent, this relationship can be used as a geothermometer. Metapelites always contain zircon and quartz, thus the Nb and Cr signatures of metapelites indicate rutiles that can be used for thermometry. The result is effectively a single-mineral geothermometer, which is to our knowledge the first of its kind in provenance studies. Several other trace elements are variably enriched in rutile, but the processes creating these variations are so far not understood. In a case study, Al, Si, V, Cr, Fe, Zr, Nb and W contents in rutiles were obtained by electron microprobe from three sediment samples from Upstate New York. A Pleistocene glacial sand, whose source was granulite-facies rocks of the southern Adirondacks, has detrital rutile geochemical signatures which are consistent with the local Geology; a predominantly metapelitic source with a minor metabasitic contribution. Calculated temperatures for the metapelitic rutiles from the glacial sand are consistent with a predominantly granulite-facies source. The two other samples are from Paleozoic clastic wedges deposited in the foreland of the Taconian and Acadian orogenies. Here several geochemical patterns of detrital rutiles are comparable to rutiles derived from the

  1. Investigating Alpine fissure rutilated quartz to constrain timing and conditions of post-metamorphic hydrothermal fluid flow

    NASA Astrophysics Data System (ADS)

    Shulaker, D. Z.; Schmitt, A. K.; Zack, T.; Bindeman, I. N.

    2013-12-01

    -metamorphic hydrothermal fluid flow and mineralization. Discrepancies in thermometers are attributed to differences between experimental calibrations of isotopic and trace element thermometers, and the conditions of post-metamorphic hydrothermal fluid flow. Only rutile-quartz oxygen isotope exchange [3] has been calibrated close to natural T conditions for rutilated quartz (500°C). This may help to extend the applicability of the Ti-in-quartz and Zr-in-rutile to T below experimental calibrations (>600°C; [4] and >700°C; [5], resp.). [1] Janots et al., 2012, Chem. Geol., 326-327, 61-71 [2] Mullis, 1996, Schweiz. Mineral. Petrogr. Mitt., 76, 159-164 [3] Matthews, 1994, J. Met. Geol., 12, 211-219 [4] Thomas et al., 2010, Contrib. Mineral. Petrol., 160, 743-759 [5] Ferry and Watson, 2007, Contrib. Mineral. Petrol., 154, 429-437

  2. Nature of Rutile Nuclei in Anatase-to-Rutile Phase Transition.

    PubMed

    Zhu, Sheng-Cai; Xie, Song-Hai; Liu, Zhi-Pan

    2015-09-01

    The solid phase transition of TiO2, in particular anatase to rutile, has been extensively studied in the past 30 years. To seek the nucleation site at the beginning of phase transition is highly challenging, which asks for new theoretical techniques with high spatial and temporal resolution. This work reports the first evidence on the atomic structure of the nucleation sites in the TiO2 anatase-to-rutile phase transition. Novel automated theoretical methods, namely stochastic surface walking based pathway sampling methods, are utilized to resolve the lowest energy pathways at the initial stage of phase transition. We show that among common anatase surfaces, only the (112) ridged surface provides the nucleation site for phase transition, which can lead to the formation of both TiO2-II and brookite thin slabs. The TiO2-II phase is kinetically preferred product; the propagation into the subsurface is still hindered by high barriers that is the origin for the slow kinetics of nuclei formation. The rutile nuclei are thus not rutile phase but nascent metastable TiO2-II phase in an anatase matrix. The phase transition kinetics is found to be sensitive to the compressive strain and the crystallographic directions. The results rationalize the size and morphology dependence of the anisotropic phase transition kinetics of anatase particles and could facilitate the rational design of material via controlled solid phase transition. PMID:26289453

  3. 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

  4. Quasiparticle and optical properties of rutile and anatase TiO2

    NASA Astrophysics Data System (ADS)

    Kang, Wei; Hybertsen, Mark S.

    2010-08-01

    Quasiparticle excitation energies and optical properties of TiO2 in the rutile and anatase structures are calculated using many-body perturbation-theory methods. Calculations are performed for a frozen crystal lattice; electron-phonon coupling is not explicitly considered. In the GW method, several approximations are compared and it is found that inclusion of the full frequency dependence as well as explicit treatment of the Ti semicore states are essential for accurate calculation of the quasiparticle energy-band gap. The calculated quasiparticle energies are in good agreement with available photoemission and inverse photoemission experiments. The results of the GW calculations, together with the calculated static screened Coulomb interaction, are utilized in the Bethe-Salpeter equation to calculate the dielectric function γ2(ω) for both the rutile and anatase structures. The results are in good agreement with experimental observations, particularly the onset of the main absorption features around 4 eV. For comparison to low-temperature optical-absorption measurements that resolve individual excitonic transitions in rutile, the low-lying discrete excitonic energy levels are calculated with electronic screening only. The lowest energy exciton found in the energy gap of rutile has a binding energy of 0.13 eV. In agreement with experiment, it is not dipole allowed but the calculated exciton energy exceeds that measured in absorption experiments by about 0.22 eV and the scale of the exciton binding energy is also too large. The quasiparticle energy alignment of rutile is calculated for nonpolar (110) surfaces. In the GW approximation, the valence-band maximum is 7.8 eV below the vacuum level, showing a small shift from density-functional theory results.

  5. 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...

  6. 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...

  7. Anatase-rutile phase transformation of titanium dioxide bulk material: a DFT + U approach

    NASA Astrophysics Data System (ADS)

    Vu, Nam H.; Le, Hieu V.; Cao, Thi M.; Pham, Viet V.; Le, Hung M.; Nguyen-Manh, Duc

    2012-10-01

    The anatase-rutile phase transformation of TiO2 bulk material is investigated using a density functional theory (DFT) approach in this study. According to the calculations employing the Perdew-Burke-Ernzerhof (PBE) exchange-correlation functional with the Vanderbilt ultrasoft pseudopotential, it is suggested that the anatase phase is more energetically stable than rutile, which is in variance with the experimental observations. Consequently, the DFT + U method is employed in order to predict the correct structural stability in titania from electronic-structure-based total energy calculations. The Hubbard U term is determined by examining the band structure of rutile with various values of U from 3 to 10 eV. At U = 5 eV, a theoretical bandgap for rutile is obtained as 3.12 eV, which is in very good agreement with the reported experimental bandgap. Hence, we choose the DFT + U method (with U = 5 eV) to investigate the transformation pathway using the newly-developed solid-state nudged elastic band (ss-NEB) method, and consequently obtain an intermediate transition structure that is 9.794 eV per four-TiO2 above the anatase phase. When the Ti-O bonds in the transition state are examined using charge density analysis, seven Ti-O bonds (out of 24 bonds in the anatase unit cell) are broken, and this result is in excellent agreement with a previous experimental study (Penn and Banfield 1999 Am. Miner. 84 871-6).

  8. 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.

  9. 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

  10. 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

  11. 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

  12. 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.

  13. Ion implantation induced blistering of rutile single crystals

    NASA Astrophysics Data System (ADS)

    Xiang, Bing-Xi; Jiao, Yang; Guan, Jing; Wang, Lei

    2015-07-01

    The rutile single crystals were implanted by 200 keV He+ ions with a series fluence and annealed at different temperatures to investigate the blistering behavior. The Rutherford backscattering spectrometry, optical microscope and X-ray diffraction were employed to characterize the implantation induced lattice damage and blistering. It was found that the blistering on rutile surface region can be realized by He+ ion implantation with appropriate fluence and the following thermal annealing.

  14. 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.

  15. 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.

  16. 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.

  17. 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

  18. Hydrogen Impurity Defects in Rutile TiO2.

    PubMed

    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

  19. OH in Rutile: an Oxygen and Water Barometer

    NASA Astrophysics Data System (ADS)

    Johnson, E. A.; Manning, C. E.; Antignano, A.; Tropper, P.

    2005-12-01

    Dehydration of the subducting lithosphere induces oxidation and partial melting in the mantle wedge above subduction zones, and storage of water in the form of hydroxyl in high-pressure mineral phases may be an important mechanism for transfer of water to the mantle. It is therefore important to quantify water content of fluids and oxygen fugacity in subduction zones, but these variables can be difficult to measure or infer in many rocks. This study investigates the possibility of determining oxygen fugacity or water activity based on OH concentration measurements in rutile. The solubility of OH in pure rutile has been determined using rutile grains from aqueous fluid solubility experiments (Tropper and Manning 2005, Am Min, 90, 502). In pure rutile, H+ is stoichiometrically incorporated into the structure via reduction of Ti4+ to Ti3+, resulting in a change in color from pale yellow to deep blue. Synthetic rutile crystals were equilibrated in pure H2O or a H2O-NaCl solution at 1-2 GPa and 600-1100°C. The runs were unbuffered with respect to oxygen fugacity but were close to the NNO buffer (Newton and Manning 2005, J Petr, 46, 701). Rutile OH concentrations were determined using FTIR spectroscopy and the calibration of Maldener (2001, Min Pet, 71, 21). At a constant pressure of 1 GPa, OH concentrations of rutile in equilibrium with pure H2O increase exponentially from 600 to 1100°C. The data are fit with the equation [OH] = 17.7exp(4.00×10-3T) (R=0.998), where [OH] is in ppm H2O wt. and T is in °C. Increasing pressure from 1 to 2 GPa at 1100°C results in an increase in OH solubility from 1540 to 2220 ppm H2O. OH solubility in rutile decreases from 2220 to 1290 ppm H2O by lowering the water activity of the fluid from 1 to 0.49 at P = 2 GPa and T = 1100°C. Using the solubility data and the exchange reaction, Ti3+O(OH) + O2 = Ti4+O2 + <

  20. 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.

  1. Mineral intergrowths replaced by "elbow-twinned" rutile in altered rocks

    USGS Publications Warehouse

    Force, E.R.; Richards, R.P.; Scott, K.M.; Valentine, P.C.; Fishman, N.S.

    1996-01-01

    Some aggregates of rutile, classically considered to be "elbow" twinned, instead are topotactic replacements of ilmenite or other hexagonal titaniferous precursors. Twinned rutile can be differentiated from the reticulated rutile of topotactic replacements by the angle of prism intersections, junction morphology, and the overall form of the aggregate. In a special case of topotactic replacement of ilmenite, rutile forms pseudomorphs of "trellis"-textured ilmenite lamellae in {111} of precursor magnetite. We trace the progress of rutile formation through the alteration of fine-grained magnetite-bearing host rocks. The sequential two-step topotaxy from magnetite through ilmenite to rutile requires rutile prisms to parallel the intersections of {111} planes in precursor magnetite. Some coarse reticulated rutile may result from the same paragenetic sequence.

  2. 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.

  3. Rutile solubility and titanium coordination in silicate melts

    NASA Astrophysics Data System (ADS)

    Dickinson, James E., Jr.; Hess, Paul C.

    1985-11-01

    The solubility of rutile has been determined in a series of compositions in the K 2O-Al 2O 3-SiO 2 system ( K ∗ = K 2O /(K 2O + Al 2O 3) = 0.38-0.90), and the CaO-Al 2O 3-SiO 2 system ( C ∗ = CaO/(CaO + Al 2O 3) = 0.47-0.59 ). Isothermal results in the KAS system at 1325°C, 1400°C, and 1475°C show rutile solubility to be a strong function of the K ∗ ratio. For example, at 1475°C the amount of TiO 2 required for rutile saturation varies from 9.5 wt% ( K ∗ = 0.38 ) to 11.5 wt% ( K ∗ = 0.48 ) to 41.2 wt% ( K ∗ = 0.90 ). In the CAS system at 1475°C, rutile solubility is not a strong function of C ∗. The amount of TiO 2 required for saturation varies from 14 wt% ( C ∗ = 0.48 ) to 16.2 wt% ( C ∗ = 0.59 ). The solubility changes in KAS melts are interpreted to be due to the formation of strong complexes between Ti and K + in excess of that needed to charge balance Al 3+. The suggested stoichiometry of this complex is K 2Ti 2O 5 or K 2Ti 3O 7. In CAS melts, the data suggest that Ca 2+ in excess of A1 3+ is not as effective at complexing with Ti as is K +. The greater solubility of rutile in CAS melts when C ∗ is less than 0.54 compared to KAS melts of equal K ∗ ratio results primarily from competition between Ti and Al for complexing cations (Ca vs. K). TiK β x-ray emission spectra of KAS glasses ( K ∗ = 0.43-0.60 ) with 7 mole% added TiO 2, rutile, and Ba 2TiO 4, demonstrate that the average Ti-O bond length in these glasses is equal to that of rutile rather than Ba 2TiO 4, implying that Ti in these compositions is 6-fold rather than 4-fold coordinated. Re-examination of published spectroscopic data in light of these results and the solubility data, suggests that the 6-fold coordination polyhedron of Ti is highly distorted, with at least one Ti-O bond grossly undersatisfied in terms of Pauling's rules.

  4. 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.

  5. 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.

  6. Optical properties of pulsed laser deposited rutile titanium dioxide films on quartz substrates determined by Raman scattering and transmittance spectra

    NASA Astrophysics Data System (ADS)

    Hu, Z. G.; Li, W. W.; Wu, J. D.; Sun, J.; Shu, Q. W.; Zhong, X. X.; Zhu, Z. Q.; Chu, J. H.

    2008-11-01

    Optical response of rutile TiO2 films grown under different laser energy by pulsed laser deposition has been investigated by Raman scattering and spectral transmittance. Dielectric functions in the photon energy range of 1.24-6.5 eV have been extracted by fitting the experimental data with the Adachi's model [S. Adachi, Phys. Rev. B 35, 7454 (1987)]. The refractive index dispersion in the transparent region is mainly ascribed to the higher A1-A2 electronic transitions for the rutile TiO2 films. Owing to slightly different crystalline structures and film densities, the optical band gap linearly increases with increasing packing density. The phenomena were confirmed by different theoretical evaluation methods.

  7. 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.

  8. 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.

  9. A DFT + U study of (Rh, Nb)-codoped rutile TiO2

    NASA Astrophysics Data System (ADS)

    Ghuman, Kulbir Kaur; Singh, Chandra Veer

    2013-02-01

    A systematic study of electronic structure and band gap states is conducted to analyze the monodoping and charge compensated codoping of rutile TiO2 with Rh and Nb, using the DFT + U approach. Doping of rutile TiO2 with Rh atoms induces hybridized O 2p and Rh 4d band gap states leading to a red shift of the optical absorption edge, consistent with previous experimental studies. Since Rh monodoping may induce recombination centers, charge compensated codoping with Rh and Nb is also explored. This codoping induces an electron transfer from Nb induced states to Rh 4d states, which suppresses the formation of Rh4+, thereby leading to a reduction in recombination centers and to the formation of more stable Rh3+. A combination of band gap reduction by 0.5 eV and the elimination of band gap states that account for recombination centers makes (Rh, Nb)-codoped TiO2 a more efficient and stable photocatalyst.

  10. Growth of rectangular hollow tube crystals with rutile-type structure in supercritical fluids

    NASA Astrophysics Data System (ADS)

    Niwa, K.; Ikegaya, H.; Taguchi, T.; Muto, S.; Tokunaga, T.; Hasegawa, M.

    2014-05-01

    Super critical fluids are well known as suitable solvents for dissolution and extraction processes, because it exhibits extreme high solubility and reactivity. However further experimental development using supercritical fluid would offer new insight in material science, especially the synthesis and crystal growth of novel materials. We report the successful growth of single crystals with the rutile-type structure (TiO2, Co-doped TiO2, SiO2, GeO2 and SnO2) in supercritical fluids (water or oxygen) using a laser heated diamond-anvil cell up to a pressure of 7 GPa. The resultant product showed the rectangular hollow tube morphology, a several tens of microns in length and a wall thickness of less than 500 nm. TEM analyses demonstrated that this rectangular hollow tube single crystals were surrounded by the {110} faces and grown along the [001] direction. The preferential growth of {110} faces is consistent with the lowest surface energy of {110} faces of the rutile-type structure. In addition, the rapid cooling rate in LHDAC and high solubility of supercritical fluids also play an important role for the formation of the rectangular hollow tube. The details of the synthesis procedure, characterization and growth mechanism are discussed in this paper.

  11. 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

  12. Hierarchical structures of rutile exposing high-index facets

    NASA Astrophysics Data System (ADS)

    Truong, Quang Duc; Kato, Hideki; Kobayashi, Makoto; Kakihana, Masato

    2015-05-01

    Recently, shape-controlled synthesis of crystals exposing high-index facets has attracted much research interest due to their importance for both fundamental studies and technological applications. Herein, crystals of rutile-type TiO2 with hierarchical structures exposing high-index facets have been synthesized by a facile hydrothermal method using water-soluble titanium complex as a precursor and picolinic acid as structure-directing and shape-controlling agents. The synthesized particles were composed of several branches of pyramidal crystals with relatively smooth surface. On the basis of investigation results, it was speculated that the mutual π-stacking and selective adsorption of picolinic acid on specific {111} facets resulted in the formation of rutile crystals bound by high-index surfaces such as {331}.

  13. 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.

  14. Rutile Solubility in Supercritical Albite-H2O fluids: Implications for Element Mobility in Subduction Zones

    NASA Astrophysics Data System (ADS)

    Antignano, A.; Manning, C. E.

    2006-12-01

    Supercritical fluids with compositions intermediate between H2O and silicate are widely invoked as important transport agents in subduction zones. This proposal is in part motivated by the expectation that such fluids might have greater ability to dissolve and transport key trace elements at high P and T. As a test of this hypothesis, we measured the solubility of rutile (TiO2) in supercritical albite (ab, NaAlSi3O8)-H2O at 900°C, 1.5 GPa, from Xab = 0 to 0.3. At this P and T, rutile has very low solubility in H2O and there is full miscibility between H2O and ab melt. Experiments were conducted in a piston-cylinder apparatus with NaCl-graphite furnaces. In each, a 1.6 mm OD Pt inner capsule with a synthetic rutile crystal was lightly crimped and placed in a 3.5 OD Pt capsule with ultra pure H2O and powdered Amelia albite. Equilibrium was achieved after 4 hrs. Solubility was determined by the weight loss of the rutile grain. Quench textures consistent with supercritical behavior were observed in all runs. Residual corundum is present in the H2O-rich runs, but it decreases with increasing ab concentration. Results show that rutile solubility initially rises sharply with increasing ab concentration from 38 ppm in pure H2O to 739 ppm at Xab =0.05 (44 wt%). With further increase in ab, rutile solubility increases only slightly, to 922 ppm at Xab =0.25 (83 wt%). No significant solubility increase was noted near the critical compositon (~50 wt% ab). Our results show that intermediate fluids do not significantly enhance Ti solubility above dilute silicate-bearing solutions. The presence of residual Al2O3 and the sharp initial rise in rutile solubility at low Xab imply that, by analogy with silicate melts, Ti is present in solution as Na-Ti-O complexes (e.g., Dickenson and Hess, 1985, GCA, 49, 2289). However, the lack of residual corundum at high Xab suggests a transiton to different Ti species, perhaps aqueous NaAlSi3O8-like complexes. Our results give insight into rutile

  15. 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.

  16. Theoretical analysis of STM experiments at rutile TiO 2 surfaces

    NASA Astrophysics Data System (ADS)

    Gülseren, O.; James, R.; Bullett, D. W.

    1997-04-01

    A first-principles atomic orbital-based electronic structure method is used to investigate the low index surfaces of rutile titanium dioxide (TiO 2). The method is relatively cheap in computational terms, making it attractive for the study of oxide surfaces, many of which undergo large reconstructions, and may be governed by the presence of oxygen vacancy defects. Calculated surface charge densities are presented for low-index surfaces of TiO 2, and the relation of these results to experimental scanning tunnelling microscopy images is discussed. Atomic resolution images at these surfaces tend to be produced at positive bias, probing states which largely consist of unoccupied Ti 3d bands, with a small contribution from O 2p. These experiments are particularly interesting since the O atoms tend to sit up to 1 Å above the Ti atoms, so providing a play-off between electronic and geometric structure in image formation.

  17. 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.

  18. 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.

  19. 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...

  20. 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...

  1. Ab initio simulations on rutile-based titania nanowires

    NASA Astrophysics Data System (ADS)

    Zhukovskii, Yu F.; Evarestov, R. A.

    2012-08-01

    The rod symmetry groups for monoperiodic (1D) nanostructures have been applied for construction of models for bulk-like TiO2 nanowires (NWs) cut from a rutile-based 3D crystal along the chosen [001] and [110] directions of crystallographic axes. In this study, we have considered nanowires described by both the Ti-atom centered rotation axes as well as the hollow site centered axes passing through the interstitial positions between the Ti and O atoms closest to the axes. The most stable [001]-oriented TiO2 NWs with rhombic cross sections are found to display the energetically preferable {110} facets only while the nanowires with quasi-square sections across the [110] axis are formed by the alternating { 1bar 10 } and {001} facets. For simulations on rutile-based nanowires possessing different diameters for each NW type, we have performed large-scale ab initio Density Functional Theory (DFT) and hybrid DFT-Hartree Fock (DFT-HF) calculations with total geometry optimization within the Generalized Gradient Approximation (GGA) in the form of the Perdew-Becke-Ernzenhof (PBE) exchange-correlation functionals (PBE and PBE0, respectively), using the formalism of linear combination of localized atomic functions (LCAO). We have simulated both structural and electronic properties of TiO2 NWs depending both on orientation and position of symmetry axes as well as on diameter and morphology of nanowires.

  2. Rutile solubility in H2O-NaAlSi3O8 fluids at High T and P: Implications form HFSE mobility in Subduction zones

    NASA Astrophysics Data System (ADS)

    Antignano, A.; Manning, C. E.

    2005-12-01

    The trace element signatures of arc magmas are characterized by HFSE depletion relative to the LILE. Rutile, a common accessory phase in high-pressure assemblages, is an important reservoir for the HFSE and is often invoked to explain the HFSE depletion of arc magmas. This model is in part based on experimental studies, which show that rutile has very low solubility in pure H2O. However, rutile is also a common accessory to eclogite-facies vein assemblages of albite, paragonite and quartz, which likely precipitated from slab-derived fluids. This observation requires either that fluid fluxes were unrealistically high, or that current estimates of Ti solubility are too low. A possible solution to this problem is that dissolved silicate components can enhance Ti solubility via complexing. To test this, we measured the solubility of rutile in H2O-NaAlSi3O8 (albite) bearing fluids at high T and P. Experiments were conducted using a piston-cylinder apparatus with NaCl-graphite furnaces. A single synthetic rutile crystal was loaded into a 1.6 mm OD Pt inner capsule, which was lightly crimped and then placed in a 3.5 OD Pt outer capsule with ultra pure H2O and powdered Amelia albite. Solubility was determined by the weight loss of the rutile grain after 10 hrs. A time series demonstrates that equilibrium is achieved after 8-10 hrs. Preliminary results at 800°C, 1.0 GPa, show that rutile solubility rises with increasing NaAlSi3O8 concentration from 1.15(12) millimolal at 2.18 wt% NaAlSi3O8 to 3.77(13) at 8.80 wt% NaAlSi3O8. Corundum mats + fluid are observed in 3.4-8.80 wt% NaAlSi3O8 and are interpreted to be the result of incongruent dissolution of albite. Quenched melt spheres where observed in an experiment containing ~15 wt% NaAlSi3O8, but not at 8.80 wt%. At 8.80 wt% NaAlSi3O8, rutile solubility is higher by a factor of 6 relative to that in pure H2O. Our results suggest that TiO2 solubility is increased by complexing with Na-Al-Si-bearing fluid components. It has

  3. Growth and structure of MBE grown TiO2 anatase films with rutile nano-crystallites

    SciTech Connect

    Shao, Rui; Wang, Chong M.; McCready, David E.; Droubay, Timothy C.; Chambers, Scott A.

    2007-03-15

    We have grown TiO2 anatase films with rutile nanocrystalline inclusions using molecular beam epitaxy under different growth conditions. This model system is important for investigating the role of rutile/anatase interfaces in heterogeneous photocatalysis. To control the film structure, we grew a pure anatase (001) layer at a slow rate and then increased the growth rate to drive the nucleation of rutile particles. Structure analysis indicates that the rutile phase has four preferred orientations in the anatase film.

  4. Enhanced Photoelectrochemical Performance from Rationally Designed Anatase/Rutile TiO2 Heterostructures.

    PubMed

    Cao, Fengren; Xiong, Jie; Wu, Fangli; Liu, Qiong; Shi, Zhiwei; Yu, Yanhao; Wang, Xudong; Li, Liang

    2016-05-18

    In a photoelectrochemical (PEC) cell for water splitting, the critical issue is charge separation and transport, which is usually completed by designing semiconductor heterojunctions. TiO2 anatase-rutile mixed junctions could largely improve photocatalytic properties, but impairs PEC water splitting performance. We designed and prepared two types of TiO2 heterostructures with the anatase thin film and rutile nanowire phases organized in different sequences. The two types of heterostructures were used as PEC photoanodes for water splitting and demonstrated completely opposite results. Rutile nanowires on anatase film demonstrated enhanced photocurrent density and onset potential, whereas strong negative performance was obtained from anatase film on rutile nanowire structures. The mechanism was investigated by photoresponse, light absorption and reflectance, and electrochemical impedance spectra. This work revealed the significant role of phase sequence in performance gain of anatase-rutile TiO2 heterostructured PEC photoanodes. PMID:27136708

  5. 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

  6. 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.

  7. 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

    2016-02-01

    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.

  8. Density functional theory study of rutile VO2 surfaces

    NASA Astrophysics Data System (ADS)

    Mellan, Thomas A.; Grau-Crespo, Ricardo

    2012-10-01

    We present the results of a density functional theory investigation of the surfaces of rutile-like vanadium dioxide, VO2(R). We calculate the surface energies of low Miller index planes and find that the most stable surface orientation is the (110). The equilibrium morphology of a VO2(R) particle has an acicular shape, laterally confined by (110) planes and topped by (011) planes. The redox properties of the (110) surface are investigated by calculating the relative surface free energies of the non-stoichiometric compositions as a function of oxygen chemical potential. It is found that the VO2(110) surface is oxidized with respect to the stoichiometric composition, not only at ambient conditions but also at the more reducing conditions under which bulk VO2 is stable in comparison with bulk V2O5. The adsorbed oxygen forms surface vanadyl species much more favorably than surface peroxo species.

  9. Hydrogen Bonds and Vibrations of Water on (110) Rutile

    SciTech Connect

    Kumar, Nitin; Neogi, Sanghamitra; Kent, Paul R; Bandura, Andrei V.; Wesolowski, David J; Cole, David R; Sofo, Jorge O.

    2009-01-01

    We study the relation between hydrogen bonding and the vibrational frequency spectra of water on the (110) surface of rutile (α-TiO2) with three structural layers of adsorbed water. Using ab-initio molecular dynamics simulations at 280, 300 and 320K, we find strong, crystallographically-controlled adsorption sites, in general agreement with synchrotron X-ray and classical MD simulations. We demonstrate that these sites are produced by strong hydrogen bonds formed between the surface oxygen atoms and sorbed water molecules. The strength of these bonds is manifested by substantial broadening of the stretching mode vibrational band. The overall vibrational spectrum obtained from our simulations is in good agreement with inelastic neutron scattering experiments. We correlate the vibrational spectrum with different bonds at the surface in order to transform these vibrational measurements into a spectroscopy of surface interactions.

  10. Potentiometric titrations of rutile suspensions to 250 C

    SciTech Connect

    Machesky, M.L.; Wesolowski, D.J.; Palmer, D.A.; Ichiro-Hayashi, Ken

    1998-04-15

    A stirred hydrogen electrode concentration cell was used to conduct potentiometric titrations of rutile suspensions from 25 to 250 C in NaCl and tetramethylammonium chloride media (0.03 to 1.1 m). Hydrothermal pretreatment of the rutile improved titration reproducibility, decreased titration hysteresis, and facilitated determination of the point of zero net proton charge (pHznpc). These pHznpc values are 5.4, 5.1, 4.7, 4.4, 4.3 ({+-} 0.2 pH units), and 4.2 ({+-} 0.3 pH units) at 25, 50, 100, 150, 200, and 250 C, respectively. The difference between these pHznpc values and 1/2 pK{sub w} (the neutral pH of water) is rather constant between 25 and 250 C ({minus} 1.45 {+-} 0.2). This constancy is useful for predictive purposes and, more fundamentally, may reflect similarities between the hydration behavior of surface hydroxyl groups and water. A three-layer, 1pKa surface complexation model with three adjustable parameters (two capacitance values and one counterion binding constant) adequately described all titration data. The most apparent trend in these data for pH values greater than the pHznpc was the increase in proton release (negative surface charge) with increasing temperature. This reflects more efficient screening by Na{sup +} relative to Cl{sup {minus}}. Replacing Na{sup +} with the larger tetramethylammonium cation for some conditions resulted in decreased proton release due to the less efficient screening of negative surface charge by this larger cation.

  11. 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.

  12. Determination of electron and hole lifetimes of rutile and anatase TiO2 single crystals

    NASA Astrophysics Data System (ADS)

    Yamada, Yasuhiro; Kanemitsu, Yoshihiko

    2012-09-01

    The dynamical behavior of photoexcited states of TiO2 governs the activities of TiO2-based solar cells and photocatalysts. We determined the lifetimes of photoexcited electrons and holes in rutile and anatase TiO2 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 TiO2.

  13. 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

  14. 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.

  15. 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.

  16. 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

  17. 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

  18. Surface protonation at the rutile (110) interface: explicit incorporation of solvation structure within the refined MUSIC model framework.

    PubMed

    Machesky, Michael L; Predota, Milan; Wesolowski, David J; Vlcek, Lukas; Cummings, Peter T; Rosenqvist, Jörgen; Ridley, Moira K; Kubicki, James D; Bandura, Andrei V; Kumar, Nitin; Sofo, Jorge O

    2008-11-01

    The detailed solvation structure at the (110) surface of rutile (alpha-TiO2) 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 A 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 degrees 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 pHznpc values agree to within 0.1 pH unit with those measured at all temperatures between 10 and 250 degrees C. A slightly smaller manual adjustment of the DFT-derived Ti-O surface bond lengths was sufficient to bring the predicted pHznpcvalue of the rutile (110) surface at 25 degrees 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 strength

  19. 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.

  20. 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.

  1. Ultralong Rutile TiO2 Nanowire Arrays for Highly Efficient Dye-Sensitized Solar Cells.

    PubMed

    Li, Hailiang; Yu, Qingjiang; Huang, Yuewu; Yu, Cuiling; Li, Renzhi; Wang, Jinzhong; Guo, Fengyun; Jiao, Shujie; Gao, Shiyong; Zhang, Yong; Zhang, Xitian; Wang, Peng; Zhao, Liancheng

    2016-06-01

    Vertically aligned rutile TiO2 nanowire arrays (NWAs) with lengths of ∼44 μm have been successfully synthesized on transparent, conductive fluorine-doped tin oxide (FTO) glass by a facile one-step solvothermal method. The length and wire-to-wire distance of NWAs can be controlled by adjusting the ethanol content in the reaction solution. By employing optimized rutile TiO2 NWAs for dye-sensitized solar cells (DSCs), a remarkable power conversion efficiency (PCE) of 8.9% is achieved. Moreover, in combination with a light-scattering layer, the performance of a rutile TiO2 NWAs based DSC can be further enhanced, reaching an impressive PCE of 9.6%, which is the highest efficiency for rutile TiO2 NWA based DSCs so far. PMID:27097727

  2. 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.

  3. Zr-doped rutile TiO2: a nuclear quadrupole interaction study

    NASA Astrophysics Data System (ADS)

    Banerjee, D.; Das, S. K.; Das, P.; Thakare, S. V.; Butz, T.

    2010-04-01

    Role of Zr atom on the quadrupole interaction of 181Ta in rutile TiO2 has been investigated by time differential perturbed angular correlation (TDPAC) study. The quadrupole frequency remains same as that in the pure rutile TiO2 but its distribution increases with the amount of Zr. This indicates a metal-metal interaction between probe atom and Zr-atom in the nearest neighbour.

  4. First-principles GGA+U study of the different conducting properties in pentavalent-ion-doped anatase and rutile TiO2

    NASA Astrophysics Data System (ADS)

    Yang, Kesong; Dai, Ying; Huang, Baibiao; Feng, Yuan Ping

    2014-07-01

    The electronic properties of pentavalent-ion (Nb5+, Ta5+, and I5+) doped anatase and rutile TiO2 are studied using spin-polarized GGA + U calculations. Our calculated results indicate that these two phases of TiO2 exhibit different conductive behavior upon doping. For doped anatase TiO2, some up-spin-polarized Ti 3d states lie near the conduction band bottom and cross the Fermi level, showing an n-type half-metallic character. For doped rutile TiO2, the Fermi level is pinned between two up-spin-polarized Ti 3d gap states, showing an insulating character. In addition to the Nb (Ta)-doped anatase TiO2, we propose that the I-doped anatase TiO2 can also be a potential transparent conducting oxide, which is worthy of further experimental verification. These findings clarify the long-standing controversy of whether GGA + U calculation can successfully predict the conducting property in the Nb (Ta)-doped anatase phase and the insulating property in the rutile phase. Moreover, our results show that the symmetry breaking can cause a metal-insulating transition in pentavalent-ion-doped anatase TiO2, though this symmetry breaking may not occur spontaneously because of the relatively high energy barrier.

  5. 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

  6. 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

  7. 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.

  8. Mechanism of multi-defect induced ferromagnetism in undoped rutile TiO{sub 2}

    SciTech Connect

    Wang, Hongxia Zong, Zhaocun; Yan, Yu

    2014-06-21

    Based on first-principles calculations, the coexistence of Ti vacancies (V{sub Ti}) and O vacancies (V{sub O}) is first considered to study the origin of the ferromagnetic ordering in undoped rutile TiO{sub 2}. The calculations show that V{sub O} can induce local magnetic moments in TiO{sub 2}, however, the ferromagnetic (FM) exchange interaction of two V{sub O} is not strong enough to induce room-temperature (RT) ferromagnetism on their own in undoped TiO{sub 2}. The FM coupling between two V{sub Ti} is about four times stronger than that between two V{sub O}. More importantly, the FM coupling between two V{sub Ti} is further enhanced after V{sub O} is introduced. Our results indicate that the electrons induced by V{sub O} mediate the long-range FM exchange interaction between two distant V{sub Ti}. This maybe the ferromagnetism mechanism in undoped TiO{sub 2}: V{sub Ti} produce local moments while the electrons induced by V{sub O} mediated the long-range FM exchange interaction. The results are in excellent agreement with the experimental evidences that V{sub O} alone cannot induce RT ferromagnetism while V{sub O} can promote the ferromagnetic ordering in undoped TiO{sub 2}.

  9. Vanadium and niobium behavior in rutile as a function of oxygen fugacity: evidence from natural samples

    NASA Astrophysics Data System (ADS)

    Liu, Lei; Xiao, Yilin; Aulbach, Sonja; Li, Dongyong; Hou, Zhenhui

    2014-06-01

    Vanadium occurs in multiple valence states in nature, whereas Nb is exclusively pentavalent. Both are compatible in rutile, but the relationship of V-Nb partitioning and dependence on oxygen fugacity (expressed as fO2) has not yet been systematically investigated. We acquired trace-element concentrations on rutile grains ( n = 86) in nine eclogitic samples from the Dabie-Sulu orogenic belt by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and combined them with published results in order to assess the direct and indirect effects of oxygen fugacity on the partitioning of V and Nb into rutile. A well-defined negative correlation between Nb (7-1,200 ppm) and V concentrations (50-3,200 ppm) was found, documenting a competitive relationship in the rutile crystal that does not appear to be controlled by bulk rock or mineral compositions. Based on the published relationship of RtDV and V valence with ∆QFM, we suggest that the priority order of V incorporation into rutile is V4+ > V3+ > V5+. The inferred Nb-V competitive relationship in rutile from the Dabie-Sulu orogenic belt could be explained by decreasing fO2 due to dehydration reactions involving loss of oxidizing fluids during continental subduction: The increased proportion of V3+ (expressed as V3+/∑V) and attendant decrease in RtDV is suggested to lead to an increase in rutile lattice sites available for Nb5+. A similar effect may be observed under more oxidizing conditions. When V5+/∑V increases, RtDV shows a dramatic decline and Nb concentration increases considerably. This is possibly documented by rutile in highly metasomatized and oxidized MARID-type (MARID: mica-amphibole-rutile-ilmenite-diopside) mantle xenoliths from the Kaapvaal craton, which also show a negative V-Nb covariation. In addition, their Nb/Ta covaries with V concentrations: For V concentrations <1,250 ppm, Nb/Ta ranges between 35 and 45, whereas for V > 1,250 ppm, Nb/Ta is considerably lower (5-15). This

  10. Fabrication of phase and morphology controlled pure rutile and rutile/anatase TiO2 nanostructures in functional ionic liquid/water

    NASA Astrophysics Data System (ADS)

    Shahi, Satwant Kaur; Kaur, Navneet; Singh, Vasundhara

    2016-01-01

    In this paper, pure rutile and anatase-rutile TiO2 nanoparticles have been successfully synthesised via a green route by hydrolysis of titanium tetrachloride with room temperature acidic ionic liquid 3-methyl-1-(3-sulfonylpropyl) imidazolium trifluoromethanesulfonate [HO3S(CH2)3MIM][CF3SO3] in aqueous medium. The influence of pH of the solution by varying molar ratio of substrate and ionic liquid has been investigated in both sol-gel and hydrothermal synthesis of TiO2 with significant variation in phase, phase composition (ratio of rutile to anatase) and morphology as indicated by various structural analysis such as XRD, TEM, BET, Raman and UV-vis absorption spectroscopy. The results indicate formation of a bunch of aligned thin flaky nano-rods of TiO2 which look like nano-flowers with a crystal size of 3-5 nm by sol-gel method, while in case of hydrothermal method well-defined rutile solid nanorods of TiO2 were formed with variable length in the range of 120-170 nm and 20-24 nm in width. The photocatalytic activity of the prepared TiO2 samples has been determined by the photodegradation of methyl orange dye (20 ppm) under UV light. Best photocatalytic activity was exhibited by sample S-2 prepared via sol-gel method.

  11. 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

  12. 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.

  13. 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. PMID:26199854

  14. 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

  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. Structure-property correlation in epitaxial (2 0 0) rutile films on sapphire substrates

    NASA Astrophysics Data System (ADS)

    Bayati, M. R.; Joshi, Sh.; Molaei, R.; Narayan, R. J.; Narayan, J.

    2012-03-01

    We have investigated the influence of the deposition variables on photocatalytic properties of epitaxial rutile films. Despite a large lattice misfit of rutile with sapphire substrate, (2 0 0) epitaxial layers were grown on (0 0 0 1)sapphire by domain matching epitaxy paradigm. Using φ-scan XRD and cross section TEM, the epitaxial relationship was determined to be rutile(1 0 0)||sapphire(0 0 0 1), rutile(0 0 1)||sapphire(1 0 -1 0), and rutile(0 1 0)||sapphire(1 -2 1 0). Based on the XRD patterns, increasing the repetition rate introduced tensile stress along the film normal direction, which may arise as a result of trapped defects. Formation of such defects was studied by UV-VIS, PL, and XPS techniques. AFM studies showed that the film roughness increases with the repetition rate. Finally, photocatalytic performance of the layers was investigated through measuring decomposition rate of 4-chlorophenol on the films surface. The films grown at higher frequencies revealed higher photocatalytic efficiency. This behavior was mainly related to formation of point defects which enhance the charge separation.

  17. Preparation of rutile and anatase phases titanium oxide film by RF sputtering.

    PubMed

    Huang, Hong-Hsin; Huang, Chia-Chen; Huang, Ping-Chih; Yang, Cheng-fu; Hsu, Ching-Yun

    2008-05-01

    Titanium oxide films were prepared by RF magnetron sputtering onto glass substrates. The effects of RF power and deposition temperature on crystalline structure, morphology and energy gap were investigated, which were analyzed by X-ray diffraction, SEM and UV-Vis spectrometer, respectively. Results show that rutile phase is the favored structure during deposition. Applying RF power in the range of 50-250 W, the amorphous, rutile, and both rutile and anatase phases TiO2 films were obtained in sequence, while the content of anatase is similar in the range of 34-37% although the RF power increases. Increasing the deposition temperature, the anatase phase coexists in the rutile phase in the range of 100-200 degrees C, and the content of anatase increases from 20 to 41% with the deposition temperature. In addition, according to the morphology observation, the granulous surface is found in rutile phase while facetted surface in anatase phase when titanium oxide films deposited at various RF powers and substrate temperatures. The band gap energy of titanium oxide evaluated from (alphahv)1/2 versus energy plots show that the energy gap decreases with RF power increasing. PMID:18572703

  18. Lithium insertion into mesoscopic and single-crystal TiO{sub 2} (rutile) electrodes

    SciTech Connect

    Kavan, L.; Fattakhova, D.; Krtil, P.

    1999-04-01

    Electrochemical behavior of single-crystal and mesoscopic TiO{sub 2} (rutile) was studied in propylene carbonate solutions at potentials negative to the flatband potential. In electrolytic solutions containing sodium or tetrabutylammonium (Bu{sub 4}N{sup +}), the injected charge is compensated by protonization of the surface and/or by adsorption of cations in the double layer. In electrolytic solutions containing Li{sup +}, the insertion into the rutile lattice occurs at potentials below 1.5 V (Li/Li{sup +}). At higher potentials, the charge is compensated mainly by a nonfaradaic process. Lithium insertion into rutile proceeds at a potential ca. 0.4 V more negative than the insertion potential into anatase. The maximum insertion capacity of rutile is also lower than that of anatase. The insertion of lithium into rutile is accompanied by an increase of the electrode mass, while the mass/charge relations show hystereses between anodic and cathodic potential sweeps. This behavior is explained in terms of a free convection in the electrode vicinity.

  19. 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.

  20. Synthesis of anatase and rutile TiO2 nanostructures from natural ilmenite

    NASA Astrophysics Data System (ADS)

    Wahyuingsih, Sayekti; Ramelan, Ari Handono; Pramono, Edi; Sulistya, Ariantama Djati; Argawan, Panji Rofa; Dharmawan, Frenandha Dwi; Rinawati, Ludfiaastu; Hanif, Qonita Awliya; Sulistiyono, Eko; Firdiyono, Florentinus

    2016-02-01

    Nanostructure anatase and rutile type TiO2 were synthesized from dissolution roasted ilmenite from natural ilmenite sand as the starting materials. Anatase TiO2 and rutile TiO2 (high crystallinity) with the diameters of 20-100 nm were obtained by calcined soluble ilmenite sand produced by leaching process. Calcinations of the xerogel TiO2 from liquor products were conducted for 4 hours at temperature of 450 °C. The samples were characterized by XRD (X-ray diffraction), STA (simultant thermal analysis), TEM (Transmission Electron Microscopy), and BET surface area. Titania Anatase-Rutile form as a mixture were produced by titania slag with the hydrolysis product. While, in another route, complete titania anatase phase was produced through hydrolysis and condensation steps of leach liquors. This synthesis methods provide a simple route to fabricate nanostructure TiO2 from low cost material.

  1. Room temperature synthesis of rutile nanorods and their applications on cloth

    NASA Astrophysics Data System (ADS)

    Fei, Bin; Deng, Zhaoxiang; Xin, John H.; Zhang, Yihe; Pang, Geoffrey

    2006-04-01

    In order to achieve better photocatalytic performance, rutile nanorods dispersed in anatase and brookite phases were synthesized from titanium isopropoxide (TIP) in a concentrated HNO3 solution at room temperature (23 °C). X-ray diffraction results indicated that the percentage of rutile increased with increasing peptization time. Scanning electron microscopy and and high-resolution transmission electron microscopy measurements revealed that the nanosized titania particles mainly consisted of granular anatase and brookite, and rod-like rutile. It was interesting that the stability of the colloid increased with increasing nanoparticle concentration, and the tricrystalline titania showed a photocatalytic activity higher than that of pure anatase. These nanocrystals were applied onto cotton fabrics, and achieved a promising bactericidal photocatalytic activity and excellent protection against UV radiation.

  2. The superior lithium storage capabilities of ultra-fine rutile TiO 2 nanoparticles

    NASA Astrophysics Data System (ADS)

    Chen, Jun Song; Lou, Xiong Wen

    The lithium storage capabilities of ultra-fine rutile TiO 2 nanoparticles have been studied. Ultra-fine rutile TiO 2 nanoparticles with only several nanometers in size have been prepared by a modified wet-chemical method with a high yield. Unexpectedly, the rutile TiO 2 nanoparticles with 3 nm in size exhibit superior lithium storage properties. Specifically, they show long term cycling stability upon extended cycling for at least 300 cycles with a capacity loss of only 0.17% per cycle, and good rate capability up to a 30 C rate. The excellent reversible lithium storage capabilities could be attributed to the ultra-fine size giving rise to a very short diffusion path, and the relatively large surface area which provides more sites for lithium insertion.

  3. Thermal stability of sputter deposited nanomosaic rutile TiO{sub 2}

    SciTech Connect

    Aita, Carolyn Rubin

    2009-07-15

    A domain structure based on the rutile lattice with a large density of (1/2)<011>{l_brace}011{r_brace}-type stacking faults is found in sputter deposited TiO{sub 2} films [J. Vac. Sci. Technol. A 24, 2054 (2006)]. The thermal stability of nanomosaic rutile at moderate temperature is reported here. Films are annealed at 973 K for 0.25-15 h, characterized by x-ray diffraction. A Johnson-Mehl-Avrami-Kolmogorov analysis indicates impeded crystallite growth. A dislocation-locking mechanism is proposed for this behavior. Partial dislocations with (1/2)<011> Burgers vectors that bound the stacking faults glide on intersecting {l_brace}011{r_brace} slip planes and react to produce sessile stair rod dislocations. Without the high temperature required for dislocation climb, (1/2)<011>{l_brace}011{r_brace}-type faults inherent to nanomosaic rutile provide thermal stability against massive crystallite growth.

  4. Controlled formation of anatase and rutile TiO2 thin films by reactive magnetron sputtering

    NASA Astrophysics Data System (ADS)

    Rafieian, Damon; Ogieglo, Wojciech; Savenije, Tom; Lammertink, Rob G. H.

    2015-09-01

    We discuss the formation of TiO2 thin films via DC reactive magnetron sputtering. The oxygen concentration during sputtering proved to be a crucial parameter with respect to the final film structure and properties. The initial deposition provided amorphous films that crystallise upon annealing to anatase or rutile, depending on the initial sputtering conditions. Substoichiometric films (TiOx<2), obtained by sputtering at relatively low oxygen concentration, formed rutile upon annealing in air, whereas stoichiometric films formed anatase. This route therefore presents a formation route for rutile films via lower (<500 °C) temperature pathways. The dynamics of the annealing process were followed by in situ ellipsometry, showing the optical properties transformation. The final crystal structures were identified by XRD. The anatase film obtained by this deposition method displayed high carriers mobility as measured by time-resolved microwave conductance. This also confirms the high photocatalytic activity of the anatase films.

  5. The effect of electron localization on the electronic structure and migration barrier of oxygen vacancies in rutile.

    PubMed

    Zhu, Linggang; Hu, Qing-Miao; Yang, Rui

    2014-02-01

    By applying the on-site Coulomb interaction (Hubbard term U) to the Ti d orbital, the influence of electron localization on the electronic structure as well as the transport of oxygen vacancies (VO) in rutile was investigated. With U = 4.5 eV, the positions of defect states in the bandgap were correctly reproduced. The unbonded electrons generated by taking out one neutral oxygen atom are spin parallel and mainly localized on the Ti atoms near VO, giving rise to a magnetic moment of 2 μB, in agreement with the experimental finding. With regard to the migration barrier of VO, surprisingly, we found that U = 4.5 eV only changed the value of the energy barrier by ±0.15 eV, depending on the diffusion path. The most probable diffusion path (along [110]) is the same as that calculated by using the traditional GGA functional. To validate the GGA + U method itself, a hybrid functional with a smaller supercell was used, and the trend of the more probable diffusion path was not changed. In this regard, the traditional GGA functional might still be reliable in the study of intrinsic-defect transportation in rutile. Analyzing the atomic distortion and density of states of the transition states for different diffusion paths, we found that the anisotropy of the diffusion could be rationalized according to the various atomic relaxations and the different positions of the valence bands relative to the Fermi level of the transition states. PMID:24441015

  6. 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.

  7. Doping and compensation in Nb-doped anatase and rutile TiO2

    NASA Astrophysics Data System (ADS)

    Lee, Hsin-Yi; Robertson, John

    2013-06-01

    The substitutional Nb donor states in anatase and rutile TiO2 are calculated using the screened exchange hybrid density functional. The calculations find that Nb forms a shallow state in anatase and a deep state in rutile TiO2, as in experiment. Donors in anatase are found to become compensated in O-rich conditions because oxygen interstitial acceptors acquire a negative formation energy for Fermi energies high in the band gap. O-poor conditions permit doping, not by creating O vacancies but by inhibiting the formation of oxygen interstitials which compensate doping.

  8. 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.

  9. 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

  10. 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).

  11. 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

  12. Non-innocent adsorption of Co-pyrphyrin on rutile(110).

    PubMed

    Gurdal, Yeliz; Luber, Sandra; Hutter, Jürg; Iannuzzi, Marcella

    2015-09-21

    Solar-light driven water splitting is a promising way for the sustainable production of molecular hydrogen, the latter representing an efficient carrier for energy storage and conversion into common liquid fuels. In search of novel catalysts for high-performance water splitting devices, Co-pyrphyrin (CoPy) has been recently synthesized and successfully used as a homogeneous water reduction catalyst. We investigate the adsorption of this molecule on the rutile TiO2(110) surface as a possible first step towards the design of a heterogeneous water reduction system. We find that the adsorption of the molecule is stabilized by the interaction of the cyano groups with the under-coordinated Ti centers present at the surface. This interaction induces the rehybridization of the molecular orbitals localized on the cyano groups and the realignment of the lowest unoccupied molecular states. Moreover, the highest occupied molecular orbital of CoPy@rutile(110) is localized on CoPy and the energy gap turns out to be significantly smaller than the gap of pristine rutile(110). This implies that direct or indirect injection of electrons from CoPy to the rutile(110) surface is in principle possible upon the absorption of light in the visible range. On the other hand, the electronic properties of the Co(ii) center are not modified by the adsorption, which suggests that CoPy and its derivatives may be used in water electrolysis for hydrogen production also in the adsorbed state. PMID:26264077

  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. 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.

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

    DOE PAGESBeta

    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

  18. 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.

  19. Characterization of individual molecular adsorption geometries by atomic force microscopy: Cu-TCPP on rutile TiO2 (110).

    PubMed

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

    2015-09-01

    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 TiO2 (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 TiO2. 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. PMID:26342363

  20. Characterization of individual molecular adsorption geometries by atomic force microscopy: Cu-TCPP on rutile TiO2 (110)

    NASA Astrophysics Data System (ADS)

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

    2015-09-01

    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 TiO2 (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 TiO2. 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.

  1. The Hf-Nd Systematics of Rutile-Bearing Eclogites From Koidu, Sierra Leone

    NASA Astrophysics Data System (ADS)

    Tibbetts, N. J.; Bizimis, M.; Salters, V. J.; Rudnick, R. L.

    2008-12-01

    Xenoliths from the Cretaceous Koidu kimberlite complex, Sierra Leone, West Africa, provide a rare opportunity to investigate the origin of rutile-bearing eclogites with variable, but superchondritic Nb/Ta, Nb/La and Ti/Zr ratios (Rudnick et al, 2000). Previous studies of the trace element and δ18O values of mineral separates and reconstructed whole rock compositions of two suites (high and low MgO) of eclogites lead to two inferred origins: as cumulates (high MgO eclogites, Barth et al., 2002) or residues of altered Archean oceanic crust (low MgO eclogites, Barth et al., 2001). We present the first Hf-Nd isotope data on clinopyroxenes (cpx) and garnets (gt) from Koidu eclogites. The reconstructed whole rock (cpx+gt) Hf isotopic compositions are heterogeneous, ranging in ɛHf from 0.2 to + 41 at the time of kimberlite eruption (85 Ma). Nd isotopic compositions are equally variable (ɛNd = 0.1 to +37), placing all eclogites at drastically more radiogenic values than terrestrial basalts. However, a significant part of the Hf- budget can reside in the rutile, which will most likely have a less radiogenic hafnium isotopic composition compared to the silicates. One can construct a limiting case by using mass balance arguments to calculate the hypothetical hafnium isotopic composition of the rutile. The bulk rock hafnium isotopic composition was constrained to be 4Ga old subducted oceanic crust. Even with a high modal abundance of rutile and a high Hf concentration in rutile, the calculated isotopic compositions are unrealistic and calculated rutile ages far exceed the age of the Universe. Using a younger age for the eclogite (2 or 3 Ga) does not significantly affect the calculated result. These first-order approximations show that the addition of rutile does not change the whole rock isotopic composition significantly from the radiogenic Hf-Nd compositions based on cpx and garnet alone. Our findings do not support geochemical models that predict 143Nd/144Nd and 176Hf

  2. Properties of hydrogen and hydrogen-vacancy complexes in the rutile phase of titanium dioxide

    NASA Astrophysics Data System (ADS)

    Filippone, F.; Mattioli, G.; Alippi, P.; Amore Bonapasta, A.

    2009-12-01

    The interaction of atomic H with host atoms and oxygen vacancies (VO) in the rutile phase of the TiO2 metal oxide has been investigated by using density-functional theory-local spin density (DFT-LSD) and DFT-LSD+U theoretical methods. The achieved results show that H in rutile presents quite different and peculiar properties with respect to other semiconductors and metal oxides. It behaves indeed neither as an amphoteric impurity, as it does in Si and GaAs, nor as a shallow donor, as it has been proposed in ZnO. Moreover, H in rutile represents a failure of a theoretical model proposing a universal alignment of the H-induced electronic level in the energy gaps of semiconductors, which predicts a shallow donor behavior of H in ZnO and TiO2 . Present results show indeed that H behaves as a deep donor in rutile and always forms an OH+ complex, independent of the position of the Fermi energy. This very unusual behavior of H can be accounted for by a peculiar property of TiO2 regarding its capability of localizing extra electrons at Ti+3 sites. The electron lost by H can be accommodated indeed by a Ti+4 atom which evolves in a Ti+3 defect. This accounts for the deep behavior of H and implies that the electronic level it induces in the TiO2 energy gap has, actually, a Ti+3 character quite similar to that characterizing an O vacancy (VO) , thus distinguishing H in rutile from H in other semiconductors. Finally, H can form stable H-VO complexes where it takes the place of the missing O atom by forming a bond with a prevailing ionic character, at variance with a multicenter bond model proposed for the same complexes in ZnO.

  3. 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

  4. Multi-Timescale Investigation of Radiation Damage near TiO2 Rutile Grain Boundaries

    SciTech Connect

    Xian-Ming Bai; Blas P. Uberuaga

    2012-04-01

    Although grain boundaries (GBs) have been experimentally demonstrated to serve as sinks for absorbing radiation induced defects and improving the radiation tolerance of materials, the detailed atomistic interactions between defects and GBs leading to this enhanced tolerance are not well understood. In oxide ceramics the interactions are further complicated as defects can be charged and grain boundaries may exhibit space charge and charge dipole effects. Here, we use two atomistic modeling methods to examine the role of GBs in a model oxide system, rutile TiO2, in modifying defect production during irradiation events. The GB studied is a symmetric tilt GB with a rotation axis of [100] and a rotation angle of 15.25{sup o}. We use molecular dynamics to investigate defect production near the GB at both 300K and 1000 K and find that the damage production is sensitive to the initial distance of the primary knock-on atom (PKA) from the GB. We find three distinct regimes in which GBs have different effects on modifying defect production. Similar to GBs in metals, the GB absorbs more interstitials than vacancies at certain distances while this behavior of biased loading of interstitials diminishes at other distances. Further, we obtain the statistics of both interstitial and vacancy clusters 2 produced in collision cascades in terms of their compositions at two temperatures. We find that perfectly stoichiometric defect clusters (Schottky and anti-Schottky clusters) represent a small fraction of the total defect clusters produced. Moreover, a significant reduction in the number of interstitial clusters at 1000 K compared to 300 K is thought to be a consequence of enhanced migration of interstitials towards the GB. Finally the kinetic properties of certain defect clusters are investigated with temperature accelerated dynamics, without any priori assumptions of migration mechanisms. We find that small interstitial clusters become mobile at high temperatures while small vacancy

  5. Strong metal-support interaction and catalytic properties of anatase and rutile supported palladium catalyst Pd/TiO 2

    NASA Astrophysics Data System (ADS)

    Li, Yuanzhi; Fan, Yining; Yang, Hanpei; Xu, Bolian; Feng, Lingyun; Yang, Mingfeng; Chen, Yi

    2003-04-01

    In situ EPR investigation by using CO as probe molecules shows that even pre-reduced by H 2 at lower temperature results in SMSI for anatase titania supported palladium catalyst, but not for rutile titania supported palladium catalyst. The reason of the different behavior between rutile and anatase titania supported palladium catalyst is discussed. The very different catalytic properties between anatase and rutile titania supported palladium catalyst pre-reduced at lower temperature, and the rapid change of conversion and selectivity of titania supported palladium catalyst with the elevation of pre-reduction temperature further confirm the above-mentioned results.

  6. Electron Transport at the TiO₂ Surfaces of Rutile, Anatase, and Strontium Titanate: The Influence of Orbital Corrugation.

    PubMed

    Sarkar, Tarapada; Gopinadhan, Kalon; Zhou, Jun; Saha, Surajit; Coey, J M D; Feng, Yuan Ping; Ariando; Venkatesan, T

    2015-11-11

    The two-dimensional electron gas in SrTiO3 created by an overlayer of amorphous LaAlO3 is compared with those at the TiO2-terminated surfaces of rutile and anatase. Differences in conductivity are explained in terms of the limiting Ti-O-Ti bond angles (orbital corrugation), band dispersion, and polaron formation. At 300 K, the sheet conductivity and mobility of anatase exceed those for SrTiO3 or rutile by one or two orders of magnitude, respectively. The electrons in rutile become localized below 25 K. PMID:26509804

  7. Potential Energy Surfaces of Oxygen Vacancies in Rutile TiO2: Configuration Coordinate and Migration Barrier Schemes

    NASA Astrophysics Data System (ADS)

    Kazempour, Ali

    2013-09-01

    Applying the screened hybrid functional Heyd-Scuseria-Ernzerhof (HSE) method, we studied the polaronic degree of freedom of different charged oxygen vacancies Vo in rutile TiO2. The HSE method not only corrects the band gap, but also allows for correct polaron localization. Due to the important role of phonon in oxygen vacancy associated levels in the gap, we calculated configuration coordinate (CC) potential energy surfaces for all charged Vo's. Our calculated CC diagrams with effective impression on host states, show significant improvement of electron-lattice interaction compared to semi(local) DFT methods. The obtained values of stokes shifts for sequential transitions of charged vacancies agree well with experimental evidences which confirm Ti3+ centers are responsible for photoluminescence. In addition, we explored the effect of polaron localization on diffusive mechanism of Vo along most open [001] direction. Calculated values of migration barriers for V o2+ are found to be in quantitative agreement with experimental migration energy [E. Iguchi and K. Yajima, J. Phys. Soc. Jpn.32 (1971) 1415] of 2.4 eV. These results highlight the small polaronic behavior of Vo's and is consistent with studies suggest the polaronic hopping model for electron transport of n-type conductivity in reduced TiO2 [J.-F. Baumard and F. Gervais, Phys. Rev. B15 (1977) 2316-2323].

  8. Plasmonic photocatalysis properties of Au nanoparticles precipitated anatase/rutile mixed TiO2 nanotubes

    NASA Astrophysics Data System (ADS)

    Wen, Yan; Liu, Bitao; Zeng, Wei; Wang, Yuhua

    2013-09-01

    Anatase/rutile mixed titania nanotubes (TiO2 NTs) precipitated with gold nanoparticles (Au NPs), i.e. Au/TiO2, have been synthesized and investigated on visible photocatalysis properties. A deposition-precipitation (DP) method was adopted to reduce the gold precursor to Au NPs within the preformed TiO2 NTs by the emulsion electrospinning technique. The optimal visible photocatalytic activity was found in the sample Au3(DP350)/TiO2 with a loading of 3 wt% Au NPs and calcining at 350 °C. Through transmission electron microscopy, Au NPs of 4.16 nm diameter were observed at the interface between the anatase and rutile phases in the optimal Au3(DP350)/TiO2 sample, and these joint active sites at the interface were beneficial for charge separation. The obtained optimal photocatalytic efficiency of Au3(DP350)/TiO2 was ascribed to the synergistic effect of the enhanced visible absorption and the anatase/rutile mixed-phase composition, and the possible mechanism for this was discussed in detail.Anatase/rutile mixed titania nanotubes (TiO2 NTs) precipitated with gold nanoparticles (Au NPs), i.e. Au/TiO2, have been synthesized and investigated on visible photocatalysis properties. A deposition-precipitation (DP) method was adopted to reduce the gold precursor to Au NPs within the preformed TiO2 NTs by the emulsion electrospinning technique. The optimal visible photocatalytic activity was found in the sample Au3(DP350)/TiO2 with a loading of 3 wt% Au NPs and calcining at 350 °C. Through transmission electron microscopy, Au NPs of 4.16 nm diameter were observed at the interface between the anatase and rutile phases in the optimal Au3(DP350)/TiO2 sample, and these joint active sites at the interface were beneficial for charge separation. The obtained optimal photocatalytic efficiency of Au3(DP350)/TiO2 was ascribed to the synergistic effect of the enhanced visible absorption and the anatase/rutile mixed-phase composition, and the possible mechanism for this was discussed in

  9. The unexpectedly rich reconstructions of rutile TiO2(011)-(2 × 1) surface and the driving forces behind their formation: an ab initio evolutionary study.

    PubMed

    Wang, Qinggao; Oganov, Artem R; Feya, Oleg D; Zhu, Qiang; Ma, Dongwei

    2016-07-20

    In this paper, we employ state-of-the-art theoretical approaches to elucidate the structures of the (011) surface of rutile (R-)TiO2. An unexpectedly rich chemistry has been uncovered. Titanyl-TiO2 and titanyl-Ti2O3 reconstructions can be used for rationalizing the experimental findings, matching the STM images and the changes in the band gap. From the viewpoint of thermodynamics, the predicted MF(111)-TiO reconstruction is more reasonable than the previously proposed MF(111)-TiO3 model, although there is a structural similarity. The richness of surface phases, the formation of which is driven by thermodynamic conditions and surface stress release, implies the multifunctionality of the R-TiO2(011) surface. After the clarification of TiO2(011) and TiO2(110) surface structures {PRL, 2014, 113, 266101} (the most important surfaces of rutile), the origin of the Brønsted acidity of R-TiO2, which has remained a mystery at the atomic level, can also be addressed in the near future. PMID:27086932

  10. 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.

  11. 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

  12. 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

  13. 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

  14. 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.

  15. 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.

  16. Charge and magnetic states of rutile TiO2 doped with Cr ions.

    PubMed

    Kim, Rokyeon; Cho, Suyeon; Park, Won-Goo; Cho, Deok-Yong; Oh, Se-Jung; Saint-Martin, Romuald; Berthet, Patrick; Park, Je-Geun; Yu, Jaejun

    2014-04-01

    We observe that the electronic and magnetic properties of Cr-doped rutile TiO2 single crystals are highly dependent on growth conditions. The ferromagnetic component of magnetic susceptibility is observed to be enhanced for samples grown under oxygen-rich conditions. To understand the charge state of Cr dopants and their role in response to an external magnetic field, we carry out density functional theory calculations for Cr-doped rutile TiO2. Using the results of formation energy calculations in the presence of oxygen vacancies and Cr atom substitution at the Ti sites, we demonstrate that the Cr3+ state is a source of Curie-Weiss-type magnetic response, whereas the Cr4+ defect states contribute to the ferromagnetic component. We also provide the electronic structures of various defect configurations and attempt to explain the optical and electronic properties of the Cr-doped system. PMID:24651728

  17. 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.

  18. 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

  19. Direct View at Excess Electrons in TiO2 Rutile and Anatase

    NASA Astrophysics Data System (ADS)

    Setvin, Martin; Franchini, Cesare; Hao, Xianfeng; Schmid, Michael; Janotti, Anderson; Kaltak, Merzuk; Van de Walle, Chris G.; Kresse, Georg; Diebold, Ulrike

    2014-08-01

    A combination of scanning tunneling microscopy and spectroscopy and density functional theory is used to characterize excess electrons in TiO2 rutile and anatase, two prototypical materials with identical chemical composition but different crystal lattices. In rutile, excess electrons can localize at any lattice Ti atom, forming a small polaron, which can easily hop to neighboring sites. In contrast, electrons in anatase prefer a free-carrier state, and can only be trapped near oxygen vacancies or form shallow donor states bound to Nb dopants. The present study conclusively explains the differences between the two polymorphs and indicates that even small structural variations in the crystal lattice can lead to a very different behavior.

  20. 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.

  1. Hydrogen shallow donors in ZnO and rutile TiO2

    NASA Astrophysics Data System (ADS)

    Weber, Jörg; Lavrov, Edward V.; Herklotz, Frank

    2012-05-01

    A combined study of IR absorption, photoconductivity, photoluminescence and Raman measurements in ZnO samples supports the theoretical suggestions of a shallow bond-centered hydrogen donor and a shallow hydrogen donor within the oxygen vacancy. In rutile TiO2 we also identify a shallow hydrogen donor in contrast to recent theoretical predictions. A possible solution to this obvious discrepancy is proposed.

  2. Transformation of rutile to TiO{sub 2}-II in a high pressure hydrothermal environment

    SciTech Connect

    Spektor, Kristina; Tran, Dung Trung; Leinenweber, Kurt; Häussermann, Ulrich

    2013-10-15

    The high pressure transformation of rutile to TiO{sub 2}-II with the α-PbO{sub 2} structure is known to be kinetically hindered. In this study we show that a hydrothermal environment at 6 GPa and 650 °C provides appreciable rates for producing single phase bulk samples of TiO{sub 2}-II. So obtained TiO{sub 2}-II was characterized by scanning electron microscopy, powder X-ray diffraction, Raman and Far-IR spectroscopy. The structural properties are identical to TiO{sub 2}-II from dry transitions. Transmission electron microscopy studies strongly indicate that Ostwald ripening processes play an important role in the hydrothermally assisted transformation and subsequent growth of TiO{sub 2}-II crystals. TiO{sub 2}-II is thermally stable to about 550 °C. At 600 °C the onset of the transformation to rutile is observed. The thermal expansion in the temperature range from room temperature to 500 °C is highly anisotropic, virtually affecting only the c unit cell parameter (α{sub c}=7.1(2)×10{sup −6} °C{sup −1}). The pressure–temperature conditions for the hydrothermally assisted transformation of rutile are viable for industrial production settings, and in light of the large technological significance of TiO{sub 2}, TiO{sub 2}-II may present an interesting target for large-scale synthesis. - Graphical abstract: Highly crystalline TiO{sub 2}-II, which is the high pressure form of titania with the α-PbO{sub 2} structure, can be prepared from rutile at 6 GPa and 650 °C when employing a hydrothermal environment. Display Omitted.

  3. UV to NIR photon conversion in Nd-doped rutile and anatase titanium dioxide films for silicon solar cell application

    NASA Astrophysics Data System (ADS)

    Le Boulbar, E.; Millon, E.; Ntsoenzok, E.; Hakim, B.; Seiler, W.; Boulmer-Leborgne, C.; Perrière, J.

    2012-06-01

    Undoped and Nd-doped titanium dioxide anatase and rutile films have been grown by pulsed-laser deposition at 700 °C under 0.1 mbar O2. By selecting adequate substrates, TiO2 films doped with 1, 2 or 5 at.% Nd were grown and constituted with polycrystalline rutile, highly oriented (2 0 0) rutile film, or oriented (0 0 4) anatase. An UV to NIR photon conversion is evidenced in the films. Indeed, intense and well-resolved emission lines from Nd3+ have been observed upon excitation above the TiO2 bandgap at room temperature. The sensitised emission of Nd3+ is found to be much efficient in rutile than in anatase structure. Low temperature photoluminescence measurements lead to fine resolved peaks corresponding to the Nd3+ 4f transitions with different spectral characteristic according to the host matrix used. Photoluminescence dependence temperature evidences that the light emission from Nd3+ in anatase-based films is probably influenced by the presence of self-trapped excitons or by orbital interaction. Mechanisms of sensitisation host to Nd3+ are proposed for both matrixes. Finally, the Nd dopant concentration and the microstructure of TiO2 rutile films are found to affect the photoluminescence emission intensity. Rutile film (2 0 0) oriented is the most adapted host matrix to sensitise 1 at.% Nd3+ ions for an emission around 1064 nm making such Nd-doped layers interesting for photon conversion by down shifting process.

  4. 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.

  5. 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. PMID:15120128

  6. 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.

  7. 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.

  8. Pyrocatechol as a surface capping molecule on rutile TiO 2 (110)

    NASA Astrophysics Data System (ADS)

    Syres, K. L.; Thomas, A. G.; Cant, D. J. H.; Hardman, S. J. O.; Preobrajenski, A.

    2012-02-01

    A 'cap and dip' method of adsorbing ruthenium di-2,2‧-bipyridyl-4,4‧-dicarboxylic acid diisocyanate (N3 dye) on a rutile TiO2 (110) surface was investigated using pyrocatechol as a capping molecule. This method involves cleaning the rutile surface in ultra-high vacuum (UHV), depositing pyrocatechol onto the surface to 'cap' the adsorption sites, removing from vacuum, 'dipping' in an N3 dye solution and returning to vacuum. Photoemission measurements following the return of the crystal to vacuum suggest that the pyrocatechol keeps the surface free from contamination on exposure to atmosphere. Photoemission spectra also indicate that the pyrocatechol capping molecules are replaced by the N3 dye in solution and that the N3 dye is adsorbed intact on the rutile TiO2 (110) surface. This technique may allow other large molecules, which are thermally unstable to evaporation in UHV, to be easily deposited onto TiO2 surfaces.

  9. Plasmonic photocatalysis properties of Au nanoparticles precipitated anatase/rutile mixed TiO2 nanotubes.

    PubMed

    Wen, Yan; Liu, Bitao; Zeng, Wei; Wang, Yuhua

    2013-10-21

    Anatase/rutile mixed titania nanotubes (TiO2 NTs) precipitated with gold nanoparticles (Au NPs), i.e. Au/TiO2, have been synthesized and investigated on visible photocatalysis properties. A deposition-precipitation (DP) method was adopted to reduce the gold precursor to Au NPs within the preformed TiO2 NTs by the emulsion electrospinning technique. The optimal visible photocatalytic activity was found in the sample Au3(DP350)/TiO2 with a loading of 3 wt% Au NPs and calcining at 350 °C. Through transmission electron microscopy, Au NPs of 4.16 nm diameter were observed at the interface between the anatase and rutile phases in the optimal Au3(DP350)/TiO2 sample, and these joint active sites at the interface were beneficial for charge separation. The obtained optimal photocatalytic efficiency of Au3(DP350)/TiO2 was ascribed to the synergistic effect of the enhanced visible absorption and the anatase/rutile mixed-phase composition, and the possible mechanism for this was discussed in detail. PMID:23963545

  10. 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.

  11. High-Q sapphire-rutile frequency-temperature compensated microwave dielectric resonators.

    PubMed

    Tobar, M E; Krupka, J; Hartnett, J G; Ivanov, E N; Woode, R A

    1998-01-01

    A sapphiro-rutile composite resonator was constructed from a cylindrical sapphire monocrystal with two thin disks of monocrystal rutile held tightly against the ends. Because rutile exhibits low loss and an opposite temperature coefficient of permittivity to sapphire, it is an ideal material for compensating the frequency-temperature dependence of a sapphire resonator. Most of the electromagnetic modes in the composite structure exhibited turning points (or compensation points) in the frequency-temperature characteristic. The temperatures of compensation for the WG quasi TM modes were measured to be below 90 K with Q-factors of the order of a few million depending on the mode. For WG quasi TE modes, the temperatures of compensation were measured to be between 100 to 160 K with Q-factors of the order of a few hundreds of thousands, depending on the mode. The second derivatives of the compensation points were measured to be of the order 0.1 ppm/K(2 ), which agreed well with the predicted values. PMID:18244235

  12. Tin-doped rutile titanium dioxide nanowires: luminescence, gas sensor, and field emission properties.

    PubMed

    Wu, Jyh Ming

    2012-02-01

    Sn-doped rutile TiO2 nanowires were synthesized by a thermal reactive evaporation route. Field emission scanning electron microscopy (FESEM) imaging reveals that the Sn-doped TiO2 nanowires exhibited diameters of 80-150 nm and 2-3 microns in length. High-resolution transmission electron microscopy (HRTEM) imaging makes it possible to observe that Sn-doped TiO2 nanowires show a certain lattices fringe of approximately 0.32 nm, which demonstrates that the nanowires are single crystalline with rutile structure and grow along the [110] axis. Cathodoluminescence (CL) reflected that on the surface of Sn-doped TiO2 nanowires, many oxygen vacancies and defect states were formed during the crystal growth. These defect states raised a broad emission peak around the red-orange band. The ethanol sensing properties of Sn-doped rutile TiO2 nanowires at a temperature of 190 degrees C for the ethanol concentrations of 50, 100, 150, 200, 400, 500, and 600 ppm, correspond to the sensor' sensitivity of 7, 12, 18, 19, 23, and 26%, respectively. The sensitivity increased with an increase in the ethanol concentration. As-synthesized TiO2 nanowires revealed a turn-on field, approximately 5.1 V/microm, at a current density of 1 microAcm(-2). PMID:22629973

  13. 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.

  14. 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.

  15. 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.

  16. Competition between ferromagnetism and antiferromagnetism in the rutile C r1 -xVxO2 system

    NASA Astrophysics Data System (ADS)

    Mustonen, Otto; Vasala, Sami; Chou, Ta-Lei; Chen, Jin-Ming; Karppinen, Maarit

    2016-01-01

    We present a comprehensive computational and experimental examination of the C r1 -xVxO2 (0 ≤x ≤0.5 ) system. The entire series crystallizes in the rutile structure, but the compounds exhibit significantly different magnetic properties depending on x . Lattice parameter a increases linearly with x , but the c parameter is slightly reduced due to vanadium-vanadium bonding. The V-for-Cr substitution creates C r3 +-V5 + pairs; this leads to competition between ferromagnetic (C r4 +-C r4 + ) and antiferromagnetic (C r3 +-C r3 + ) interactions such that the materials change from ferromagnetic to antiferromagnetic with increasing x . Weak ferromagnetic interactions arising from C r4 + are observed even in the seemingly antiferromagnetic phases with the exception of x =0.5 , which contains only C r3 + . Density functional theory calculations are performed, but they incorrectly predict the x =0.5 phase to be a half-metal. This is caused by an incorrect prediction of the oxidation states of chromium and vanadium.

  17. 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.

  18. 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.

  19. First-principles molecular dynamics simulations of uranyl ion interaction at the water/rutile TiO2(110) interface

    NASA Astrophysics Data System (ADS)

    Sebbari, K.; Roques, J.; Simoni, E.; Domain, C.; Perron, H.; Catalette, H.

    2012-08-01

    The effects of temperature and solvation on uranyl ion adsorption at the water/rutile TiO2(110) interface are investigated by Density Functional Theory (DFT) in both static and Born-Oppenheimer molecular dynamics approaches. According to experimental observations, uranyl ion can form two surface complexes in a pH range from 1.5 to 4.5. Based on these observations, the structures of the complexes at 293 K are first calculated in agreement with vacuum static calculations. Then, an increase in temperature (293 to 425 K) induces the reinforcement of uranyl ion adsorption due to the release of water molecules from the solvation shell of uranyl ion. Finally, temperature can modify the nature of the surface species.

  20. 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. PMID:27033403

  1. Different orientations of large rigid organic chromophores at the rutile TiO2 surface controlled by different binding geometries of specific anchor groups

    NASA Astrophysics Data System (ADS)

    Gundlach, L.; Szarko, J.; Socaciu-Siebert, L. D.; Neubauer, A.; Ernstorfer, R.; Willig, F.

    2007-03-01

    Polarization and angle-resolved two-photon photoelectron spectroscopy was employed to determine the adsorption geometry of di-tert-butyl-perylene when anchored via two different acid groups on rutile TiO2(110) . With the carboxylic acid group as anchor and a rigid bridge group the binding geometry of the chromophore was found with the long molecular axis perpendicular to the surface. In contrast, with the phosphonic acid as anchor group the long axis of perylene showed a tilt angle of around 66° with respect to the surface normal and an alignment in the direction perpendicular to [001]. Our experimental results agree with adsorption geometries recently predicted from DFT calculations by Persson’s group.

  2. 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.

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

    NASA Astrophysics Data System (ADS)

    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.

  4. Facile fabrication of rutile monolayer films consisting of well crystalline nanorods by following an IL-assisted hydrothermal route

    SciTech Connect

    Peng Peng; Liu Xiaodi; Sun, Chuansheng; Ma Jianmin; Zheng Wenjun

    2009-05-15

    In this study, rutile films consisting of rectangular nanorods were facilely deposited on glass substrates from strongly acid solution of TiCl{sub 4}. The highly ordered array of nanorods was realized in presence of ionic liquid (IL) of [Bmim]Br by following a hydrothermal process. In this process, Degussa P25 nanoparticles served as seeds that were pre-deposited on the substrates to facilitate the array of rutile nanorods. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and Raman spectrum were used to characterize the obtained nanorod films. The measurements showed that the nanorods were rectangular with width of 100-200 nm and length of more than 1 {mu}m, and grew up typically along c-axis to form the arrays against the substrate. The presence of IL was found vital for the formation of rutile nanorods, and the suitable molar ratio of [Bmim]Br to TiCl{sub 4} ranged from 500:1 to 1500:1. The excessive [Bmim]Br may hinder the precipitation of rutile particles. - Graphical abstract: The rutile film consisting of rectangular nanorods is successfully deposited on glass substrate in presence of ionic liquid (IL) of [Bmim]Br. The nanorods were rectangular with width of 100-200 nm and length of more than 1 {mu}m, which grew up typically along c-axis to form the arrays against the substrate.

  5. Nanoparticle Formation in Surface Layer of Oxide Materials and Improvement of Photocatalytic Properties of Rutile Titanium Dioxide

    NASA Astrophysics Data System (ADS)

    Ishikawa, Junzo; Tsuji, Hiroshi; Sugahara, Hiromitsu; Gotoh, Yasuhito

    2003-08-01

    Negative-ion implantation could be used to create nanoparticles in oxide insulators with finely controlled accuracy for both depth and size. For 50-nm-thick SiO2 film on Si, Ag nanoparticles with 3 nm in diameter were created in the center of the film with distribution thickness of 17 nm. Cu negative-ion implanted silica glass and soda-lime glass showed a high nonlinear susceptance of the 3rd order in nonlinear optical property. Cu and Ag double-implanted silica glass showed an absorption peak between two absorption peaks of surface plasmon resonance (SPR) for Cu and Ag nanoparticles. The optical absorption peak due to SPR of nanoparticle in oxide could be changed by forming nanoparticles with different kinds of elements and alloy. For application of metal nanoparticle to photocatalyst, Ag negative ions were implanted into rutile TiO2. The Ag-implanted rutile samples showed improved photocatalytic efficiency after proper annealing in a decolorization test of methylene blue solution under fluorescent light. The better one was the Ag-implanted rutile TiO2 (Ag: 65 keV, 5×1016 ions/cm2, 500°C annealed), which showed a photocatalytic efficiency higher by 2.2 times than that of unimplanted rutile TiO2. In the evaluation under fluorescent light through UV-cut filter for 19 h, the Ag-implanted rutile showed 6.7 times higher efficiency.

  6. 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

  7. Electronic absorption by Ti3+ ions and electron delocalization in synthetic blue rutile

    NASA Astrophysics Data System (ADS)

    Khomenko, V. M.; Langer, K.; Rager, H.; Fett, A.

    Polarized absorption spectra, σ and π, in the spectral range 30000-400 cm-1 (3.71-0.05 eV) were obtained on crystal slabs // [001] of deep blue rutile at various temperatures from 88 to 773 K. The rutile crystals were grown in Pt-capsules from carefully dried 99.999% TiO2 rutile powder at 50 kbar/1500 °C using graphite heating cells in a belt-type apparatus. Impurities were below the detection limits of the electron microprobe (about 0.005 wt% for elements with Z>=13). The spectra are characterized by an unpolarized absorption edge at 24300 cm-1, two weak and relatively narrow (Δν1/2 3500-4000 cm-1), slightly σ-polarized bands ν1 at 23500 cm-1 and ν2 at 18500 cm-1, and a complex, strong band system in the NIR (near infra red) with sharp weak peaks in the region of the OH stretching fundamentals superimposed on the NIR system in the σ-spectra. The NIR band system and the UV edge produce an absorption minimum in both spectra, σ and π, at 21000 cm-1, i.e. in the blue, which explains the colour of the crystals. Bands ν1 and ν2 are assigned to dd transitions to the Jahn-Teller split upper Eg state of octahedral Ti3+. The NIR band system can be fitted as a sum of three components. Two of them are partly π-polarized, nearly Gaussian bands, both with large half widths 6000-7000 cm-1, ν3 at 12000 cm-1 and the most intense ν4 at 6500 cm-1. The third NIR band ν5 of a mixed Lorentz-Gaussian shape with a maximum at 3000 cm-1 forms a shoulder on the low-energy wing of ν4. Energy positions, half band widths and temperature behaviour of these bands are consistent with a small polaron type of Ti3+Ti4+ charge transfer (CT). Polarization dependence of CT bands can be explained on the basis of the structural model of defect rutile by Bursill and Blanchin (1983) involving interstitial titanium. Two OH bands at 3322 and 3279 cm-1 in σ-spectra show different stability during annealing, indicating two different positions of proton in the rutile structure, one of them

  8. 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.

  9. 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

  10. Preparation of rutile TiO(2) coating by thermal chemical vapor deposition for anticoking applications.

    PubMed

    Tang, Shiyun; Wang, Jianli; Zhu, Quan; Chen, Yaoqiang; Li, Xiangyuan

    2014-10-01

    To inhibit the metal catalytic coking and improve the oxidation resistance of TiN coating, rutile TiO2 coating has been directly designed as an efficient anticoking coating for n-hexane pyrolysis. TiO2 coatings were prepared on the inner surface of SS304 tubes by a thermal CVD method under varied temperatures from 650 to 900 °C. The rutile TiO2 coating was obtained by annealing the as-deposited TiO2 coating, which is an alternative route for the deposition of rutile TiO2 coating. The morphology, elemental and phase composition of TiO2 coatings were characterized by SEM, EDX and XRD, respectively. The results show that deposition temperature of TiO2 coatings has a strong effect on the morphology and thickness of as-deposited TiO2 coatings. Fe, Cr and Ni at.% of the substrate gradually changes to 0 when the temperature is increased to 800 °C. The thickness of TiO2 coating is more than 6 μm and uniform by metalloscopy, and the films have a nonstoichiometric composition of Ti3O8 when the deposition temperature is above 800 °C. The anticoking tests show that the TiO2 coating at a deposition temperature of 800 °C is sufficiently thick to cover the cracks and gaps on the surface of blank substrate and cut off the catalytic coke growth effect of the metal substrate. The anticoking ratio of TiO2 coating corresponding to each 5 cm segments is above 65% and the average anticoking ratio of TiO2 coating is up to 76%. Thus, the TiO2 coating can provide a very good protective layer to prevent the substrate from severe coking efficiently. PMID:25192018

  11. Carbon nanotubes enhanced Seebeck coefficient and power factor of rutile TiO2.

    PubMed

    Lai, Yao-Cheng; Tsai, Hsin-Jung; Hung, Chia-I; Fujishiro, Hiroyuki; Naito, Tomoyuki; Hsu, Wen-Kuang

    2015-03-28

    The Seebeck coefficient, according to Ioffe's approximation, is inversely proportional to carrier density and decreases with doping. Herein, we find that the incorporation of multi-walled carbon nanotubes into rutile TiO2 improves the electrical conductivity and Seebeck coefficient at a low filling fraction of tubes; moreover, the former was due to the lengthening of the mean free path and doping modified carrier mobility for the latter. Tube-oxide mixing also causes significant phonon drag at the interfaces and the reduced thermal conductivity was verified by the promoted figure of merit. PMID:25729788

  12. 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.

  13. 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

  14. 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.

  15. Effect of particle size on the phase behavior of Li-intercalated TiO 2-rutile

    NASA Astrophysics Data System (ADS)

    Koudriachova, M. V.

    With the aid of ab initio calculations, we compare the phase behavior upon lithiation of rutile particles of different sizes and morphologies. A rationale for the differences in their structural behavior is provided by combining concepts from Crystal Field Theory and semi-empirical concepts, such as bond length variation, minimal volume expansion, with accounts for the effects of diffusion and the anisotropy of the Li-distribution. It is shown that the phase behavior of spaghetti-like nano-particles differs from bulk rutile as a result of an extended single phase insertion domain and increased disorder of Li-ions. As Li-ions strive to minimize their repulsions by increasing their mutual separation a regular network of Li-ions is formed, being a precursor to the transformation of the rutile host lattice into spinel.

  16. 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.

  17. Trace element mobility during rutile replacement by titanite: Open vs. closed system examples from the Franciscan Complex, CA

    NASA Astrophysics Data System (ADS)

    Cruz-Uribe, A. M.; Zack, T.; Feineman, M. D.; Barth, M. G.

    2010-12-01

    Rutile has long been regarded as an important reservoir for high field strength elements (HFSE) during subduction zone chemical cycling, whereas titanite can accommodate both HFSE and rare earth elements (REE). The behavior of HFSE, along with the concentration and distribution of REE in titanite replacing rutile, can help elucidate the processes controlling the fate of HFSE and the addition of REE by fluids and/or melts during this transition. Recent work has suggested that diffusion can also play a significant role in the behavior of HFSE during the rutile to titanite transition (Lucassen et al., 2010). Here we present examples of titanite replacement of rutile from both hot (amphibolite) and cold (eclogite-blueschist) subduction settings. Trace element concentrations in rutile rimmed by titanite were determined by LA-ICP-MS for three samples from the Franciscan Complex, CA. Detailed rutile-titanite traverses with 12-15 µm spatial resolution were performed across grains from one migmitized garnet amphibolite from Catalina Island mélange and eclogite samples from Ring Mountain, Tiburon Penninsula, and Junction School, Healdsburg, CA. Nb profiles across large rutile grains (500-700 µm) within melt segregations from Catalina Island amphibolite show clear evidence for Nb back-diffusion into rutile during titanite growth at the grain boundary. These diffusion features are not present in rutile from the eclogite samples, which is consistent with the low temperatures proposed for this reaction in Franciscan eclogites. One of the most remarkable features of the Catalina titanites is the considerable enrichment of U (20-100 ppm) that is not present in the rutile (0.1-1 ppm). This is accompanied by strong enrichment in REE, particularly middle (M)REE, up to 3000 times chondritic values. Significant U and MREE enrichment in the Catalina titanites strongly suggest interaction with a late fluid, possibly associated with pegmatitic restite following the primary melting

  18. Fabrication of hierarchically structured rutile TiO2 nanorods on mica particles and their superhydrophilic coating without UV irridiation

    NASA Astrophysics Data System (ADS)

    Gao, Qiang; Wu, Xiaomei; Fan, Yueming; Zhou, Xiya

    2014-01-01

    In this work, we report a facile strategy to fabricate hierarchical rutile TiO2 thin film on mica substrates through hydrolysis of TiCl4 ethanolic solution in water. Scanning electron microscopy (SEM) and transmission electron microscope (TEM) analysis reveal that the rutile TiO2 film is composed of nanorods and nanoparticles. The nanorod crystals grew along the [1 0 1] direction, forming predominantly exposed {1 1 0} facets. Interestingly, rutile TiO2 coated mica particles can be directly applied as a general kind of building blocks to construct large-area super hydrophilic surfaces without UV irradiation by the simple spin-coating technique. The superhydrophilicity originates from the combination of the special rough structures of hierarchical nanorods and nanoflowers and the increased hydroxyl content caused by calcinations. More importantly, this property is very stable for half a year and could be used in self-cleaning surfaces.

  19. 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

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

    NASA Astrophysics Data System (ADS)

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

    2009-04-01

    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 multi-component 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 Ca 2+ and Sr 2+ 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 1 1 0 surface [Zhang Z., Fenter P., Cheng L., Sturchio N. C., Bedzyk M. J., Předota M., Bandura A., Kubicki J., Lvov S. N., Cummings P. T., Chialvo A. A., Ridley M. K., Bénézeth 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

  1. 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., Jr.; 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.

  2. Rapid Charge Transport in Dye-Sensitized Solar Cells Made from Vertically Aligned Single-Crystal Rutile TiO2 Nanowires

    SciTech Connect

    Feng, X.; Zhu, K.; Frank, A. J.; Grimes, C. A.; Mallouk, T. E.

    2012-03-12

    A rapid solvothermal approach was used to synthesize aligned 1D single-crystal rutile TiO2 nanowire (NW) arrays on transparent conducting substrates as electrodes for dye-sensitized solar cells. The NW arrays showed a more than 200 times faster charge transport (see picture) and a factor four lower defect state density than conventional rutile nanoparticle films.

  3. TiO2 thin films with rutile phase prepared by DC magnetron co-sputtering at room temperature: Effect of Cu incorporation

    NASA Astrophysics Data System (ADS)

    Wang, Hui; Li, Yujie; Ba, Xin; Huang, Lin; Yu, Ying

    2015-08-01

    The thin films for pure TiO2 and that incorporated with Cu ion were deposited by DC magnetron co-sputtering with Ar gas. The crystal texture, surface morphology, energy gap and optical properties of the prepared films have been investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectrometer (XPS), UV-vis spectrophotometer, and Raman spectroscopy. The results show that as-deposited TiO2 film mainly possesses anatase structure at room temperature with pure Ar gas, but the introduction of Cu can alter the phase structure of crystallite TiO2. XRD patterns and Raman spectra indicate that the Cu incorporation with high concentration (ACu/ATi + ACu ≈ 20%) favors the formation of rutile phase. Moreover, the Cu incorporation into TiO2 lattice induces band gap narrowing. Band structures and density of states have been analyzed based on density functional theory (DFT) and periodic models in order to investigate the influence of the Cu incorporation on the electronic structure of TiO2. Both experimental data and electronic structure calculations evidence the fact that the change in film structure from the anatase to the rutile phase can be ascribed to the possible incorporation of Cu1+ in the sites previously occupied by Ti4+, and the presence of Cu results in important effect on the electronic states, which is mainly related to the 3d Cu orbitals in the gap and in the vicinity of the valence band edges for TiO2.

  4. Perpendicular rutile nanosheets on anatase nanofibers: Heterostructured TiO 2 nanocomposites via a mild solvothermal method

    NASA Astrophysics Data System (ADS)

    Zhang, Qijun; Sun, Chenghua; Yan, Jun; Hu, Xiujie; Zhou, Shuyun; Chen, Ping

    2010-07-01

    A novel hierarchically heterostructured TiO 2 nanocomposite, which consists of rutile nanosheets perpendicular standing on anatase nanofibers, is successfully created through a two-step approach. Firstly, the fibrous anatase TiO 2 framework is fabricated by a facile electrospinning method, then a layer of relative uniform rutile nanosheets grow on the fibers after a mild solvothermal reaction process. This work provides a convenient and effective route for fabricating desired three-dimensional nanocomposite and should be easily extended through to many other materials system.

  5. Adsorption properties versus oxidation states of rutile TiO{sub 2}(110)

    SciTech Connect

    Martinez, Umberto; Hammer, Bjoerk

    2011-05-21

    Using density functional theory we have studied the adsorption properties of different atoms and molecules deposited on a stoichiometric, reduced, and oxidized rutile TiO{sub 2}(110) surface. Depending on the oxidation state of the surface, electrons can flow from or to the substrate and, therefore, negatively or positively charged species are expected. In particular, we have found that a charge transfer process from or to the surface always occurs for highly electronegative or highly electropositive species, respectively. For atoms or molecules with intermediate electron affinity, the direction of the charge flow depends on the oxidation state of the rutile surface and on the adsorption site. Generally, the charging effect leads to more stable complexes. However, the increase in the binding energy of the adsorbates is highly dependent on the electronic states of the surface prior to the adsorption event. In this work we have analyzed in details these mechanisms and we have also established a direct correlation between the enhanced binding energy of the adsorbates and the induced gap states.

  6. 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.

  7. 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. PMID:25757057

  8. Temperature stable low loss PTFE/rutile composites using secondary polymer

    NASA Astrophysics Data System (ADS)

    Rajesh, S.; Murali, K. P.; Ratheesh, R.

    2011-07-01

    Rutile filled PTFE composites have been fabricated through Sigma Mixing, Extrusion, Calendering and Hot pressing (SMECH) process. Dielectric constant (\\varepsilonr') and loss tangent (tan δ) of filled composites at microwave frequency region were measured by waveguide cavity perturbation technique using a Vector Network Analyzer. The temperature coefficient of dielectric constant (tau_{\\varepsilonr'}) was measured in the 0-100°C temperature range. In order to tailor the temperature coefficient of dielectric constant of the composite, thermoplastic Poly (ether ether ketone) (PEEK) has been used as a secondary polymer. Flexible laminate having a dielectric constant, \\varepsilonr'˜10.4, loss tangent tan δ˜0.0045 and tau_{\\varepsilonr'}˜-40 ppm/K was realized in Polytetrafluroethylene (PTFE)/rutile composites with the addition of 8 wt% PEEK. The reduction in tau_{\\varepsilonr'} is mainly attributed to the positive tau_{\\varepsilonr'} of PEEK and increased interface region in the composites as a result of the PEEK addition.

  9. Colossal Dielectric Behavior of Ga+Nb Co-Doped Rutile TiO2.

    PubMed

    Dong, Wen; Hu, Wanbiao; Berlie, Adam; Lau, Kenny; Chen, Hua; Withers, Ray L; Liu, Yun

    2015-11-18

    Stimulated by the excellent colossal permittivity (CP) behavior achieved in In+Nb co-doped rutile TiO2, in this work we investigate the CP behavior of Ga and Nb co-doped rutile TiO2, i.e., (Ga(0.5)Nb(0.5))(x)Ti(1-x)O2, where Ga(3+) is from the same group as In(3+) but with a much smaller ionic radius. Colossal permittivity of up to 10(4)-10(5) with an acceptably low dielectric loss (tan δ = 0.05-0.1) over broad frequency/temperature ranges is obtained at x = 0.5% after systematic synthesis optimizations. Systematic structural, defect, and dielectric characterizations suggest that multiple polarization mechanisms exist in this system: defect dipoles at low temperature (∼10-40 K), polaronlike electron hopping/transport at higher temperatures, and a surface barrier layer capacitor effect. Together these mechanisms contribute to the overall dielectric properties, especially apparent observed CP. We believe that this work provides comprehensive guidance for the design of new CP materials. PMID:26512874

  10. Molecular dynamics simulations of structural transformation of perfluorooctane sulfonate (PFOS) at water/rutile interfaces.

    PubMed

    He, Guangzhi; Zhang, Meiyi; Zhou, Qin; Pan, Gang

    2015-09-01

    Concentration and salinity conditions are the dominant environmental factors affecting the behavior of perfluorinated compounds (PFCs) on the surfaces of a variety of solid matrices (suspended particles, sediments, and natural minerals). However, the mechanism has not yet been examined at molecular scales. Here, the structural transformation of perfluorooctane sulfonate (PFOS) at water/rutile interfaces induced by changes of the concentration level of PFOS and salt condition was investigated using molecular dynamics (MD) simulations. At low and intermediate concentrations all PFOS molecules directly interacted with the rutile (110) surface mainly by the sulfonate headgroups through electrostatic attraction, yielding a typical monolayer structure. As the concentration of PFOS increased, the molecules aggregated in a complex multi-layered structure, where an irregular assembling configuration was adsorbed on the monolayer structure by the van der Waals interactions between the perfluoroalkyl chains. When adding CaCl2 to the system, the multi-layered structure changed to a monolayer again, indicating that the addition of CaCl2 enhanced the critical concentration value to yield PFOS multilayer assemblies. The divalent Ca(2+) substituted for monovalent K(+) as the bridging counterion in PFOS adsorption. MD simulation may trigger wide applications in study of perfluorinated compounds (PFCs) from atomic/molecular scale. PMID:25966457

  11. 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.

  12. 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

  13. Calcium adsorption at the rutile-water interface: A potentiometric study in NaCl media to 250 C

    SciTech Connect

    Ridley, M.K.; Machesky, M.L.; Wesolowski, D.J.; Palmer, D.A.

    1999-10-01

    Calcium adsorption by rutile was studied potentiometrically from 25 to 250 C, at ionic strengths of 0.03 and 0.30 m in NaCl media, using two complementary experimental methodologies. In the first, net proton adsorption in the presence and absence of Ca{sup 2+} was monitored, and in the second, samples were periodically withdrawn during the course of a titration to determine Ca{sup 2+} adsorption directly. These experiments revealed that Ca{sup 2+} adsorption systematically increased with temperature relative to the pH of zero net proton charge in NaCl media alone (pH{sub znpc(NaCl)} - pH). That is, as temperature increased, Ca{sup 2+} adsorption commenced at progressively more positive pH{sub znpc(NaCl)} - pH values. Increasing ionic strength from 0.03 to 0.30 m NaCl suppressed Ca{sup 2+} adsorption at all temperatures as a result of either increased competition from Na{sup +} or greater complexation of Ca{sup 2+} by Cl{sup {minus}}. Finally, there was no apparent trend in the proton stoichiometric ratios (moles H{sup +} released/moles Ca{sup 2+} adsorbed) with increasing temperature. This suggests that the electrostatic and/or chemical processes involved in Ca{sup 2+} adsorption do not change greatly with increasing temperature. Favorable entropic effects, related to the increasing ease of releasing Ca{sup 2+} waters of hydration, are believed to be primarily responsible for the increase in adsorption with temperature.

  14. 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

  15. Small-scale transport of trace elements Nb and Cr during growth of titanite: an experimental study at 600 °C, 0.4 GPa

    NASA Astrophysics Data System (ADS)

    Lucassen, Friedrich; Franz, Gerhard; Rhede, Dieter

    2012-12-01

    Trace element distribution in titanite overgrowths on rutile has been investigated experimentally at 600 °C, 400 MPa and fO2 near NiNiO buffer. Compositionally homogenous Cr- or Nb-doped synthetic rutile single crystals or Nb-containing natural rutile crystals were the source of Cr, Nb and Ti to synthesize titanite using the double-capsule technique. All element exchange with the source of Si, Ca and Al occurred via a NaCl-H2O fluid. Titanite forms quickly and exclusively around the rutile crystals. The titanite overgrowth separates rutile from the bulk fluid, and all elements from rutile dissolution have to pass through the titanite rim. Trace element concentrations in titanite show a considerable scatter in experiments with and without Al, although the average concentrations of Cr or Nb of titanite around compositionally homogeneous synthetic rutile approach the expected values for closed system conditions. Variability of Al with Cr or Nb in the titanite is not correlated. The Al zoning is irregular and patchy, and also the distribution of trace elements does not show systematic trends in the spatial distribution. In experiments using zoned natural rutile, the concentrations of Nb in titanite are related to the Nb zoning in rutile, but the contents also vary unsystematically. Under the controlled conditions of the experiment, the explanation for the strongly irregular spatial distribution is most likely due to variations in elemental concentrations during transport from the rutile along the titanite grain boundaries. The transport pathway is complex because grain boundary migration is important during titanite growth. Such irregular element distribution is also found in a natural sample of titanite overgrowth on rutile from an eclogite with retrograde overprint in the amphibolite facies. Transport of Ti and trace elements was focused on grain boundaries and shielded from the rutile as a source of these elements. We conclude that this type of zoning is not

  16. Visible light photocatalytic activity of rutile TiO2 fiber clusters in the degradation of terephthalic acid

    NASA Astrophysics Data System (ADS)

    Yener, H. Banu; Helvacı, Şerife Ş.

    2015-09-01

    Rutile TiO2 nanoparticles, in different structural and morphological properties, were produced by the hydrolysis of titanium tetrachloride in a highly acidic reaction media at moderate temperatures without calcination. Their photocatalytic activities were investigated in the liquid-phase degradation of terephthalic acid under visible light illumination. The parameters, which are the concentration of the titanium tetrachloride solution (0.1-1 M) and reaction temperature (60-95 °C), effective on the properties of the particles, and their photocatalytic performances, were investigated. The XRD patterns indicated a pure rutile crystal structure at moderate temperatures without need of calcination. The FEGSEM images showed the formation of flower-, pinecone-, and sphere-like clusters consisting of interconnected nanofibers. The N2 adsorption-desorption isotherms pointed out the microporous structure of the clusters. Band gap energies were found to be varying between 3.02 and 3.08 eV due to the well-developed rutile crystallite structure. Systematic studies elucidated that the optimum reactant concentration and reaction temperature are 0.5 M TiCl4 and 95 °C, respectively. The rutile clusters synthesized at the optimum reaction conditions exhibited 99 % of the photocatalytic degradation of TPA under visible light illumination at shorter irradiation times compared with commercial P25 TiO2.

  17. 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.

  18. 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.

  19. The hydroxylated and reduced rutile TiO2(011)-2 × 1 surfaces: A first-principles study

    NASA Astrophysics Data System (ADS)

    Yuan, Feng; Zhang, Haifeng; Lu, Shixiang; Xu, Wenguo

    2014-10-01

    The hydroxylated and reduced rutile TiO2(011)-2 × 1 surfaces have been investigated by means of first-principles density functional theory calculations. For the H adsorption and O vacancy on the rutile TiO2(011)-2 × 1 surface, we investigated three different surface O sites. Based on the adsorption and formation energy calculations, we find that the top O is an energetically preferential site for the adsorption of H atom or the formation of O vacancy. The calculated electronic structures indicate that the energetically preferential O site cannot create a band gap state; only the O vacancy at the side O site gives rise to a Ti-3d like defect level at the edge of the conduction band. It is worth mentioning that all considered configurations of the H adsorption and O vacancy on the rutile TiO2(011)-2 × 1 surface obviously enhance the optical absorptions in the areas of infrared, not just the rutile TiO2(011)-2 × 1 surface only has a good absorption edge in the visible light region.

  20. 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...

  1. Single step synthesis of rutile TiO2 nanoflower array film by chemical bath deposition method

    NASA Astrophysics Data System (ADS)

    Dhandayuthapani, T.; Sivakumar, R.; Ilangovan, R.

    2016-05-01

    Titanium oxide (TiO2) nanostructures such as nanorod arrays, nanotube arrays and nanoflower arrays have been extensively investigated by the researchers. Among them nanoflower arrays has shown superior performance than other nanostructures in Dye sensitized solar cell, photocatalysis and energy storage applications. Herein, a single step synthesis for rutile TiO2 nanoflower array films suitable for device applications has been reported. Rutile TiO2 nanoflower thin film was synthesized by chemical bath deposition method using NaCl as an additive. Bath temperature induced evolution of nanoflower thin film arrays was observed from the morphological study. X-ray diffraction study confirmed the presence of rutile phase polycrystalline TiO2. Micro-Raman study revealed the presence of surface phonon mode at 105 cm-1 due to the phonon confinement effect (finite size effect), in addition with the rutile Raman active modes of B1g (143 cm-1), Eg (442 cm-1) and A1g (607 cm-1). Further, the FTIR spectrum confirmed the presence of Ti-O-Ti bonding vibration. The Tauc plot showed the direct energy band gap nature of the film with the value of 2.9 eV.

  2. Hydrothermal synthesis of rutile-anatase TiO2 nanobranched arrays for efficient dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Kwon, Soon Jin; Im, Hyo Been; Nam, Jung Eun; Kang, Jin Kyu; Hwang, Taek Sung; Yi, Kwang Bok

    2014-11-01

    Rutile-anatase TiO2 nanobranched arrays were prepared in two sequential hydrothermal-synthesis steps. The morphologies and crystalline nanostructures of the samples were investigated by controlling growth time and the concentration of the titanium precursor. All samples were characterized by field-emission scanning electron microscopy and X-ray diffraction analysis. It was found that treating the surfaces of rutile TiO2 nanorods with aqueous TiCl4 solutions allows the anatase TiO2 nanobranches to grow perpendicular to the main rutile TiO2 nanorods attached to the FTO glass. Irregularly shaped, dense TiO2 structures formed in the absence of TiCl4 treatment. A light-to-electricity conversion efficiency of 3.45% was achieved using 2.3 μm tall TiO2 nanobranched arrays in a dye-sensitized solar cell. This value is significantly higher than that observed for pure rutile TiO2 nanorods.

  3. 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.

  4. 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...

  5. 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.

  6. 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.

  7. 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.

  8. Voltage-dependent resistance of undoped rutile, TiO{sub 2}, ceramics

    SciTech Connect

    Liu, Yang; West, Anthony R.

    2013-12-23

    Lightly reduced rutile ceramics are n-type semiconductors whose resistance increases reversibly by 1–2 orders of magnitude, depending on temperature, on application of a small dc bias of 10–100 V cm{sup −1}. A similar effect is seen on changing the oxygen partial pressure surrounding the sample during impedance measurements and the bias dependence is attributed to changes in the equilibria between various ionised oxygen species adsorbed on sample surfaces, leading to changes in the mobile electron concentration in the sample bulk. The increase in resistance of n-type TiO{sub 2} with dc bias mirrors the decrease in resistance seen with p-type semiconductors such as acceptor-doped BaTiO{sub 3} and represents an effect, which has certain memristive characteristics but also significant differences.

  9. 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.

  10. Transport properties in single-crystalline rutile TiO2 nanorods

    NASA Astrophysics Data System (ADS)

    Chen, R. S.; Chen, C. A.; Wang, W. C.; Tsai, H. Y.; Huang, Y. S.

    2011-11-01

    Electronic transport properties of the single-crystalline titanium dioxide (TiO2) nanorods (NRs) with single rutile phase have been investigated. The conductivity values for the individual TiO2 NRs grown by metal-organic chemical vapor deposition are in the range of 1-10 Ω-1 cm-1. The temperature-dependent measurement shows the presence of two shallow donor levels/bands with activation energies at 8 and 28 meV, respectively. On the photoconductivity (PC), the TiO2 NRs exhibit the much higher normalized PC gain and sensitive excitation-power dependence than the polycrystalline nanotubes. The results demonstrate the superior photoconduction efficiency and distinct mechanism in the monocrystalline one-dimensional TiO2 nanostructures in comparison to the polycrystalline or nanoporous counterparts.

  11. Fano resonances in photoconductivity spectra of hydrogen donors in ZnO and rutile

    NASA Astrophysics Data System (ADS)

    Lavrov, E. V.; Herklotz, F.; Weber, J.

    2015-02-01

    The results of photoconductivity studies of hydrogen donors in ZnO and rutile TiO2 are presented. It is shown that local vibrational modes of O-H bonds comprising donors in both semiconductors can be detected in photoconductivity spectra as Fano resonances at 3611 and 3290 cm-1 in the case of ZnO and TiO2, respectively. The frequencies of these features red-shift in energy down to 2668 (ZnO) and 2445 cm-1 (TiO2) if hydrogen is substituted by deuterium. Based on the frequency of the deuterium resonance it is concluded that the ionization energy of the hydrogen donor in TiO2 is less than 300 meV, which is in variance with predictions of theory. The reasons for such a discrepancy are discussed.

  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. 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.

  14. 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.

  15. 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.

  16. 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.

  17. Electrical switching effect of a single-unit-cell CrO2 layer on rutile TiO2 surface

    NASA Astrophysics Data System (ADS)

    Li, Si-Da; Liu, Bang-Gui

    2014-03-01

    Rutile CrO2 is the most important half-metallic material with nearly 100% spin polarization at the Fermi level, and rutile TiO2 is a wide-gap semiconductor with many applications. Here, we show through first-principles investigation that a single-unit-cell CrO2 layer on rutile TiO2 (001) surface is ferromagnetic and semiconductive with a gap of 0.54 eV, and its electronic state transits abruptly to a typical metallic state when an electrical field is applied. Consequently, this makes an interesting electrical switching effect which may be useful in designing spintronic devices.

  18. Trace-element characteristics of rutile in HP-UHP rocks from the Western Gneiss Complex, Norway: implications for element mobility and provenance studies

    NASA Astrophysics Data System (ADS)

    Enea, Florentina; Cuthbert, Simon; Storey, Craig; Marschall, Horst

    2014-05-01

    Trace element compositions of rutiles from the Western Gneiss Complex of the Norwegian Caledonides, a giant HP-UHP terrane representing a transiently subducted continental margin. Trace element characterisation (V, Cr, Zr, Nb, Mo, Sn, Sb, Hf, Ta, W and U) was used to fingerprint the geochemical features of rutile in both mafic and pelitic source rocks that span a range of P-T conditions from 550°C, 1.6GPa to 850°C, 4.5GPa. The results provide the first large-scale use of the Zr-in-rutile geothermometer in the WGC, and this method is shown to be more reliable than exchange thermometers based on the major phases in these rocks. On Nb versus Cr plots, which have been used to discriminate mafic from pelitic rutiles in other HP terranes, WGC rutiles that equilibrated below 650°C successfully discriminate mafic from pelitic HP and UHP rutiles. However, those equilibrated above 650°C show mafic eclogite rutile compositions overlapping into the pelite field. This indicates trace element mixing above 650°C due to mobility of fluids or melts and their migration from the predominant felsic host rocks into the eclogite bodies. This finding is supported by distinct trace-element differences between hydrothermal vein rutiles in HP versus UHP eclogites from the WGC, and is also consistent with previous studies of Sr isotopic compositions in WGC eclogites. In addition, the results have implications for the the use of Nb/Cr plots to discriminate mafic from pelitic rutile in sedimentary provenance studies, as some rutiles of mafic eclogitic origin will tend to be misrepresented. Extremely niobian rutiles (up to 118,000 μg/g) were found in enigmatic eclogites enclosed within a large, mantle-derived, orogenic peridotite massif. The reasons for this are not yet fully understood, but suggest either metasomatism after Scandian tectonic emplacement into the subducted continental crust by fluids sourced from the nearby felsic gneisses, or by deep mantle (carbonatitic?) fluids during

  19. Deducing the depth of origin of granulite xenoliths from zircon-rutile thermometry: a case study from Tanzania

    NASA Astrophysics Data System (ADS)

    Aeiker, D. M.; Mansur, A. T.; Rudnick, R. L.; Picolli, P.; McDonough, W. F.

    2006-05-01

    We have applied the zircon-rutile geothermometer of Watson et al. (2006) to granulite-facies xenoliths and high-grade surface metamorphic rocks from the Mozambique Fold Belt (MFB), Tanzania, in order to determine whether the xenoliths derive from the present-day lower crust or from near-surface granulite terranes. Diffusion of Ti in zircon is expected to be exceedingly slow and reflect the temperature at which the zircons grew. In contrast, Zr diffuses relatively rapidly in rutile, and, as cooling rates decrease, the blocking temperature of rutile systematically decreases. Thus, in granulites that experienced very slow cooling (such as those in the present-day lower crust), Zr-in-rutile temperatures should be significantly lower than the temperatures recorded by coexisting zircons. In contrast, granulite-facies rocks found at or near the surface experienced uplift during the final phase of the orogeny, and may have cooled at a markedly faster rate (5 to 10°C/m.y.). In this case, zircon and rutile are expected to return similar temperatures (i.e., within 30-50°C, assuming a peak T of 800°C). We have measured Zr in rutile using EPMA and Ti in zircon using LA-ICP-MS from three granulite-facies xenoliths carried in rift-related basalts erupted through the MFB (two from the Kisite locality) and on the margin of the Tanzanian craton (one from the Labait locality). The two xenoliths from the MFB show contrasting results: a gt-bio orthogneiss yields zircon temperatures ranging from 780 to 1030°C (mean = 850 ± 30°C, 1 σ), which are significantly higher than those recorded in coexisting rutile (620 to 750°C, mean = 680 ± 23°C). In contrast, a gt-opx mafic granulite from Kisite yields zircon and rutile temperatures that are indistinguishable from each other at 780 ± 30°C; these temperatures are also notably cooler than those from zircon in the gt-bio orthogneiss. It thus appears that the orthogneiss derived from the present-day lower crust (and cooled very slowly

  20. 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

  1. 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.

  2. Concentration-driven phase control for low temperature synthesis of phase-pure anatase and rutile titanium oxide.

    PubMed

    Wang, Zhifeng; Xiao, Chunyan; Yamada, Shuhei; Yoshinaga, Kohji; Bu, Xiu R; Zhang, Ming

    2015-06-15

    It is highly desirable to develop controlled synthetic methods at low temperature (<100 °C) for defined phases of titanium oxide nanoparticle. We present here a simple low temperature approach which is based on the peroxide route. This approach allows the preparation of phase-pure rutile and anatase without the use of any additives or surfactants or external acids. The formation of crystalline phases is found to be dependent on reaction temperature and highly dependent on concentration. Phase-pure rutile is obtained in two concentration zones while phase-pure anatase is obtained in one concentration zone. The relationship between phases and reaction conditions (concentration and temperature) fits well with the nucleation diffusion rate model. PMID:25746180

  3. Room temperature synthesized rutile TiO2 nanoparticles induced by laser ablation in liquid and their photocatalytic activity

    NASA Astrophysics Data System (ADS)

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

    2009-07-01

    TiO2 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 TiO2 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 TiO2 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.

  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. Effect of cobalt implantation on structural and optical properties of rutile TiO2(110)

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

    Photo-absorption properties of Co implantation in rutile TiO2(110) have been investigated. Nearly five times enhancement in absorbance of visible light and 1.7 times increase in UV light have been observed. Formation of crystalline CoTiO3 and Ti1- x Co x O2 phases at high and low fluences, respectively, demonstrates a crucial role in increasing the photo-absorbance, especially in the visible regime. Ti-rich nanostructures and Ti3+ vacancies that develop after ion implantation also reveal significant contribution in these observations. These Co implanted rutile TiO2 surfaces will be useful for visible light photo-catalysis.

  6. Microemulsion-mediated solvothermal synthesis and photocatalytic properties of crystalline titania with controllable phases of anatase and rutile.

    PubMed

    Shen, Xiaojun; Zhang, Jinlong; Tian, Baozhu

    2011-08-30

    Titanium oxide with different ratios of anatase to rutile has been prepared by the microemulsion-mediated solvothermal method. The resulting samples were investigated by X-ray diffraction, Raman spectroscopy, scanning electron microscopy, UV-vis diffuse reflectance spectra, transmission electron microscopy and Brunauer-Emmett-Teller analysis. The contents of anatase and rutile in the TiO(2) particles have been successfully controlled by simply adjusting the amount of urea in the aqueous phase of the microemulsion. Both the degradation of Rhodamine B in aqueous solutions and mineralization of TOC revealed that the catalyst containing 47.6% anatase have presented the highest photocatalytic activity. A proposed mechanism is discussed to interpret the evolution of the phases based on the effect of different amount of urea. PMID:21684078

  7. 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.

  8. The growth of TiO 2 (rutile) single crystals using the FZ method under high oxygen pressure

    NASA Astrophysics Data System (ADS)

    Park, Jong Kwan; Shim, Kwang Bo; Auh, Keun Ho; Tanaka, Isao

    2002-04-01

    High purity TiO 2 (rutile) single crystals were grown using the floating zone process by applying oxygen pressures of 0.3, 0.4, 0.5, and 0.8 MPa, respectively. All of the as-grown single crystals were dark blue and transparent, and differed only slightly from their appearance by observation of the naked eye. Crystals grown under high oxygen pressure had just a few low-angle grain boundaries, except for the periphery of the crystal, compared to the rutile crystals grown under ambient oxygen pressure. In particular, a single crystal grown under an oxygen pressure of 0.5 MPa contains no low-angle grain boundaries, indicating that it can be used for optical devices.

  9. The effect of concentration on Li diffusivity and conductivity in rutile TiO2.

    PubMed

    Yildirim, Handan; Greeley, Jeffrey P; Sankaranarayanan, Subramanian K R S

    2012-04-01

    Li transport characteristics are studied by means of density functional theory (DFT) and molecular dynamics (MD) simulations in order to investigate concentration effects on Li chemical diffusivity and conductivity in TiO(2) rutile. Our MD simulations predict one-dimensional diffusion of Li ions via jumps between the octahedral sites along the channels parallel to the c-axis. The diffusion barrier and diffusion coefficient (at room temperature) for the isolated Li, determined by means of DFT calculations, correspond to 60 meV and 9.1 × 10(-6) cm(2) s(-1), respectively. Such a small barrier suggests rapid mass transport along the channels. MD simulations are performed to evaluate the concentration dependent diffusivity profiles. The changes in Li energetics and dynamics are studied as a function of Li content, which is varied primarily between 10% and 50%. In addition, we consider a couple of compositions over 50% although this is above the intercalation limit. Our results suggest that Li diffusivity is strongly dependent on the Li ∶ TiO(2) ratio, and it decreases with increasing Li concentration. For instance, at room temperature, we find Li diffusivity for high concentrations (50% Li) to be three orders of magnitude slower than that for lower concentrations (10% Li). Our analyses on the energetics and dynamics suggest that the changes in the diffusivities originate from successive increases in the barriers with increasing concentration. The decrease in diffusivity as a function of increasing Li content is attributed to the fact that additional Li ions successively block the energetically preferred vacant sites along the channels. Our analyses also show that increasing Li concentration enhances the Li-Li repulsion within the channels, and as a result, diffusion is hindered. We also compare concentration-dependent diffusivities for Li diffusion in anatase, rutile and amorphous TiO(2). Interestingly, we find differing concentration dependence of the

  10. 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.

  11. The temperature dependence of the nuclear quadrupole interaction of 44Ti(EC)44Sc in rutile

    NASA Astrophysics Data System (ADS)

    Butz, T.; Vianden, R.

    2013-05-01

    The temperature dependence of the Nuclear Quadrupole Interaction on 44Sc in rutile was measured by Time Differential Perturbed Angular Correlation in the temperature range from 300 K to 945 K. Whereas \\upomega _Q = eQV_zz/4hbar with Vzz denoting the largest component of the electric field gradient tensor in magnitude increases with increasing temperature, the asymmetry parameter η remains essentially constant. This observation fits into the systematic with other probes provided the sign of Vzz is negative.

  12. Improved lithium storage properties of electrospun TiO2 with tunable morphology: from porous anatase to necklace rutile

    NASA Astrophysics Data System (ADS)

    Yang, Yang; Wang, Haiying; Zhou, Qiwen; Kong, Mengqi; Ye, Haitao; Yang, Gang

    2013-10-01

    Three-dimensional TiO2 with tunable morphology and crystalline phase was successfully prepared by the electrospinning technique and subsequent annealing. Porous-shaped anatase TiO2, cluster-shaped anatase TiO2, hierarchical-shaped rutile (minor) TiO2 and nano-necklace rutile (major) TiO2 were achieved at 500, 600, 700 and 800 °C, respectively. The mechanism of the formation of these tailored morphologies and crystallinity was investigated. Lithium insertion properties were evaluated by galvanostatic and potentiostatic modes in half-cell configurations. By combining the large surface area, open mesoporosity and stable crystalline phase, the porous-shaped anatase TiO2 exhibited the highest capacity, best rate and cycling performance among the four samples. The present results demonstrated the usefulness of three-dimensional TiO2 as an anode for lithium storage with improved electrode performance.Three-dimensional TiO2 with tunable morphology and crystalline phase was successfully prepared by the electrospinning technique and subsequent annealing. Porous-shaped anatase TiO2, cluster-shaped anatase TiO2, hierarchical-shaped rutile (minor) TiO2 and nano-necklace rutile (major) TiO2 were achieved at 500, 600, 700 and 800 °C, respectively. The mechanism of the formation of these tailored morphologies and crystallinity was investigated. Lithium insertion properties were evaluated by galvanostatic and potentiostatic modes in half-cell configurations. By combining the large surface area, open mesoporosity and stable crystalline phase, the porous-shaped anatase TiO2 exhibited the highest capacity, best rate and cycling performance among the four samples. The present results demonstrated the usefulness of three-dimensional TiO2 as an anode for lithium storage with improved electrode performance. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr02819d

  13. 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

  14. 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}.

  15. Stereospecific growth of densely populated rutile mesoporous TiO2 nanoplate films: a facile low temperature chemical synthesis approach

    NASA Astrophysics Data System (ADS)

    Lee, Go-Woon; Ambade, Swapnil B.; Cho, Young-Jin; Mane, Rajaram S.; Shashikala, V.; Yadav, Jyotiprakash; Gaikwad, Rajendra S.; Lee, Soo-Hyoung; Jung, Kwang-Deog; Han, Sung-Hwan; Joo, Oh-Shim

    2010-03-01

    We report for the first time, using a simple and environmentally benign chemical method, the low temperature synthesis of densely populated upright-standing rutile TiO2 nanoplate films onto a glass substrate from a mixture of titanium trichloride, hydrogen peroxide and thiourea in triply distilled water. The rutile TiO2 nanoplate films (the phase is confirmed from x-ray diffraction analysis, selected area electron diffraction, energy-dispersive x-ray analysis, and Raman shift) are 20-35 nm wide and 100-120 nm long. The chemical reaction kinetics for the growth of these upright-standing TiO2 nanoplate films is also interpreted. Films of TiO2 nanoplates are optically transparent in the visible region with a sharp absorption edge close to 350 nm, confirming an indirect band gap energy of 3.12 eV. The Brunauer-Emmet-Teller surface area, Barret-Joyner-Halenda pore volume and pore diameter, obtained from N2 physisorption studies, are 82 m2 g - 1, 0.0964 cm3 g - 1 and 3.5 nm, respectively, confirming the mesoporosity of scratched rutile TiO2 nanoplate powder that would be ideal for the direct fabrication of nanoscaled devices including upcoming dye-sensitized solar cells and gas sensors.

  16. 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. PMID:25323028

  17. Molecular dynamics study on surface structure and surface energy of rutile TiO 2 (1 1 0)

    NASA Astrophysics Data System (ADS)

    Song, Dai-Ping; Liang, Ying-Chun; Chen, Ming-Jun; Bai, Qing-Shun

    2009-03-01

    The formula for surface energy was modified in accordance with the slab model of molecular dynamics (MDs) simulations, and MD simulations were performed to investigate the relaxed structure and surface energy of perfect and pit rutile TiO 2(1 1 0). Simulation results indicate that the slab with a surface more than four layers away from the fixed layer expresses well the surface characteristics of rutile TiO 2 (1 1 0) surface; and the surface energy of perfect rutile TiO 2 (1 1 0) surface converges to 1.801±0.001 J m -2. The study on perfect and pit slab models proves the effectiveness of the modified formula for surface energy. Moreover, the surface energy of pit surface is higher than that of perfect surface and exhibits an upper-concave parabolic increase and a step-like increase with increasing the number of units deleted along [0 0 1] and [1 1 0], respectively. Therefore, in order to obtain a higher surface energy, the direction along which atoms are cut out should be chosen in accordance with the pit sizes: [ 1¯10] direction for a small pit size and [0 0 1] direction for a big pit size; or alternatively the odd units of atoms along [1 1 0] direction are removed.

  18. 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.

  19. 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.

  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. 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).

  2. Rutile-bearing refractory eclogites: missing link between continents and depleted mantle

    PubMed

    Rudnick; Barth; Horn; McDonough

    2000-01-14

    A mass imbalance exists in Earth for Nb, Ta, and possibly Ti: continental crust and depleted mantle both have subchondritic Nb/Ta, Nb/La, and Ti/Zr, which requires the existence of an additional reservoir with superchondritic ratios, such as refractory eclogite produced by slab melting. Trace element compositions of minerals in xenolithic eclogites derived from cratonic lithospheric mantle show that rutile dominates the budget of Nb and Ta in the eclogites and imparts a superchondritic Nb/Ta, Nb/La, and Ti/Zr to the whole rocks. About 1 to 6 percent by weight of eclogite is required to solve the mass imbalance in the silicate Earth, and this reservoir must have an Nb concentration >/= 2 parts per million, Nb/La >/= 1.2, and Nb/Ta between 19 and 37-values that overlap those of the xenolithic eclogites. As the mass of eclogite in the continental lithosphere is significantly lower than this, much of this material may reside in the lower mantle, perhaps as deep as the core-mantle boundary. PMID:10634776

  3. 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}.

  4. 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

  5. Microemulsion-mediated hydrothermal synthesis and characterization of nanosize rutile and anatase particles

    SciTech Connect

    Wu, M.; Long, J.; Huang, A.; Luo, Y.; Feng, S.; Xu, R.

    1999-12-21

    Uniform nanoparticles of rutile and anatase were prepared, respectively, by a new approach, a microemulsion-mediated method, in which the microemulsion medium was further treated by hydrothermal reaction. Herein, the combined procedure of microemulsion and hydrothermal synthesis to prepare nanoparticles is referred to as a microemulsion-mediated hydrothermal (MMH) method. This MMH method could lead to the formation of crystalline titania powders under much milder reaction conditions than the normally reported microemulsion-mediated methods, in which posttreatment of calcination was necessary. In this work, a kind of solution was formed by dissolving tetrabutyl titanate into hydrochloric acid or nitric acid, and the solution was dispersed in an organic phase for the preparation of the microemulsion medium. The aqueous cores of water/Triton X-100/hexanol/cyclohexane microemulsions were used as constrained microreactors for a controlled growth of titania particles under hydrothermal conditions. The product of hydrothermal synthesis was separated and dried for characterization. The phase components and the morphologies and grain sizes of products were determined by X-ray diffraction (XRD) and by transmission electron microscopy (TEM). The effects of changing the variables of the reaction conditions, such as the use of acid, the concentrations of acid, the reaction temperatures, and/or the reaction times on the phases and morphologies of the titania product are described.

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

    DOE PAGESBeta

    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

  7. 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.

  8. 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

  9. 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.

  10. 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.