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Sample records for single-crystalline rutile tio2

  1. Growth of aligned single-crystalline rutile TiO2 nanowires on arbitrary substrates and their application in dye-sensitized solar cells

    SciTech Connect

    Kumar, Akshay; Madaria, Anuj R.; Zhou, Chongwu

    2010-05-06

    TiO{sub 2} is a wide band gap semiconductor with important applications in photovoltaic cells and photocatalysis. In this paper, we report synthesis of single-crystalline rutile phase TiO{sub 2} nanowires on arbitrary substrates, including fluorine-doped tin oxide (FTO), glass slides, tin-doped indium oxide (ITO), Si/SiO{sub 2}, Si(100), Si(111), and glass rods. By controlling the growth parameters such as growth temperature, precursor concentrations, and so forth, we demonstrate that anisotropic growth of TiO{sub 2} is possible leading to various morphologies of nanowires. Optimization of the growth recipe leads to well-aligned vertical array of TiO{sub 2} nanowires on both FTO and glass substrates. Effects of various titanium precursors on the growth kinetics, especially on the growth rate of nanowires, are also studied. Finally, application of vertical array of TiO{sub 2} nanowires on FTO as the photoanode is demonstrated in dye-sensitized solar cell with an efficiency of 2.9 ± 0.2%.

  2. Antibacterial activity of single crystalline silver-doped anatase TiO2 nanowire arrays

    NASA Astrophysics Data System (ADS)

    Zhang, Xiangyu; Li, Meng; He, Xiaojing; Hang, Ruiqiang; Huang, Xiaobo; Wang, Yueyue; Yao, Xiaohong; Tang, Bin

    2016-05-01

    Well-ordered, one-dimensional silver-doped anatase TiO2 nanowire (AgNW) arrays have been prepared through a hydrothermal growth process on the sputtering-deposited AgTi layers. Electron microscope analyses reveal that the as-synthesized AgNW arrays exhibit a single crystalline phase with highly uniform morphologies, diameters ranging from 85 to 95 nm, and lengths of about 11 μm. Silver is found to be doped into TiO2 nanowire evenly and mainly exists in the zerovalent state. The AgNW arrays show excellent efficient antibacterial activity against Escherichia coli (E. coli), and all of the bacteria can be killed within 1 h. Additionally, the AgNW arrays can still kill E. coli after immersion for 60 days, suggesting the long-term antibacterial property. The technique reported here is environmental friendly for formation of silver-containing nanostructure without using any toxic organic solvents.

  3. 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

  4. 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.

  5. A facile strategy to fabricate high-quality single crystalline brookite TiO2 nanoarrays and their photoelectrochemical properties

    NASA Astrophysics Data System (ADS)

    Choi, Mingi; Yong, Kijung

    2014-10-01

    Vertically aligned high-quality single crystalline brookite TiO2 nanoarrays were synthesized for the first time using an environmentally benign one-step hydrothermal reaction. They have a unique bullet-shaped structure which has a length of 700-1000 nm and a width of 150-250 nm with a sharpened tip structure. By adjusting the concentration of NaOH in hydrothermal reaction, we could also synthesize other types of TiO2 nanostructures including anatase TiO2 nanotubes/nanowires. The morphologies and crystal structures of the products were confirmed by scanning electron microscopy, transmission electron microscopy and X-ray diffraction analysis. Their vertically aligned structures facilitate their application as photoanodes in photoelectrochemical cells, and the photoelectrochemical properties such as photocurrent density and open circuit voltage were measured in a three-electrode electrochemical cell with TiO2 nanoarrays, Ag/AgCl and a Pt flag as the working, reference and counter electrodes, respectively, incorporating a 0.1 M NaOH electrolyte solution. The fabricated brookite TiO2 nanoarrays exhibited a highly enhanced photocurrent density and a longer electron lifetime compared with anatase TiO2 nanoarrays with similar lengths.Vertically aligned high-quality single crystalline brookite TiO2 nanoarrays were synthesized for the first time using an environmentally benign one-step hydrothermal reaction. They have a unique bullet-shaped structure which has a length of 700-1000 nm and a width of 150-250 nm with a sharpened tip structure. By adjusting the concentration of NaOH in hydrothermal reaction, we could also synthesize other types of TiO2 nanostructures including anatase TiO2 nanotubes/nanowires. The morphologies and crystal structures of the products were confirmed by scanning electron microscopy, transmission electron microscopy and X-ray diffraction analysis. Their vertically aligned structures facilitate their application as photoanodes in photoelectrochemical

  6. 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.

  7. Well-Defined Nanostructured, Single-Crystalline TiO2 Electron Transport Layer for Efficient Planar Perovskite Solar Cells.

    PubMed

    Choi, Jongmin; Song, Seulki; Hörantner, Maximilian T; Snaith, Henry J; Park, Taiho

    2016-06-28

    An electron transporting layer (ETL) plays an important role in extracting electrons from a perovskite layer and blocking recombination between electrons in the fluorine-doped tin oxide (FTO) and holes in the perovskite layers, especially in planar perovskite solar cells. Dense TiO2 ETLs prepared by a solution-processed spin-coating method (S-TiO2) are mainly used in devices due to their ease of fabrication. Herein, we found that fatal morphological defects at the S-TiO2 interface due to a rough FTO surface, including an irregular film thickness, discontinuous areas, and poor physical contact between the S-TiO2 and the FTO layers, were inevitable and lowered the charge transport properties through the planar perovskite solar cells. The effects of the morphological defects were mitigated in this work using a TiO2 ETL produced from sputtering and anodization. This method produced a well-defined nanostructured TiO2 ETL with an excellent transmittance, single-crystalline properties, a uniform film thickness, a large effective area, and defect-free physical contact with a rough substrate that provided outstanding electron extraction and hole blocking in a planar perovskite solar cell. In planar perovskite devices, anodized TiO2 ETL (A-TiO2) increased the power conversion efficiency by 22% (from 12.5 to 15.2%), and the stabilized maximum power output efficiency increased by 44% (from 8.9 to 12.8%) compared with S-TiO2. This work highlights the importance of the ETL geometry for maximizing device performance and provides insights into achieving ideal ETL morphologies that remedy the drawbacks observed in conventional spin-coated ETLs.

  8. Ti3+-self doped brookite TiO2 single-crystalline nanosheets with high solar absorption and excellent photocatalytic CO2 reduction

    NASA Astrophysics Data System (ADS)

    Xin, Xiaoye; Xu, Tao; Wang, Lan; Wang, Chuanyi

    2016-03-01

    Black brookite TiO2 single-crystalline nanosheets with outstanding photocatalytic activity toward CO2 reduction is prepared by a facile oxidation-based hydrothermal reaction method combined with post-annealing treatment. Large amount of Ti3+ defects are introduced into the bulk of brookite nanoparticles, which increases the solar energy absorption and enhances the photocatalytic activity.

  9. Ti3+-self doped brookite TiO2 single-crystalline nanosheets with high solar absorption and excellent photocatalytic CO2 reduction

    PubMed Central

    Xin, Xiaoye; Xu, Tao; Wang, Lan; Wang, Chuanyi

    2016-01-01

    Black brookite TiO2 single-crystalline nanosheets with outstanding photocatalytic activity toward CO2 reduction is prepared by a facile oxidation-based hydrothermal reaction method combined with post-annealing treatment. Large amount of Ti3+ defects are introduced into the bulk of brookite nanoparticles, which increases the solar energy absorption and enhances the photocatalytic activity. PMID:27021203

  10. 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.

  11. 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

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

    NASA Astrophysics Data System (ADS)

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

    2016-02-01

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

  13. 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

  14. 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.

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

    PubMed

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

    2011-11-01

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

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

    PubMed Central

    2016-01-01

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

  18. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

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

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

    PubMed

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

    2015-09-01

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

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

    PubMed

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

    2010-08-01

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

  2. 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.

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

    PubMed

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

    2012-12-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2012-05-01

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

  5. 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.

  6. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2009-06-01

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

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

    PubMed Central

    2009-01-01

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

  9. 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

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

    PubMed Central

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

    2016-01-01

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

  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. 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).

  13. 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.

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

    PubMed

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

    2007-11-01

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

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

    SciTech Connect

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

    2015-04-27

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-02-01

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

  17. 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.

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

    PubMed

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

    2015-03-21

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

  19. 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.

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

    PubMed

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

    2013-09-24

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

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

    SciTech Connect

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

    2010-10-14

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

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

    SciTech Connect

    Zehr, Robert T.; Henderson, Michael A.

    2010-07-20

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

  3. 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.

  4. 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.

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

    SciTech Connect

    Shen, Mingmin; Henderson, Michael A.

    2012-08-07

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

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

    PubMed

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

    2009-07-15

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

  7. 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

  8. 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).

  9. 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

  10. 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

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

    PubMed

    Iwaszuk, Anna; Nolan, Michael

    2011-08-24

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

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

    PubMed

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

    2009-12-01

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

  13. 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.

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

    SciTech Connect

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

    2013-01-10

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

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

    PubMed

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

    2010-06-11

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

  16. 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

  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. Cluster synthesis of monodisperse rutile-TiO2 nanoparticles and dielectric TiO2-vinylidene fluoride oligomer nanocomposites

    SciTech Connect

    Balasubramanian, B; Kraemer, KL; Valloppilly, SR; Ducharme, S; Sellmyer, DJ

    2011-09-13

    The embedding of oxide nanoparticles in polymer matrices produces a greatly enhanced dielectric response by combining the high dielectric strength and low loss of suitable host polymers with the high electric polarizability of nanoparticles. The fabrication of oxide-polymer nanocomposites with well-controlled distributions of nanoparticles is, however, challenging due to the thermodynamic and kinetic barriers between the polymer matrix and nanoparticle fillers. In the present study, monodisperse TiO2 nanoparticles having an average particle size of 14.4 nm and predominant rutile phase were produced using a cluster-deposition technique without high-temperature thermal annealing and subsequently coated with uniform vinylidene fluoride oligomer (VDFO) molecules using a thermal evaporation source, prior to deposition as TiO2-VDFO nanocomposite films on suitable substrates. The molecular coatings on TiO2 nanoparticles serve two purposes, namely to prevent the TiO2 nanoparticles from contacting each other and to couple the nanoparticle polarization to the matrix. Parallel-plate capacitors made of TiO2-VDFO nanocomposite film as the dielectric exhibit minimum dielectric dispersion and low dielectric loss. Dielectric measurements also show an enhanced effective dielectric constant in TiO2-VDFO nanocomposites as compared to that of pure VDFO. This study demonstrates for the first time a unique electroactive particle coating in the form of a ferroelectric VDFO that has high-temperature stability as compared to conventionally used polymers for fabricating dielectric oxide-polymer nanocomposites.

  19. Cluster synthesis of monodisperse rutile-TiO2 nanoparticles and dielectric TiO2-vinylidene fluoride oligomer nanocomposites.

    PubMed

    Balasubramanian, Balamurugan; Kraemer, Kristin L; Valloppilly, Shah R; Ducharme, Stephen; Sellmyer, David J

    2011-10-01

    The embedding of oxide nanoparticles in polymer matrices produces a greatly enhanced dielectric response by combining the high dielectric strength and low loss of suitable host polymers with the high electric polarizability of nanoparticles. The fabrication of oxide-polymer nanocomposites with well-controlled distributions of nanoparticles is, however, challenging due to the thermodynamic and kinetic barriers between the polymer matrix and nanoparticle fillers. In the present study, monodisperse TiO(2) nanoparticles having an average particle size of 14.4 nm and predominant rutile phase were produced using a cluster-deposition technique without high-temperature thermal annealing and subsequently coated with uniform vinylidene fluoride oligomer (VDFO) molecules using a thermal evaporation source, prior to deposition as TiO(2)-VDFO nanocomposite films on suitable substrates. The molecular coatings on TiO(2) nanoparticles serve two purposes, namely to prevent the TiO(2) nanoparticles from contacting each other and to couple the nanoparticle polarization to the matrix. Parallel-plate capacitors made of TiO(2)-VDFO nanocomposite film as the dielectric exhibit minimum dielectric dispersion and low dielectric loss. Dielectric measurements also show an enhanced effective dielectric constant in TiO(2)-VDFO nanocomposites as compared to that of pure VDFO. This study demonstrates for the first time a unique electroactive particle coating in the form of a ferroelectric VDFO that has high-temperature stability as compared to conventionally used polymers for fabricating dielectric oxide-polymer nanocomposites.

  20. 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.

  1. 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

  2. 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.

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

    PubMed

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

    2016-09-21

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

  4. 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.

  5. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

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

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

    DOE PAGESBeta

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

    2016-02-24

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

  9. In situ scanning tunneling microscopy study of Ca-modified rutile TiO2(110) in bulk water

    PubMed Central

    Bonanni, Beatrice; Kosmala, Tomasz; Di Giovannantonio, Marco; Diebold, Ulrike; Wandelt, Klaus; Goletti, Claudio

    2015-01-01

    Summary Despite the rising technological interest in the use of calcium-modified TiO2 surfaces in biomedical implants, the Ca/TiO2 interface has not been studied in an aqueous environment. This investigation is the first report on the use of in situ scanning tunneling microscopy (STM) to study calcium-modified rutile TiO2(110) surfaces immersed in high purity water. The TiO2 surface was prepared under ultrahigh vacuum (UHV) with repeated sputtering/annealing cycles. Low energy electron diffraction (LEED) analysis shows a pattern typical for the surface segregation of calcium, which is present as an impurity on the TiO2 bulk. In situ STM images of the surface in bulk water exhibit one-dimensional rows of segregated calcium regularly aligned with the [001] crystal direction. The in situ-characterized morphology and structure of this Ca-modified TiO2 surface are discussed and compared with UHV-STM results from the literature. Prolonged immersion (two days) in the liquid leads to degradation of the overlayer, resulting in a disordered surface. X-ray photoelectron spectroscopy, performed after immersion in water, confirms the presence of calcium. PMID:25821684

  10. 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

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

    NASA Astrophysics Data System (ADS)

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

    2005-09-01

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

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

    PubMed

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

    2014-01-01

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

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

    PubMed

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

    2016-01-01

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

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

    PubMed Central

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

    2016-01-01

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

  15. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2014-07-01

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

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

    PubMed

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

    2013-09-01

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

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

    PubMed

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

    2012-01-28

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

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

    NASA Astrophysics Data System (ADS)

    Selman, Abbas M.; Hassan, Z.

    2013-12-01

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

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

    PubMed

    Uberuaga, Blas P; Bai, Xian-Ming

    2011-11-01

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

  1. Potential neurological lesion after nasal instillation of TiO(2) nanoparticles in the anatase and rutile crystal phases.

    PubMed

    Wang, Jiangxue; Chen, Chunying; Liu, Ying; Jiao, Fang; Li, Wei; Lao, Fang; Li, Yufeng; Li, Bai; Ge, Cuicui; Zhou, Guoqiang; Gao, Yuxi; Zhao, Yuliang; Chai, Zhifang

    2008-12-15

    Nanoscale titanium dioxide (TiO(2)) is massively produced and widely used in living environment, which hence make the potential risk to human health. Central nervous system (CNS) is the potential susceptible target of inhaled nanoparticles, but the studies on this aspect are limited so far. We report the accumulation and toxicity results in vivo of two crystalline phases of TiO(2) nanoparticles (80nm, rutile and 155nm, anatase; purity >99%). The female mice were intranasally instilled with 500microg of TiO(2) nanoparticles suspension every other day for 30 days. Synchrotron radiation X-ray fluorescence analysis (SRXRF) and inductively coupled plasma mass spectrometry (ICP-MS) were used to determine the contents of titanium in murine brain. Then, the pathological examination of brain tissue, oxidative stress-mediated responses, and levels of neurochemicals in the brain of exposed mice were also analyzed. The obvious morphological changes of hippocampal neurons and increased GFAP-positive astrocytes in the CA4 region were observed, which were in good agreements with higher Ti contents in the hippocampus region. Oxidative stress occurred obviously in whole brain of exposed mice such as lipid peroxidation, protein oxidation and increased activities of catalase, as well as the excessive release of glutamic acid and nitric oxide. These findings indicate anatase TiO(2) nanoparticles exhibited higher concern on some tested biological effects. To summarize, results provided the preliminary evidence that nasal instilled TiO(2) nanoparticles could be translocated into the central nervous system and cause potential lesion of brain, and the hippocampus would be the main target within brain.

  2. 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.

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

    SciTech Connect

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

    2015-01-15

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

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

    PubMed

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

    2014-07-29

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

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

    PubMed

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

    2014-07-29

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

  6. Release of phosphorous impurity from TiO2 anatase and rutile nanoparticles in aquatic environments and its implications.

    PubMed

    Liu, Xuyang; Chen, Gexin; Erwin, Justin G; Adam, Nadia K; Su, Chunming

    2013-10-15

    Phosphorus-bearing materials as an additive have been popularly used in nanomaterial synthesis and the residual phosphorus within the nanoparticles (NPs) can be of an environmental concern. For instance, phosphorus within pristine commercial TiO2 NPs greatly influences the surface charge and aggregation behavior of the host TiO2 in aquatic environments; however, it is unknown whether and how fast phosphorus is released. In this study, we focus on the phosphorus release kinetics from five types of TiO2 NPs (i.e., 5, 10, and 50 nm anatase and 10 × 40, 30 × 40 nm rutile) under the influence of varying solution chemistries. The 50 nm anatase has the highest quantity of P (8.05 g/kg) and most leachable P dissolves within the first 2 h (i.e., 5.01 g/kg), which presents a potential pollutant source of P. Higher pH favors the phosphorus release (release order: pH 11.2 > pH 8.2 > pH 2.4), while variations in the environmentally relevant ionic strengths (0.01 M NaCl + 0.01 M NaHCO3 and 0.04 M NaCl + 0.01 M NaHCO3) and the presence of dissolved natural organic matter (10 mg/L) do not affect release rate greatly. X-ray Absorption Near Edge Structure results suggest that phosphate adsorbed on the pristine 50 nm anatase desorbs, and some dissolved phosphate again re-sorbs as a surface precipitate. The findings from this research may have important environmental implications such as accidental release of TiO2 NPs and other nanomaterials that are synthesized using phosphorus containing chemicals as an ingredient.

  7. 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

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

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

    SciTech Connect

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

    2015-06-25

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

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-02-01

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

  12. N incorporation and electronic structure in N-doped TiO2(110) rutile

    SciTech Connect

    Cheung, Sau H.; Nachimuthu, Ponnusamy; Joly, Alan G.; Engelhard, Mark H.; Bowman, Michael K.; Chambers, Scott A.

    2007-02-08

    Epitaxial TiO2-xNx film growth under anion-rich conditions is characterized by nearly balanced incorporation rates for substitutional N (NO) and interstitial Ti (Tii). Tii donors fully compensate and stabilize N3-, but preclude the formation of p-type material. Hybridization occurs between Tii(IV) and NO3-, but the value of x is limited to ~0.02 under these conditions. Tii(IV)-NO3- states occur above the valence band maximum of pure TiO2, riving rise to enhanced optical absorption in the visible up to ~2.5 eV. Much higher NO and Tii concentrations result from using cation-rich conditions.

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

    EPA Science Inventory

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

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

    EPA Science Inventory

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

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

    PubMed

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

    2016-07-28

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

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

  17. Self-induced synthesis of phase-junction TiO2 with a tailored rutile to anatase ratio below phase transition temperature

    PubMed Central

    Wang, Wei-Kang; Chen, Jie-Jie; Zhang, Xing; Huang, Yu-Xi; Li, Wen-Wei; Yu, Han-Qing

    2016-01-01

    The surface phase junction of nanocrystalline TiO2 plays an essential role in governing its photocatalytic activity. Thus, facile and simple methods for preparing phase-junction TiO2 photocatalysts are highly desired. In this work, we show that phase-junction TiO2 is directly synthesized from Ti foil by using a simple calcination method with hydrothermal solution as the precursor below the phase transition temperature. Moreover, the ratio of rutile to anatase in the TiO2 samples could be readily tuned by changing the ratio of weight of Ti foil to HCl, which is used as the hydrothermal precursor, as confirmed by the X-ray diffraction analysis. In the photocatalytic reaction by the TiO2 nanocomposite, a synergistic effect between the two phases within a certain range of the ratio is clearly observed. The results suggest that an appropriate ratio of anatase to rutile in the TiO2 nanocomposite can create more efficient solid-solid interfaces upon calcination, thereby facilitating interparticle charge transfer in the photocatalysis. PMID:26864501

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

    NASA Astrophysics Data System (ADS)

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

    2014-02-01

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

  19. Structural studies of TiO2/wood coatings prepared by hydrothermal deposition of rutile particles from TiCl4 aqueous solutions on spruce (Picea Abies) wood

    NASA Astrophysics Data System (ADS)

    Pori, Pavel; Vilčnik, Aljaž; Petrič, Marko; Sever Škapin, Andrijana; Mihelčič, Mohor; Šurca Vuk, Angela; Novak, Urban; Orel, Boris

    2016-05-01

    A low temperature approach was developed for the deposition of rutile TiO2 particles on a wood surface by hydrolysis of TiCl4 in aqueous solutions acidified with HCl, and crystallization at 75 and 90 °C (1 h). Prior to hydrothermal treatment, Picea Abies wood was first soaked in a 0.5 mmol/l aqueous solution containing anionic surfactant sodium dodecyl sulphate (SDS, Sigma Aldrich) for 2 h at 80 °C. The crystal structure of the hydrothermally made rutile particles was determined with XRD, while the morphology of the deposited TiO2 particles and their distribution in the wood were examined with SEM and EDX measurements. The penetration and amount of deposited rutile particles could be modified by changing the deposition conditions. Thicker layers were obtained from more concentrated aqueous TiCl4 solutions with and without added HCl, and with longer deposition times and higher temperatures of the hydrothermal treatment. The interaction of TiO2 particles with hemicellulose and lignin in wood was established from infrared attenuated total reflection (FT-IR ATR) and Raman spectra measurements, from which the spectra of wood were subtracted. Analysis of the subtraction spectra showed the presence of titania particles on the wood surface, revealing also the establishment of TiO2-wood coordinative bonds of titanium ions with hemicellulose and lignin. The red frequency shift of the OH stretching modes suggested interaction of the TiO2 particles with water molecules of wood. TiO2 deposited on wood treated with SDS became hydrophobic (water contact angles (WCA) of 150°), contrasting the properties of untreated wood with a deposited TiO2 particle coating, which remained hydrophilic.

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

    NASA Astrophysics Data System (ADS)

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

    2013-09-01

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

  1. On the consistency of QCBED structure factor measurements for TiO2 (rutile).

    PubMed

    Jiang, Bin; Zuo, Jian-Min; Friis, Jesper; Spence, John C H

    2003-10-01

    The same Bragg reflection in TiO2 from 12 different (CBED) patterns (from different crystals, orientations, and thicknesses) are analyzed quantitatively to evaluate the consistency of the quantitative CBED method for bond-charge mapping. The standard deviation in the resulting distribution of derived X-ray structure factors is found to be an order of magnitude smaller than that in conventional X-ray work, and the standard error (0.026% for F(x)(110)) is slightly better than obtained by the X-ray Pendellösung method applied to silicon. This is sufficiently accurate to distinguish between atomic, covalent, and ionic models of bonding. We describe the importance of extracting experimental parameters from CCD camera characterization, and of surface oxidation and crystal shape. The current experiments show that the QCBED method is now a robust and powerful tool for low-order structure factor measurement, which does not suffer from the large extinction (multiple scattering) errors that occur in inorganic X-ray crystallography, and may be applied to nanocrystals. Our results will be used to understand the role of d-electrons in the chemical bonding of TiO2.

  2. Conversion of 1,2-Propylene Glycol on Rutile TiO2(110)

    SciTech Connect

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

    2014-07-17

    We have studied the reactions of 1,2-propylene glycol (1,2-PG), DOCH(CH3)CH2OD, on partially reduced, hydroxylated and oxidized TiO2(110) surfaces using temperature programmed desorption. On reduced TiO2(110), propylene, propanal, and acetone are identified as primary carbon-containing products. While the propylene formation channel dominates at low 1,2-PG coverages, all of the above-mentioned products are observed at high coverages. The carbon-containing products are accompanied by the formation of D2O and D2. The observation of only deuterated products shows that the source of hydrogen (D) is from the 1,2-PG hydroxyls. The role of bridging oxygen vacancy (VO) sites was further investigated by titrating them via hydroxylation and oxidation. The results show that hydroxylation does not change the reactivity because the VO sites are regenerated at 500 K, which is a temperature lower than the 1,2-PG product formation temperature. In contrast, surface oxidation causes significant changes in the product distribution, with increased acetone and propanal formation and decreased propylene formation. Additionally D2 is completely eliminated as an observed product at the expense of D2O formation.

  3. On the consistency of QCBED structure factor measurements for TiO2 (Rutile)

    DOE PAGESBeta

    Jiang, Bin; Zuo, Jian -Min; Friis, Jesper; Spence, John C. H.

    2003-09-16

    The same Bragg reflection in TiO2 from twelve different CBED patterns (from different crystals, orientations and thicknesses) are analysed quantitatively in order to evaluate the consistency of the QCBED method for bond-charge mapping. The standard deviation in the resulting distribution of derived X-ray structure factors is found to be an order of magnitude smaller than that in conventional X-ray work, and the standard error (0.026% for FX(110)) is slightly better than obtained by the X-ray Pendellosung method applied to silicon. This is sufficiently accuracy to distinguish between atomic, covalent and ionic models of bonding. We describe the importance of extractingmore » experimental parameters from CCD camera characterization, and of surface oxidation and crystal shape. Thus, the current experiments show that the QCBED method is now a robust and powerful tool for low order structure factor measurement, which does not suffer from the large extinction (multiple scattering) errors which occur in inorganic X-ray crystallography, and may be applied to nanocrystals. Our results will be used to understand the role of d electrons in the chemical bonding of TiO2.« less

  4. 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.

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

    NASA Astrophysics Data System (ADS)

    Kangarlou, Haleh; Abdollahi, Arash

    2016-11-01

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

  6. The tetragonal-like to rutile structural phase transition in epitaxial VO2/TiO2 (001) thick films

    NASA Astrophysics Data System (ADS)

    Qiu, Hongbo; Yang, Memgmeng; Dong, Yongqi; Xu, Han; Hong, Bin; Gu, Yueliang; Yang, Yuanjun; Zou, Chongwen; Luo, Zhenlin; Gao, Chen

    2015-11-01

    A controllable metal-insulator transition (MIT) of VO2 has been highly desired due to its huge potential applications in memory storage, smart windows or optical switching devices. Recently, interfacial strain engineering has been recognized as an effective approach to tuning the MIT of epitaxial VO2 films. However, the strain-involved structural evolution during the MIT process is still not clear, which prevents comprehensively understanding and utilizing interfacial strain engineering in VO2 films. In this work, we have systematically studied the epitaxial VO2 thick films grown on TiO2 (001) single crystal substrate and the structural transition at the boundary of MIT region. By using in situ temperature-dependent high-resolution x-ray diffractions, a tetragonal-like (‘T-like’) to ‘rutile’ structural phase transition is identified during the MIT process. The room-temperature crystal phase of epitaxial VO2/TiO2(001) thick film is clarified to be tetragonal-like, neither strained-rutile phase nor monoclinic phase. The calculated atomic structure of this T-like phase VO2 resembles that of the M1 phase VO2, which has been verified by their similar Raman spectra. More, the crystal lattices of the coexisted phases in the MIT region were revealed in detail. The current findings will not only show some clues on the MIT mechanism study from the structural point of view, but also favor the interface engineering assisted VO2-based devices and applications in the future.

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

    PubMed

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

    2013-07-25

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

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

    NASA Astrophysics Data System (ADS)

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

    2005-06-01

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

  10. Conversion of 1,3-Propylene Glycol on Rutile TiO2(110)

    SciTech Connect

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

    2014-10-09

    The adsorption of 1,3-propylene glycol (1,3-PG) on partially reduced TiO2(110) and its conversion to products have been studied by a combination of molecular beam dosing and temperature programmed desorption (TPD). When the Ti surface sites are saturated by 1,3-PG, ~80% of the molecules undergo further reactions to yield products that are liberated during the TPD ramp. In contrast to ethylene glycol (EG) and 1,2- propylene glycol (1,2-PG) that yield only alkenes and water at very low coverages (< 0.05 ML), two additional products, HCHO and C2H4, along with propylene (CH3CHCH2) and water are observed for 1,3-PG. Identical TPD line shapes and desorption yields for HCHO and C2H4 suggest that these products result from C-C bond cleavage and are coupled. At higher 1,3-PG coverages (> 0.1 ML), propanal (CH3CH2CHO) and two additional products, 1-propanol (CH3CH2CH2OH) and acrolein (CH2CHCHO), are observed. The desorption of 1-propanol is found to be coupled with the desorption of acrolein, suggesting that these products are formed by the disproportionation of two 1,3-PG molecules. The coverage dependent TPD results further show that propylene formation dominates at low coverages (< 0.3 ML), while the decomposition and disproportionation channels increase rapidly at higher coverages and reach yields comparable to that of propylene at the 1,3-PG saturation coverage of 0.5 ML. The observed surface chemistry clearly shows how the molecular structure of glycols influences their reaction pathways on oxide surfaces.

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

    NASA Astrophysics Data System (ADS)

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

    2010-06-01

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

  12. Hydrothermal Etching Treatment to Rutile TiO2 Nanorod Arrays for Improving the Efficiency of CdS-Sensitized TiO2 Solar Cells.

    PubMed

    Wan, Jingshu; Liu, Rong; Tong, Yuzhu; Chen, Shuhuang; Hu, Yunxia; Wang, Baoyuan; Xu, Yang; Wang, Hao

    2016-12-01

    Highly ordered TiO2 nanorod arrays (NRAs) were directly grown on an F:SnO2 (FTO) substrate without any seed layer by hydrothermal route. For a larger surface area, the second-step hydrothermal treatment in hydrochloric acid was carried out to the as-prepared TiO2 NRAs. The results showed that the center portion of the TiO2 nanorods were dissolved in the etching solution to form a nanocave at the initial etching process. As the etching time extended, the tip parts of the nanocave wall split into lots of nanowires with a reduced diameter, giving rise to a remarkable increase of specific surface area for the TiO2 NRAs. The TiO2 films after etching treatment were sensitized by CdS quantum dots (QDs) to fabricate quantum dot-sensitized solar cells (QDSSCs), which exhibited a significant improvement in the photocurrent density in comparison with that of the un-treated device, this mainly attributed to the enhancement of QD loading and diffused reflectance ability. Through modifying the etching TiO2 films with TiCl4, a relatively high power conversion efficiency (PCE) of 3.14 % was obtained after optimizing the etching time.

  13. Hydrothermal Etching Treatment to Rutile TiO2 Nanorod Arrays for Improving the Efficiency of CdS-Sensitized TiO2 Solar Cells

    NASA Astrophysics Data System (ADS)

    Wan, Jingshu; Liu, Rong; Tong, Yuzhu; Chen, Shuhuang; Hu, Yunxia; Wang, Baoyuan; Xu, Yang; Wang, Hao

    2016-01-01

    Highly ordered TiO2 nanorod arrays (NRAs) were directly grown on an F:SnO2 (FTO) substrate without any seed layer by hydrothermal route. For a larger surface area, the second-step hydrothermal treatment in hydrochloric acid was carried out to the as-prepared TiO2 NRAs. The results showed that the center portion of the TiO2 nanorods were dissolved in the etching solution to form a nanocave at the initial etching process. As the etching time extended, the tip parts of the nanocave wall split into lots of nanowires with a reduced diameter, giving rise to a remarkable increase of specific surface area for the TiO2 NRAs. The TiO2 films after etching treatment were sensitized by CdS quantum dots (QDs) to fabricate quantum dot-sensitized solar cells (QDSSCs), which exhibited a significant improvement in the photocurrent density in comparison with that of the un-treated device, this mainly attributed to the enhancement of QD loading and diffused reflectance ability. Through modifying the etching TiO2 films with TiCl4, a relatively high power conversion efficiency (PCE) of 3.14 % was obtained after optimizing the etching time.

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

    PubMed Central

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

    2014-01-01

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

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

    PubMed Central

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

    2015-01-01

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

  16. 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.

  17. Adsorption and dissociation of NH3 on clean and hydroxylated TiO2 rutile (110) surfaces: a computational study.

    PubMed

    Chang, Jee-Gong; Chen, Hsin-Tsung; Ju, Shin-Pon; Chang, Ching-Sheng; Weng, Meng-Hsiung

    2011-04-30

    The adsorption and dissociation of NH(3) on the clean and hydroxylated TiO(2) rutile (110) surfaces have been investigated by the first-principles calculations. The monodentate adsorbates such as H(3)N-Ti(a), H(2)N-Ti(a), N-Ti(a), H(2)N-O(a), HN-O(a), N-O(a) and H-O(a), as well as the bidentate adsorbate, Ti-N-Ti(a) can be formed on the clean surface. It is found that the hydroxyl group enhances the adsorption of certain adsorbates on the five-fold-coordinated Ti atoms (5c-Ti), namely H(2)N-Ti(a), HN-Ti(a), N-Ti(a) and Ti-N-Ti(a). In addition, the adsorption energy increases as the number of hydroxyl groups increases. On the contrary, the opposite effect is found for those on the two-fold-coordinated O atoms (2c-O). The enhanced adsorption of NH(x) (x = 1-2) on the 5c-Ti is due to the large electronegativity of the OH group, increasing the acidity of the Ti center. This also contributes to diminish the adsorption of NH(x) (x = 1-2) on the two-fold-coordinated O atoms (2c-O) decreasing its basicity. According to potential energy profile, the NH(3) dissociation on the TiO(2) surface is endothermic and the hydroxyl group is found to lower the energetics of H(2)N-Ti(a)+H-O(a) and HN-Ti(a)+2{H-O(a)}, but slightly raise the energetic of Ti-N-Ti(a)+3{H-O(a)} compare to those on the clean surface. However, the dissociation of NH(3) is found to occur on the hydroxylated surface with an overall endothermic by 31.8 kcal/mol and requires a barrier of 37.5 kcal/mol. A comparison of NH(3) on anatase surface has been discussed. The detailed electronic analysis is also carried out to gain insights into the interaction nature between adsorbate and surface.

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

    SciTech Connect

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

    2012-12-20

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

  19. Tm-doped TiO2 and Tm2Ti2O7 pyrochlore nanoparticles: enhancing the photocatalytic activity of rutile with a pyrochlore phase

    PubMed Central

    De los Santos, Desiré M; Aguilar, Teresa; Sánchez-Coronilla, Antonio; Fernández-Lorenzo, Concha; Alcántara, Rodrigo; Piñero, Jose Carlos; Blanco, Ginesa; Martín-Calleja, Joaquín

    2015-01-01

    Summary Tm-doped TiO2 nanoparticles were synthesized using a water-controlled hydrolysis reaction. Analysis was performed in order to determine the influence of the dopant concentration and annealing temperature on the phase, crystallinity, and electronic and optical properties of the resulting material. Various characterization techniques were utilized such as X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy and UV–vis spectroscopy. For the samples annealed at 773 and 973 K, anatase phase TiO2 was obtained, predominantly internally doped with Tm3+. ICP–AES showed that a doping concentration of up to 5.8 atom % was obtained without reducing the crystallinity of the samples. The presence of Tm3+ was confirmed by X-ray photoelectron spectroscopy and UV–vis spectroscopy: the incorporation of Tm3+ was confirmed by the generation of new absorption bands that could be assigned to Tm3+ transitions. Furthermore, when the samples were annealed at 1173 K, a pyrochlore phase (Tm2Ti2O7) mixed with TiO2 was obtained with a predominant rutile phase. The photodegradation of methylene blue showed that this pyrochlore phase enhanced the photocatalytic activity of the rutile phase. PMID:25821701

  20. 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.

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

    SciTech Connect

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

    2011-08-11

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

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

    DOE PAGESBeta

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

    2015-08-11

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

  3. Molecular mechanics of the cooperative adsorption of a Pro-Hyp-Gly tripeptide on a hydroxylated rutile TiO2(110) surface mediated by calcium ions.

    PubMed

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

    2016-07-20

    The interaction of amino acids with inorganic materials at interfaces plays an important role in enhancing the biocompatibility of titanium-based alloys. The adsorption of a tripeptide, i.e. Pro-Hyp-Gly, on the hydroxylated rutile TiO2(110) surface was investigated by the MD simulations. The changes in free energy during the adsorption of both the tripeptide and calcium ions were calculated by using the PMF method in order to obtain the adsorption strength. The results suggested that the adsorption of the tripeptide on the TiO2 surface through the carboxyl groups in glycine residues can be more stable compared with other binding conformations. Special attention was focused on the cooperative adsorption of the tripeptide with the assistance of calcium ions. Calcium ions preferred to absorb at the tetradentate or monodentate sites on the negatively charged TiO2 surface. As a result of the strong attraction between the carboxyl group and calcium ions, the tripeptide can be pulled down to the surface by following the trajectory of the calcium ions, forming an indirect interaction with a sandwich structure of peptide-cation-TiO2. However, this indirect interaction could eventually transform to the direct adsorption of the tripeptide on the TiO2 surface with higher binding energy. The results may help to interpret the adsorption of peptides on inorganic materials in aqueous solution with ions. PMID:27383367

  4. Growth and characterization of well-aligned densely-packed rutile TiO(2) nanocrystals on sapphire substrates via metal-organic chemical vapor deposition.

    PubMed

    Chen, C A; Chen, Y M; Korotcov, A; Huang, Y S; Tsai, D S; Tiong, K K

    2008-02-20

    Well-aligned densely-packed rutile TiO(2) nanocrystals (NCs) have been grown on sapphire (SA) (100) and (012) substrates via metal-organic chemical vapor deposition (MOCVD), using titanium-tetraisopropoxide (TTIP, Ti(OC(3)H(7))(4)) as a source reagent. The surface morphology as well as structural and spectroscopic properties of the as-deposited NCs were characterized using field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), selected-area electron diffractometry (SAED), x-ray diffraction (XRD) and micro-Raman spectroscopy. FESEM micrographs reveal that vertically aligned NCs were grown on SA(100), whereas the NCs on the SA(012) were grown with a tilt angle of ∼33° from the normal to substrates. TEM and SAED measurements showed that the TiO(2) NCs on SA(100) with square cross section have their long axis directed along the [001] direction. The XRD results reveal TiO(2) NCs with either (002) orientation on SA(100) substrate or (101) orientation on SA(012) substrate. A strong substrate effect on the alignment of the growth of TiO(2) NCs has been demonstrated and the probable mechanism for the formation of these NCs has been discussed. PMID:21817648

  5. Growth and characterization of well-aligned densely-packed rutile TiO2 nanocrystals on sapphire substrates via metal organic chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Chen, C. A.; Chen, Y. M.; Korotcov, A.; Huang, Y. S.; Tsai, D. S.; Tiong, K. K.

    2008-02-01

    Well-aligned densely-packed rutile TiO2 nanocrystals (NCs) have been grown on sapphire (SA) (100) and (012) substrates via metal-organic chemical vapor deposition (MOCVD), using titanium-tetraisopropoxide (TTIP, Ti(OC3H7)4) as a source reagent. The surface morphology as well as structural and spectroscopic properties of the as-deposited NCs were characterized using field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), selected-area electron diffractometry (SAED), x-ray diffraction (XRD) and micro-Raman spectroscopy. FESEM micrographs reveal that vertically aligned NCs were grown on SA(100), whereas the NCs on the SA(012) were grown with a tilt angle of ~33° from the normal to substrates. TEM and SAED measurements showed that the TiO2 NCs on SA(100) with square cross section have their long axis directed along the [001] direction. The XRD results reveal TiO2 NCs with either (002) orientation on SA(100) substrate or (101) orientation on SA(012) substrate. A strong substrate effect on the alignment of the growth of TiO2 NCs has been demonstrated and the probable mechanism for the formation of these NCs has been discussed.

  6. Thermally-Driven Processes on Rutile TiO2(110)-(1x1): A Direct View at the Atomic Scale

    SciTech Connect

    Dohnalek, Zdenek; Lyubinetsky, Igor; Rousseau, Roger J.

    2010-05-01

    The technological importance of TiO2 has led to a broad effort aimed at understanding the elementary steps that underlie catalytic and photocatalytic reactions. The most stable surface, rutile TiO2(110), in particular, has became a prototypical model for fundamental studies of TiO2. In this critical review we have selected oxygen, water, and alcohols to evaluate recent progress relevant for applications in the areas of water splitting and oxidation of organic contaminants. We first focus on the characterization of defects and the distribution of excess charge that results from their formation. The subsequent section demonstrates the role of individual surface sites and the effect of available charge in the adsorption processes. The discussion of adsorbate dynamics follows, providing models for intrinsic and extrinsic diffusion processes as well as rotational dynamics of anchored alkoxy species. The final section summarizes our current understanding of TiO2(110) catalyzed reactions between water, oxygen, and their dissociation products.

  7. Manipulating the charge state of Au clusters on rutile TiO2(110) single crystal surfaces through molecular reactions probed by infrared spectroscopy.

    PubMed

    Cao, Yunjun; Hu, Shujun; Yu, Min; Wang, Tingting; Huang, Shiming; Yan, Shishen; Xu, Mingchun

    2016-07-14

    The charge state of Au clusters deposited on rutile TiO2(110) single crystal surfaces was studied by UHV-FTIRS using CO as a probe. The as-deposited Au clusters on oxidized TiO2(110) surfaces are electrically neutral and are identified by the 2105-2112 cm(-1) vibrational frequency of adsorbed CO depending on Au coverage. Annealing Au/TiO2(110) in a moderate O2 atmosphere at 400 K blue shifts the CO vibrational frequency by only 2-3 cm(-1) both on bare TiO2(110) surfaces and on Au clusters. However, NO exposure blue shifts the CO vibrational frequency by 16-26 cm(-1) for CO adsorbed on Au atoms near the interface and by 3-4 cm(-1) for CO adsorbed on top of Au clusters. As the acceptors of the intense charge transfer from Au, the Oa atoms generated through (NO)2→ N2O + Oa reactions on the small fraction of the bare TiO2(110) surface reside around the Au/TiO2(110) interface perimeter, causing the neutral Au(0) to be cationic Au(δ+) states. This is a new approach to manipulate the charge state of Au clusters on oxide surfaces, which may be helpful in regulating the catalytic redox reactions on oxide supported metal systems.

  8. Self-assembling of Zn porphyrins on a (110) face of rutile TiO2-The anchoring role of carboxyl groups

    NASA Astrophysics Data System (ADS)

    Zajac, Lukasz; Olszowski, Piotr; Godlewski, Szymon; Bodek, Lukasz; Such, Bartosz; Jöhr, Res; Pawlak, Remy; Hinaut, Antoine; Glatzel, Thilo; Meyer, Ernst; Szymonski, Marek

    2016-08-01

    The ordering of zinc containing porphyrin molecules on surface of rutile TiO2(110)-(1×1) has been investigated using scanning tunneling microscopy (STM) in ultra-high vacuum at room temperature. It is demonstrated that a carboxylic group (COOH) has a profound impact on the immobilization of the molecules. At coverages below 0.1 monolayer only molecules equipped with the group COOH could be anchored to the surface and imaged with STM. At higher coverage both species, with and without the carboxyl substituent, assemble into ordered structures, forming complete monolayers. It is found, however, that the rhomboid unit cells of these structures exhibit differences in size.

  9. Enhanced photocatalytic activity of Cl-residual rutile TiO2 nanorods after targeted co-modification with phosphoric and boric acids.

    PubMed

    Wu, Jing; Cui, Haiqin; Zhang, Xuliang; Luan, Yunbo; Jing, Liqiang

    2015-06-28

    The promotion of O2 adsorption on semiconductor surfaces for effectively capturing photogenerated electrons in the photocatalytic degradation of pollutants is highly desired. In this study, the targeted co-modification of residual chlorine rutile TiO2 nanorods with phosphoric and boric acids has been accomplished for the first time by simple wet chemical processes. The key to targeted co-modification is to connect -P-OH and -B-OH to the Cl-residual TiO2 surfaces by -Ti-OH and -Ti-Cl, respectively, consequently forming -Ti-O-P-OH and -Ti-Cl:B-OH ends. By means of the atmosphere-controlled surface photovoltage spectroscopy, the degrees for capturing photogenerated electrons by the adsorbed O2 as receptors on the resulting TiO2 nanorods are quantitatively analyzed. It is confirmed that the targeted co-modification could greatly promote the capture of the photogenerated electrons compared to the phosphate and borate modification alone. This is attributed to increased amounts of adsorbed O2 based on electrochemical O2 reduction and O2 temperature-programmed desorption measurements, further leading to the enhanced separation of photogenerated charges, characterized by an increase in the amount of produced hydroxyl radicals. This is responsible for the obviously enhanced photocatalytic activity of TiO2 nanorods towards the degradation of colorless gas-phase acetaldehyde and liquid-phase phenol. This work would provide us a feasible route for the co-modification with inorganic acids to synthesize efficient nanosized TiO2-based photocatalysts.

  10. Exceptional performance of photoelectrochemical water oxidation of single-crystal rutile TiO2 nanorods dependent on the hole trapping of modified chloride

    NASA Astrophysics Data System (ADS)

    Zhang, Xuliang; Cui, Haiqin; Humayun, Muhammad; Qu, Yang; Fan, Naiying; Sun, Xiaojun; Jing, Liqiang

    2016-02-01

    It is highly desired to effectively trap photogenerated holes for efficient photoelectrochemical (PEC) water oxidation to evolve O2 on oxide semiconductors. Herein, it is found for the first time mainly based on the time-resolved- and atmosphere-controlled- surface photovoltage responses that the modified chloride would effectively trap photogenerated holes so as to prolong the charge lifetime and hence promote charge separation of single-crystal rutile TiO2 nanorods. Its strong capacity to trap holes, comparable to the widely-used methanol and Co(II) phosphate, is well responsible for the exceptional photoactivities for PEC water oxidation to evolve O2 on rutile nanorods with a proper amount of chloride modified, about 2.5-time high as that on the resulting anatase nanoparticles, even 10-time if the surface area is considered. Moreover, it is suggested that the hole trapping role of chemically-adsorbed chloride is related to its lonely-pair electrons, and to the subsequently-produced intermediate Cl atoms with proper electronegativity for evolving O2. Interestingly, this finding is also applicable to the chloride-modified anatase TiO2. This work will provide a feasible strategy to design high-activity nanostructured semiconductor photoanodes for PEC water oxidation, even for overall water splitting.

  11. Exceptional performance of photoelectrochemical water oxidation of single-crystal rutile TiO2 nanorods dependent on the hole trapping of modified chloride

    PubMed Central

    Zhang, Xuliang; Cui, Haiqin; Humayun, Muhammad; Qu, Yang; Fan, Naiying; Sun, Xiaojun; Jing, Liqiang

    2016-01-01

    It is highly desired to effectively trap photogenerated holes for efficient photoelectrochemical (PEC) water oxidation to evolve O2 on oxide semiconductors. Herein, it is found for the first time mainly based on the time-resolved- and atmosphere-controlled- surface photovoltage responses that the modified chloride would effectively trap photogenerated holes so as to prolong the charge lifetime and hence promote charge separation of single-crystal rutile TiO2 nanorods. Its strong capacity to trap holes, comparable to the widely-used methanol and Co(II) phosphate, is well responsible for the exceptional photoactivities for PEC water oxidation to evolve O2 on rutile nanorods with a proper amount of chloride modified, about 2.5-time high as that on the resulting anatase nanoparticles, even 10-time if the surface area is considered. Moreover, it is suggested that the hole trapping role of chemically-adsorbed chloride is related to its lonely-pair electrons, and to the subsequently-produced intermediate Cl atoms with proper electronegativity for evolving O2. Interestingly, this finding is also applicable to the chloride-modified anatase TiO2. This work will provide a feasible strategy to design high-activity nanostructured semiconductor photoanodes for PEC water oxidation, even for overall water splitting. PMID:26906953

  12. Insights into Acetone Photochemistry on Rutile TiO2(110). 1. Off-Normal CH3 Ejection from Acetone Diolate.

    SciTech Connect

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

    2015-06-04

    Thermal- and photon-stimulated reactions of acetone co-adsorbed with oxygen on rutile TiO2(110) surface are studied with infrared reflection-adsorption spectroscopy (IRAS) combined with temperature programmed desorption and angle-resolved photon stimulated desorption. IRAS results show that n2-acetone diolate ((CH3)2COO) is produced via thermally-activated reactions between the chemisorbed oxygen with co-adsorbed acetone. Formation of acetone diolate is also consistent with 18O / 16O isotopic exchange experiments. During UV irradiation at 30 K, CH3 radicals are ejected from the acetone diolate with a distribution that is peaked at .-. +- 66 degrees from the surface normal along the azimuth (i.e. perpendicular to the rows of bridging oxygen and Ti5c ions). This distribution is also consistent with the orientation of the C–CH3 bonds in the n2-acetone diolate on TiO2(110). The acetone diolate peaks disappear from the IRAS spectra after UV irradiation and new peaks are observed and associated with n2-acetate. The data presented here demonstrate direct signatures of the proposed earlier 2-step mechanism for acetone photooxidation on TiO2(110)

  13. Interaction of carboxylic acids with rutile TiO2(110): IR-investigations of terephthalic and benzoic acid adsorbed on a single crystal substrate

    NASA Astrophysics Data System (ADS)

    Buchholz, Maria; Xu, Mingchun; Noei, Heshmat; Weidler, Peter; Nefedov, Alexei; Fink, Karin; Wang, Yuemin; Wöll, Christof

    2016-01-01

    The adsorption of two carboxylic acids, benzoic acid (BA) and terephthalic acid (TPA), on a single crystal rutile TiO2(110) substrate was studied using infrared reflection-absorption spectroscopy (IRRAS) in conjunction with DFT calculations. On the basis of the high-quality IR data (in particular for the OH bands), various adsorbate species with different geometries could be identified. The adsorption of both, BA and TPA, on TiO2(110) leads to deprotonation of carboxylic acids and protonation of substrate O-atoms. At low coverage, the deprotonated BA molecule adsorbs on TiO2(110) in an upright, bidentate configuration, while the TPA molecule adopts a flat-lying geometry with both carboxylates bound to the surface in a monodentate geometry. At higher coverages, a transition from flat-lying to upright-oriented TPA molecules occurs. At saturation coverage, both BA and TPA molecules undergo dimerization indicating the presence of pronounced attractive intermolecular interactions. We propose that the BA dimers are stabilized by the interaction between adjacent phenyl rings, while the TPA dimerization is attributed to the formation of double hydrogen bonds between adjacent apical carboxylic groups.

  14. Silicon Impurity Release and Surface Transformation of TiO2 Anatase and Rutile Nanoparticles in Water Environments

    EPA Science Inventory

    Surface transformation can affect the stability, reactivity, and toxicity of titanium dioxide (TiO2) nanoparticles (NPs) when released to water environments. Herein, we investigated the release kinetics of Si impurity frequently introduced during NP synthesis and the resulting ef...

  15. Release of Phosphorous Impurity from TiO2 Anatase and Rutile Nanoparticles in Aquatic Environments and Its Implications

    EPA Science Inventory

    Phosphorus-bearing materials as an additive have been popularly used in nanomaterial synthesis and the residual phosphorus within the nanoparticles (NPs) can be of an environmental concern. For instance, phosphorus within pristine commercial TiO2 NPs greatly influences the surfac...

  16. Highly hydrophilic conversion on oriented TiO2 thin films synthesized by a facile spin-coating method

    NASA Astrophysics Data System (ADS)

    Miyauchi, Masahiro; Tokudome, Hiromasa

    2007-07-01

    Single crystalline rectangular shape nanorods with an anatase or rutile TiO2 were synthesized by a soft-chemical process. These nanorods were highly dispersed in aqueous solutions and their surfaces have well-defined crystal faces, i.e., anatase (100) and rutile (110) faces. Highly oriented thin films with either an anatase and rutile phase were fabricated by facile spin coating of these colloidal solutions of nanorods without an annealing procedure. The surfaces of these films exhibited highly hydrophilic conversion under white fluorescent light bulb illumination.

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

    PubMed

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

    2013-10-01

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

  18. The influence of surface structure on H4SiO4 oligomerization on rutile and amorphous TiO2 surfaces: an ATR-IR and synchrotron XPS study.

    PubMed

    Song, Yantao; Swedlund, Peter J; McIntosh, Grant J; Cowie, Bruce C C; Waterhouse, Geoffrey I N; Metson, James B

    2012-12-11

    Silicic acid (H(4)SiO(4)) is ubiquitous in natural aquatic systems. Applications of TiO(2) in these systems will be influenced by H(4)SiO(4) sorption and oligomerization reactions on the TiO(2) surface, and this can affect many aspects of TiO(2) reactivity. The spatial arrangement of sorption sites on a metal oxide surface can promote specific lateral interactions, such as oligomerization, between sorbed species. In this work we explore the relationship between surface structure and interfacial H(4)SiO(4) oligomerization by quantifying the extent of H(4)SiO(4) sorption and oligomerization on three TiO(2) phases; a rutile phase having well-developed (110) faces (R180), a rutile phase with poorly developed (110) faces (R60), and an amorphous TiO(2) (TiO(2(am))). The in situ ATR-IR spectra measured over time as 0.2 mM H(4)SiO(4) reacted with TiO(2) were quite different on the three TiO(2) phases. The percentage of the surface H(4)SiO(4) that was present as oligomers increased over time on all phases, but after 20 h almost all H(4)SiO(4) on the R180 surface was oligomeric, while the H(4)SiO(4) on TiO(2(am)) was predominantly monomeric. The extent of H(4)SiO(4) oligomerization on R60 was intermediate. When the TiO(2) phases reacted with 1.5 mM H(4)SiO(4) the ATR-IR spectra showed oligomeric silicates dominating the surface of all three TiO(2) phases; however, after 20 h the percentage of the surface H(4)SiO(4) present as three-dimensional polymers was ∼30, 10, and 0% on R180, R60, and TiO(2(am)) respectively. The Si 2s photoelectron peak binding energy (BE) and the H(4)SiO(4) surface coverage (Γ(Si)) were measured by XPS over a range of Γ(Si). For any given Γ(Si) the Si 2s BE's were in the order R180 > R60 > TiO(2(am)). A higher Si 2s BE indicates a greater degree of silicate polymerization. The ATR-IR and XPS results support the existing model for interfacial H(4)SiO(4) oligomerization where linear trimeric silicates are formed by insertion of a solution H(4)SiO(4

  19. 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

  20. Adsorption and stability of malonic acid on rutile TiO2 (110), studied by near edge X-ray absorption fine structure and photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Syres, Karen L.; Thomas, Andrew G.; Graham, Darren M.; Spencer, Ben F.; Flavell, Wendy R.; Jackman, Mark J.; Dhanak, Vinod R.

    2014-08-01

    The adsorption of malonic acid on rutile TiO2 (110) has been studied using photoelectron spectroscopy and C K-edge, near edge X-ray fine structure spectroscopy (NEXAFS). Analysis of the O 1s and Ti 2p spectra suggest that the molecule adsorbs dissociatively in a doubly-bidentate adsorption geometry as malonate. The data are unable to distinguish between a chelating bonding mode with the backbone of the molecule lying along the [001] azimuth or a bridging geometry along the direction. Work carried out on a wiggler beamline suggests that the molecule is unstable under irradiation by high-flux synchrotron radiation from this type of insertion device.

  1. 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.

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

    EPA Science Inventory

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

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

    EPA Science Inventory

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

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

    PubMed

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

    2005-07-13

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

  5. Low-Temperature Desorption of N2O from NO on Rutile TiO2(110)-1x1

    SciTech Connect

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

    2014-05-08

    We find that NO dosed on rutile TiO2(110)-1×1 at substrate temperatures as low as 50 K readily reacts to produce N2O which desorbs promptly from the surface leaving an oxygen adatom behind. The desorption rate of N2O reaches a maximum value after 1 – 2 sec at an NO flux of 1.2 ×1014 NO/cm2∙sec and then decreases rapidly as the initially clean, reduced TiO2(110) surface with ~5% oxygen vacancies (VO’s) becomes covered with oxygen adatoms and unreacted NO. The maximum desorption rate is also found to increase as the substrate temperature is raised up to about 100 K. Interestingly, the N2O desorption during the low-temperature (LT) NO dose is strongly suppressed when molecular oxygen is predosed, whereas it persists on the surface with VO’s passivated by surface hydroxyls. Our results show that the surface charge, not the VO sites, plays a dominant role in the LT N2O desorption induced by a facile NO reduction at such low temperatures.

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

    PubMed

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

    2016-09-28

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

  7. The effect of oxygen vacancies on the binding interactions of NH3 with rutile TiO2(110) -1×1

    SciTech Connect

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

    2012-11-21

    A series of NH3 temperature-programmed desorption (TPD) spectra was taken after the NH3 dose at 70 K on rutile TiO2(110)-1×1 surfaces with the oxygen vacancy (VO) concentrations of ~0% (p-TiO2) and 5% (r-TiO2), respectively, to study the effect of VO’s on the desorption energy of NH3 as a function of the coverage, θ. Our results show that at zero coverage limit, the desorption energy of NH3 on r-TiO2 is 115 kJ/mol, which is 10 kJ/mol less than that on p-TiO2. The desorption energy from the Ti4+ sites decreases with increasing θ due to the repulsive NH3 - NH3 interactions and approaches ~ 55 kJ/mol upon the saturation of Ti4+ sites (θ = 1 monolayer, ML) on both p- and r-TiO2. The absolute saturation coverage is determined to be about 10% smaller on r-TiO2 than that on p-TiO2. Further, the trailing edges of the NH3 TPD spectra on the hydroxylated TiO2(110) (h-TiO2) appear to be the same as that on r-TiO2 while those on oxidized TiO2(110) (o-TiO2) shift to higher temperatures. We present the detailed analysis of the results and reconcile the observed differences based on the repulsive adsorbate-adsorbate interactions between neighboring NH3 molecules and the surface charge associated with the presence of VO’s. Besides NH3, no other reaction products are observed in the TPD spectra.

  8. Characterization of the Active Surface Species Responsible for UV-Induced Desorption of O2 from the Rutile TiO2(110) Surface

    SciTech Connect

    Henderson, Michael A.; Shen, Mingmin; Wang, Zhitao; Lyubinetsky, Igor

    2013-03-21

    We have examined the chemical and photochemical properties of molecular oxygen on the (110) surface of rutile TiO2 at 100 K using electron energy loss spectroscopy (EELS), photon stimulated desorption (PSD) and scanning tunneling microscopy (STM). Oxygen chemisorbs on the TiO2(110) surface at 100 K through charge transfer from surface Ti3+ sites. The charge transfer process is evident in EELS by a decrease in the intensity of the Ti3+ d-to-d transition in EELS at ~0.9 eV and formation of a new loss ~2.8 eV. Based on comparisons with the available homogeneous and heterogeneous literature for complexed/adsorbed O2, the species responsible for the 2.8 eV peak can be assigned to a surface peroxo (O2 2-) state of O2. This species was identified as the active form of adsorbed O2 on TiO2(110) for PSD. The adsorption site of this peroxo species was assigned to that of a regular five-cooridinated Ti4+ (Ti5c) site based on comparisons between the UV exposure dependent behavior of O2 in STM, PSD and EELS data. Assignment of the active form of adsorbed O2 to a peroxo species at normal Ti5c sites necessitates reevaluation of the simple mechanism in which a single valence band hole neutralizes a singly charged O2 species (superoxo or O2-) leading to desorption of O2 from a physisorbed potential energy surface. This work was supported by the U.S. Department of Energy (DOE), Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences, and the Chemical Imaging Initiative at Pacific Northwest National Laboratory (PNNL), and was performed in the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOE's Office of Biological and Environmental Research and located at PNNL.

  9. Coadsorption properties of CO2 and H2O on TiO2 rutile (110): a dispersion-corrected DFT study.

    PubMed

    Sorescu, Dan C; Lee, Junseok; Al-Saidi, Wissam A; Jordan, Kenneth D

    2012-08-21

    Adsorption and reactions of CO(2) in the presence of H(2)O and OH species on the TiO(2) rutile (110)-(1×1) surface were investigated using dispersion-corrected density functional theory and scanning tunneling microscopy. The coadsorbed H(2)O (OH) species slightly increase the CO(2) adsorption energies, primarily through formation of hydrogen bonds, and create new binding configurations that are not present on the anhydrous surface. Proton transfer reactions to CO(2) with formation of bicarbonate and carbonic acid species were investigated and found to have barriers in the range 6.1-12.8 kcal/mol, with reactions involving participation of two or more water molecules or OH groups having lower barriers than reactions involving a single adsorbed water molecule or OH group. The reactions to form the most stable adsorbed formate and bicarbonate species are exothermic relative to the unreacted adsorbed CO(2) and H(2)O (OH) species, with formation of the bicarbonate species being favored. These results are consistent with single crystal measurements which have identified formation of bicarbonate-type species following coadsorption of CO(2) and water on rutile (110).

  10. Low-frequency dielectric properties of intrinsic and Al-doped rutile TiO2 thin films grown by the atomic layer deposition technique

    NASA Astrophysics Data System (ADS)

    Kassmi, M.; Pointet, J.; Gonon, P.; Bsiesy, A.; Vallée, C.; Jomni, F.

    2016-06-01

    Dielectric spectroscopy is carried out for intrinsic and aluminum-doped TiO2 rutile films which are deposited on RuO2 by the atomic layer deposition technique. Capacitance and conductance are measured in the 0.1 Hz-100 kHz range, for ac electric fields up to 1 MVrms/cm. Intrinsic films have a much lower dielectric constant than rutile crystals. This is ascribed to the presence of oxygen vacancies which depress polarizability. When Al is substituted for Ti, the dielectric constant further decreases. By considering Al-induced modification of polarizability, a theoretical relationship between the dielectric constant and the Al concentration is proposed. Al doping drastically decreases the loss in the very low frequency part of the spectrum. However, Al doping has almost no effect on the loss at high frequencies. The effect of Al doping on loss is discussed through models of hopping transport implying intrinsic oxygen vacancies and Al related centers. When increasing the ac electric field in the MVrms/cm range, strong voltage non-linearities are evidenced in undoped films. The conductance increases exponentially with the ac field and the capacitance displays negative values (inductive behavior). Hopping barrier lowering is proposed to explain high-field effects. Finally, it is shown that Al doping strongly improves the high-field dielectric behavior.

  11. Alcohol Chemistry on Rutile TiO2(110): The Influence of Alkyl Substituents on Reactivity and Selectivity

    SciTech Connect

    Kim, Yu Kwon; Kay, Bruce D.; White, J. M.; Dohnalek, Zdenek

    2007-12-13

    Product yields and selectivities, based on ultra high vacuum temperature programmed desorption, are compared for ten C2 to C8 aliphatic alcohols dosed at 100 K on highly-ordered TiO2(110) with a 3.5 % concentration of surface oxygen vacancies. Dehydration to form an alkene and water typically dominates while two other channels, dehydrogenation to form aldehydes, and reformation of alcohol, make detectable contributions for primary alcohols. Depending on the alcohol there are two distinct dehydration pathways, one operative at low temperature (LT, 300 to 425 K) and the other at high temperature (HT, 480 to 650 K). The HT dehydration pathway is common, while the LT channel is not observed for tertiary butanol and 3- and 4-octanol. The observed trends are accounted for in terms of the inductive and steric effects of the alkyl substituents.

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

    NASA Astrophysics Data System (ADS)

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

    2012-07-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2011-03-01

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

  14. Water adsorption on rutile TiO2(110) for applications in solar hydrogen production: A systematic hybrid-exchange density functional study

    NASA Astrophysics Data System (ADS)

    Patel, M.; Mallia, G.; Liborio, L.; Harrison, N. M.

    2012-07-01

    Periodic hybrid-exchange density functional theory calculations are used to predict the structure of water on the rutile TiO2(110) surface (Θ⩽ 1 ML), which is an important first step towards understanding the photocatalytic processes that occur in solar water splitting. A detailed model describing the water-water and water-surface interactions is developed by exploring thoroughly the adsorption energetics. The possible adsorption mode—molecular, dissociative, or mixed—and the binding energy are studied as a function of coverage and arrangement, thus separation, of adsorbed species. These dependencies (coverage and arrangement) have a significant influence on the nature of the interactions involved in the H2O-TiO2 system. The importance of both direct intermolecular and surface-mediated interactions between surface species is emphasized. Finally, to gain insight into the photooxidation of adsorbed species at the surface, the electronic structure of the predicted adsorbate-substrate geometries is analyzed in terms of total and projected density of states.

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

    NASA Astrophysics Data System (ADS)

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

    2016-11-01

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

  16. H2O2-assisted photocatalysis on flower-like rutile TiO2 nanostructures: Rapid dye degradation and inactivation of bacteria

    NASA Astrophysics Data System (ADS)

    Kőrösi, László; Prato, Mirko; Scarpellini, Alice; Kovács, János; Dömötör, Dóra; Kovács, Tamás; Papp, Szilvia

    2016-03-01

    Hierarchically assembled flower-like rutile TiO2 (FLH-R-TiO2) nanostructures were successfully synthesized from TiCl4 at room temperature without the use of surfactants or templates. An initial sol-gel synthesis at room temperature allowed long-term hydrolysis and condensation of the precursors. The resulting FLH-R-TiO2 possessed relatively high crystallinity (85 wt%) and consisted of rod-shaped subunits assembling into cauliflower-like nanostructures. Hydrothermal evolution of FLH-R-TiO2 at different temperatures (150, 200 and 250 °C) was followed by means of X-ray diffraction, transmission and scanning electron microscopy. These FLH-R-TiO2 nanostructures were tested as photocatalysts under simulated daylight (full-spectrum lighting) in the degradation of methyl orange and in the inactivation of a multiresistant bacterium, Klebsiella pneumoniae. The effects of hydrothermal treatment on the structure, photocatalytic behavior and antibacterial activity of FLH-R-TiO2 are discussed.

  17. Atomic layer deposition of rutile and TiO2-II from TiCl4 and O3 on sapphire: Influence of substrate orientation on thin film structure

    NASA Astrophysics Data System (ADS)

    Möldre, Kristel; Aarik, Lauri; Mändar, Hugo; Niilisk, Ahti; Rammula, Raul; Tarre, Aivar; Aarik, Jaan

    2015-10-01

    Atomic layer deposition of TiO2 from TiCl4 and ozone on single crystal α-Al2O3 substrates was investigated and the possibility to control the phase composition by the substrate orientation was demonstrated. Epitaxial growth of rutile and high-pressure TiO2-II on α-Al2O3(0 0 0 1) and rutile on α-Al2O3(0 1 1¯ 2) were obtained at 400-600 °C. On α-Al2O3(0 0 0 1), the epitaxial relationships were determined to be [0 1 0]R // [2 1¯ 1¯ 0]S and [0 0 1]R // [0 1 1¯ 0]S for rutile and sapphire, and [0 0 1]II // [2 1¯ 1¯ 0]S and [0 1¯ 0]II // [0 1 1¯ 0]S for TiO2-II and sapphire. The TiO2-II concentration up to 50% was obtained in the films deposited at 425-500 °C. On α-Al2O3(0 1 1¯ 2), the epitaxial relationship of rutile was [0 1 0]R // [2 1¯ 1¯ 0]S and [0 0 1]R // [0 1 1¯ 0]S. The densities of epitaxial films reached 4.2-4.3 g/cm3 on substrates with both orientations but the epitaxial quality was markedly higher on α-Al2O3(0 0 0 1).

  18. Impact of nonadiabatic charge transfer on the rate of redox chemistry of carbon oxides on rutile TiO2 (110) surface

    SciTech Connect

    Yoon, Yeohoon; Wang, Yanggang; Rousseau, Roger J.; Glezakou, Vassiliki Alexandra

    2015-03-06

    We present the results of a density functional theory (DFT) within the LDA+U approximation on large models of partially reduced TiO2 (110) rutile surface to investigate the nature of charge transfer and the role of non-adiabatic effects on three prototypical redox reactions: (i) O2 adsorption (ii) CO oxidation and (iii) CO2 reduction. Charge-constrained DFT (cDFT) is used to estimate kinetic parameters for a Marcus theory rate law that accounts for adiabatic coupling effects on reaction rates. We find that for O2 adsorption, the coupling between adiabatic states is strong, leading to fast charge transfer rates. The lowest energy structures at high coverage consist of two chemisorbed O2-, one adsorbed at a VO site and the other adsorbed at an adjacent Ti5C site. For CO oxidation, however, all reactions are kinetically hindered on the ground state due to the weak adiabatic coupling at the state crossing, such that one has to overcome two kinetically unfavorable charge transfer events to drive the process (non-adiabatically) on the thermal ground state. The process can be driven by photochemical means but would result in an adsorbed radical [OCOO-] intermediate species. Similarly, CO2 reduction also proceeds via a non-adiabatic charge transfer to form an adsorbed CO2- species followed by a second non-adiabatic charge transfer to produce CO. Our analysis provides important computational guidelines for modeling these types of processes. We thank Z. Dohnalek, M. Hendersen, G. Kimmel, H. Metieu, and N. Petrik for invaluable discussions. This work was supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences and performed at the Pacific Northwest National Laboratory (PNNL). PNNL is a multi-program national laboratory operated for DOE by Battelle. Computational resources were provided at W. R. Wiley Environmental Molecular Science Laboratory (EMSL), a national scientific user facility sponsored by the

  19. O2 evolution on a clean partially reduced rutile TiO2(110) surface and on the same surface precovered with Au1 and Au2: the importance of spin conservation.

    PubMed

    Chrétien, Steeve; Metiu, Horia

    2008-08-21

    We have used spin-polarized density functional theory (DFT) to study O(2) evolution on a clean partially reduced rutile TiO(2)(110) surface (i.e., a surface having oxygen vacancies) and its interaction with Au(1) or Au(2) cluster adsorbed on it. We assume that the total spin of the electronic wave function is related to the number of unpaired spins (N(s)) and calculate the binding and the activation energies involved in O(2) evolution for fixed values of N(s). In addition to keeping N(s) constant, we assume that reactions in which the N(s) of the reactants differs from that of the products are very slow. The potential energy surfaces obtained in this way depend strongly on N(s). For example, O(2) dissociation at the vacancy site on a clean partially reduced TiO(2)(110) surface is exothermic by 0.85 eV in the triplet state and the highest activation energy in the chain of reactions leading to the O(2) dissociation is 0.67 eV. In the singlet state, O(2) dissociation is endothermic by 0.11 eV and the activation energy leading to dissociation is 1.30 eV. These observations are in qualitative agreement with scanning tunneling microscopy experiment in which O(2) dissociation on a partially reduced rutile TiO(2)(110) surface is observed at temperature as low as 120 K. In contrast, O(2) dissociation is predicted to be endothermic and is prevented by an activation barrier larger than 1 eV in all the previous DFT calculations, in which the DFT program varies N(s) to get the lowest energy state. We find that on a partially reduced rutile TiO(2)(110) with Au(1) and Au(2) preadsorbed on its surface, O(2) dissociates at the vacancy site: One oxygen atom fills the oxygen vacancy and the other becomes available for oxidation chemistry. This means that Au(1) and Au(2) supported on a partially reduced TiO(2)(110) surface is not an oxidation catalyst since the presence of oxygen turns it into a stoichiometric Au(n)/TiO(2)(110) surface. Finally, we find that the evolution of oxygen on

  20. Synthesis of SUB-10 NM TiO2 Nanowires for the Application of Dye-Sensitized Solar Cells

    NASA Astrophysics Data System (ADS)

    Liu, Jun; Liu, Zhen; Lin, Kangbao; Wei, Aixiang

    2013-04-01

    Highly oriented single-crystalline rutile TiO2 nanowires on transparent conductive fluorine-doped tin oxide (FTO) substrates are prepared by low-temperature hydrothermal method. The small lattice mismatch between FTO substrate and rutile TiO2 promote the epitaxial nucleation and growth of rutile TiO2 nanowires on FTO, with the diameter of 4-6 nm. Due to Van der waals force, the ultrafine nanowires tend to gather together, forming nanowire bundles. Using the ultrafine nanowire bundle array as the photoanode and ruthenium complex (N719) as the sensitizer, dye-sensitized solar cells (DSSCs) are assembled. The effect of the TiO2 nanowire gathering on the power conversion of the DSSCs has been investigated. Experimental result shows that the light-to-electricity conversion efficiency is increased by reducing the gathering of the nanowires through introducing toluene into reactant precursors. The DSSCs based on the bundles with smallest average width (i.e., least nanowire gathering) show the highest power conversion efficiency of 3.70%. The relatively high energy conversion efficiency is contributed to the large surface area, which enhances the adsorption of dye molecules.

  1. Synthesis of dandelion-like TiO2 microspheres as anode materials for lithium ion batteries with enhanced rate capacity and cyclic performances

    NASA Astrophysics Data System (ADS)

    Yi, Jin; Liu, Yan-lin; Wang, Yuan; Li, Xiao-ping; Hu, She-jun; Li, Wei-shan

    2012-11-01

    Dandelion-like TiO2 microspheres consisting of numerous rutile single-crystalline nanorods were synthesized for the first time by a hydrothermal method. Their crystal structure, morphology and electrochemical properties were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and galvanostatic charge and discharge tests. The results show that the synthesized TiO2 microspheres exhibit good rate and cycle performances as anode materials of lithium ion batteries. It can be found that the dandelion-like structure provides a larger specific surface area and the single-crystalline nanorod provides a stable structure and fast pathways for electron and lithium ion transport, which contribute to the rate and cycle performances of the battery.

  2. 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

  3. Titanium atoms dimerization phenomenon and magnetic properties of titanium-antisite (TiO) and chromium doped rutile TiO2, ab-initio calculation

    NASA Astrophysics Data System (ADS)

    Zarhri, Z.; Ziat, Y.; El Rhazouani, O.; Benyoussef, A.; Elkenz, A.

    2016-07-01

    The ab-initio calculations based on the Korringa Kohn Rostoker approximation approach combined with coherent potential approximation (KKR-CPA), were used to study the magnetic properties of the titanium anti-site (TiO) and chromium (Cr) doped TiO2. In the considered systems, we used different concentrations for TiO defect and Cr doping. In TiO2(0.98)(TiO)0.02, the obtained results indicate that TiO is a donor having half-metal behavior. TiO[3d] band is located at the Fermi level, although isn't 100% polarized, the ferromagnetic (FM) state is verified as being more stable than disordered local moment (DLM) state. For Ti0.98Cr0.02O2 the Cr doping introduced new states which give the material half-metallic feature. The majority spin of Cr impurities are located at the Fermi level and the conduction electrons around the Fermi level are 100% spin polarized. This indicates the stability of (FM) state. Moreover, in Ti0.98Cr0.02O2(0.98)(TiO)0.02, the top of the valence band is shifted to lower energy compared to pure TiO2, and the n-type of TiO2 is verified. The majority spin of Cr[3d] are located at 0.025 Ry close to the Fermi level. The predicted Curie temperatures (Tc) were calculated using the mean field approximation (MFA) and we predicted that TiO defect in Cr doped TiO2 makes Tc higher. This kind of defect makes the material useful for spinotronics's applications and devices.

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

    PubMed

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

    2015-09-01

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

  5. Effects of variations in precursor concentration on the growth of rutile TiO2 nanorods on Si substrate with fabricated fast-response metal-semiconductor-metal UV detector

    NASA Astrophysics Data System (ADS)

    Selman, Abbas M.; Hassan, Z.

    2015-06-01

    This study aimed to investigate the effects of variations in precursor concentration (TiCl3 solution) on the structural, morphological, and optical properties of rutile titanium dioxide (TiO2) nanorods and fabricated metal-semiconductor-metal UV detector depending on the optimal sample. The nanorods were prepared from an aqueous solution of titanium (III) chloride (TiCl3) on p-type, (1 1 1)-oriented Si substrates at different concentrations of TiCl3 solutions (2, 3, 4, and 5 mM). The experimental results showed that the TiO2 nanorods grown at 4 mM concentration exhibited optimal structural properties. A fast-response metal-semiconductor-metal UV detector was fabricated by depositing Pt contacts on the front of the optimal sample via RF reactive magnetron sputtering. Upon exposure to 365 nm light (2.3 mW/cm2) at 5 V bias voltage, the device showed 44.4 sensitivity. In addition, the internal gain was 1.45, and the photoresponse peak was 70 mA/W. The response and the recovery times were calculated to be 7.8 ms upon illumination to a pulse UV light (365 nm) at 5 V bias voltage.

  6. Effects of Carbon Allotrope Interface on the Photoactivity of Rutile One-Dimensional (1D) TiO2 Coated with Anatase TiO2 and Sensitized with CdS Nanocrystals.

    PubMed

    Pathak, Pawan; Israel, Luis Henrique; Pereira, Ellen Jessica Monterio; Subramanian, Vaidyanathan Ravi

    2016-06-01

    The assembly of a large-bandgap one-dimensional (1D) oxide-conductive carbon-chalcogenide nanocomposite and its surface, optical, and photoelectrochemical properties are presented. Microscopy, surface analysis, and optical spectroscopy results are reported to provide insights into the assembly of the nanostructure. We have investigated (i) how the various carbon allotropes (C60), reduced graphene oxide (RGO), carbon nanotubes (CNTs), and graphene quantum dots (GQDs) can be integrated at the interface of the 1D TiO2 and zero-dimensional (0D) CdS nanocrystals; (ii) the carbon allotrope and CdS loading effects; (iii) the impact of the carbon allotrope presence on 0D CdS nanocrystals; and (iv) how they promote light absorbance. Subsequently, the functioning of the integrated nanostructured assembly in a photoelectrochemical cell has been systematically investigated. These studies include (i) chronoamperometry, (ii) impedance measurements or EIS, and (iii) linear sweep voltammetry. The results indicate that the presence of a GQD interface shows the most enhancement in the photoelectrochemical properties. The optimized photocurrent values were respectively noted to be 2.8, 2.2, 1.9, and 1.6 mA/cm(2), indicating JGQD > JRGO > JCNT > Jfullerene. Furthermore, the annealing conditions have indicated that ammonia treatment leads to an increase in the photoelectrochemical responses when using any form of the carbon allotropes. PMID:27121182

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

    USGS Publications Warehouse

    Commeau, Judith A.; Valentine, Page C.

    1991-01-01

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

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

    NASA Astrophysics Data System (ADS)

    Arcila, J. F.; Hincapié, A. F.

    2013-11-01

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

  9. Determination of Phase Ratio in Polymorphic Materials by X-Ray Absorption Spectroscopy: The Case of Anatase and Rutile Phase Mixture in TiO2

    SciTech Connect

    Smith, M. F.; Klysubun, W.; Kityakarn, S.; Worayingyong, A.; Zhang, S. B.; Wei, S. H.; Onkaw, D.; Songsiriritthigul, P.; Rujirawat, S.; Limpijumnong, S.

    2009-01-01

    We demonstrate that x-ray absorption spectroscopy (XAS) can be used as an unconventional characterization technique to determine the proportions of different crystal phases in polymorphic samples. As an example, we show that ratios of anatase and rutile phases contained in the TiO{sub 2} samples obtained by XAS are in agreement with conventional x-ray diffraction (XRD) measurements to within a few percent. We suggest that XAS measurement is a useful and reliable technique that can be applied to study the phase composition of highly disordered or nanoparticle polymorphic materials, where traditional XRD technique might be difficult.

  10. Probing the local electronic structure of the cross-linked (1 × 2) reconstruction of rutile TiO2(110)

    NASA Astrophysics Data System (ADS)

    Yim, Chi Ming; Pang, Chi Lun; Thornton, Geoff

    2016-08-01

    The electronic structure of cross-linked TiO2(110)-(1 × 2) has been investigated using scanning tunneling spectroscopy (STS) and by monitoring changes in ultraviolet photoelectron spectroscopy (UPS) following exposure of the surface to O2. STS reveals two states located in the bandgap, at 0.7 and 1.5 eV below the Fermi level. The population of these two states varies over different parts of the (1 × 2)-reconstructed surface. An additional state at 1.1 eV above the Fermi level is observed at the double link part of the structure. All of the bandgap states are attenuated following exposure to O2, while the workfunction is increased. We attribute this to an electron transfer from the surface to the adsorbed oxygen.

  11. 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.

  12. Formation of a thermally stable bilayer of coadsorbed intact and deprotonated thymine exploiting the surface corrugation of rutile TiO2(110).

    PubMed

    Duncan, D A; Pfisterer, J H K; Deimel, P S; Acres, R G; Fritton, M; Feulner, P; Barth, J V; Allegretti, F

    2016-07-27

    The adsorption of thymine, a pyrimidine based nucleobase, was studied on the (110) termination of rutile titanium dioxide in order to understand the thermal stability and gross structural parameters of the interaction between a strongly polar adsorbate and a highly corrugated transition metal oxide surface. Near-edge X-ray absorption fine structure (NEXAFS), X-ray photoelectron spectroscopy (XPS), temperature programmed XPS and temperature programmed desorption indicated the growth of a room temperature stable bilayer, which could only be removed by annealing to 450 K. The remaining first layer was remarkably robust, surviving annealing up to 550 K before undergoing N-H bond scission. The comparison to XPS of a sub-monolayer exposure of 1-methyluracil shows that the origin of the room temperature stable bilayer is not intermolecular interactions. This discovery, alongside the deprotonation of one of the first layer's pyrimidinic nitrogen atoms at room temperature, suggests that the thymine molecules in the first layer bind to the undercoordinated surface Ti atoms, and the second layer thymine molecules coordinate with the bridging oxygen atoms which protrude above the Ti surface plane on the (110) surface. The NEXAFS results indicate an almost upright orientation of the molecules in both layers, with a 30 ± 10° tilt away from the surface normal.

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

    SciTech Connect

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

    1999-07-07

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

  14. Reverse micelles directed synthesis of TiO2-CeO2 mixed oxides and investigation of their crystal structure and morphology

    NASA Astrophysics Data System (ADS)

    Matějová, Lenka; Valeš, Václav; Fajgar, Radek; Matěj, Zdeněk; Holý, Václav; Šolcová, Olga

    2013-02-01

    The synthesis of TiO2-CeO2 mixed oxides based on the sol-gel process controlled within reverse micelles of non-ionic surfactant Triton X-114 in cyclohexane is reported. The crystallization, phase composition, trends in nanoparticles growth and porous structure properties are studied as a function of Ti:Ce molar composition and annealing temperature by in-situ X-ray diffraction, Raman spectroscopy and physisorption. The brannerite-type CeTi2O6 crystallizes as a single crystalline phase at Ti:Ce molar composition of 70:30 and in the mixture with cubic CeO2 and anatase TiO2 for composition 50:50. At Ti:Ce molar ratios 90:10 and 30:70 the mixtures of TiO2 anatase, rutile and cubic CeO2 appear. In these mixtures TiO2 rutile is formed at higher temperatures than conventionally. Additionally, the amount of a present amorphous phase in individual mixtures was estimated from diffraction data. The porous structure morphology depends both on molar composition and annealing temperature. This is correlated with the presence of carbon impurities of different character.

  15. Single crystalline mesoporous silicon nanowires

    SciTech Connect

    Hochbaum, A.I.; Gargas, Daniel; Jeong Hwang, Yun; Yang, Peidong

    2009-08-04

    Herein we demonstrate a novel electroless etching synthesis of monolithic, single-crystalline, mesoporous silicon nanowire arrays with a high surface area and luminescent properties consistent with conventional porous silicon materials. These porous nanowires also retain the crystallographic orientation of the wafer from which they are etched. Electron microscopy and diffraction confirm their single-crystallinity and reveal the silicon surrounding the pores is as thin as several nanometers. Confocal fluorescence microscopy showed that the photoluminescence (PL) of these arrays emanate from the nanowires themselves, and their PL spectrum suggests that these arrays may be useful as photocatalytic substrates or active components of nanoscale optoelectronic devices.

  16. Single crystalline mesoporous silicon nanowires

    SciTech Connect

    Hochbaum, Allon; Dargas, Daniel; Hwang, Yun Jeong; Yang, Peidong

    2009-08-18

    Herein we demonstrate a novel electroless etching synthesis of monolithic, single-crystalline, mesoporous silicon nanowire arrays with a high surface area and luminescent properties consistent with conventional porous silicon materials. The photoluminescence of these nanowires suggest they are composed of crystalline silicon with small enough dimensions such that these arrays may be useful as photocatalytic substrates or active components of nanoscale optoelectronic devices. A better understanding of this electroless route to mesoporous silicon could lead to facile and general syntheses of different narrow bandgap semiconductor nanostructures for various applications.

  17. Structural investigations of hybrid TiO2/CNTs nanomaterials.

    PubMed

    Lin, Kuan-Nan; Liou, Wei-Jen; Lin, Hong-Ming; Yang, Tsung-Yeh; Lin, Chung-Kwei

    2010-05-01

    In the present study, pure TiO2 and hybrid TiO2/CNTs nanomaterials are prepared by sol gel technique. Post heat treatment is performed at 600, 800, and 1000 degrees C, respectively. The structural characterizations are performed by field emission scanning electron microscopy, transmission electron microscopy, X-ray diffraction and synchrotron X-ray absorption spectroscopy techniques. Experimental results show that anatase to rutile transformation can be observed for pure TiO2 nanomaterials after heat treatment at 800 degrees C. The anatase to rutile transformation is inhibited by carbon nanotubes, and therefore only anatase phases for TiO2 nanomaterials can be observed in the hybrid nanomaterials. The 600 degrees C hybrid nanomaterials show a microstructure with CNTs covered by continuous TiO2 films of numerous small nanoparticles. After applying heat treatment on the hybrid nanomaterials at 1000 degrees C, only TiO2 nanoparticles adhere individually to the uncovered CNTs. Though all hybrid nanomaterials exhibit anatase TiO2, synchrotron X-ray absorption spectra investigations reveal that hybrid TiO2/CNTs exhibit different electronic properties as compared to those of pure TiO2 nanomaterials.

  18. On the Crystal Structural Control of Sputtered TiO2 Thin Films

    NASA Astrophysics Data System (ADS)

    Jia, Junjun; Yamamoto, Haruka; Okajima, Toshihiro; Shigesato, Yuzo

    2016-07-01

    In this study, we focused on the origin on the selective deposition of rutile and anatase TiO2 thin films during the sputtering process. The observation on microstructural evolution of the TiO2 films by transmission electron microscopy revealed the coexistence of rutile and anatase TiO2 phases in the initial stage under the preferential growth conditions for the anatase TiO2; the observations further revealed that the anatase phase gradually dominated the crystal structure with increasing film thickness. These results suggest that the bombardment during the sputtering deposition did not obviously affect the TiO2 crystal structure, and this was also confirmed by off-axis magnetron sputtering experiments. We also investigated the mechanism of the effect of Sn impurity doping on the crystal structure using first-principles calculations. It is found that the formation energy of Sn-doped rutile TiO2 is lower than that of Sn-doped anatase TiO2; this suggests that the Sn-doped TiO2 favours the rutile phase. These results offer a guideline for the utilization of selective deposition of rutile and anatase TiO2 thin films in various industrial applications.

  19. Size-tunable TiO2 nanorod microspheres synthesised via a one-pot solvothermal method and used as the scattering layer for dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Rui, Yichuan; Li, Yaogang; Zhang, Qinghong; Wang, Hongzhi

    2013-11-01

    TiO2 microspheres assembled by single crystalline rutile TiO2 nanorods were synthesized by one-pot solvothermal treatment at 180 °C based on an aqueous-organic mixture solution containing n-hexane, distilled water, titanium n-butoxide and hydrochloric acid. The spheres had a radiative structure from the center, and their diameters were controlled in the range from 1 to 5 μm by adjusting the volume of the reactant water. Nitrogen adsorption-desorption isotherms showed that all the as-prepared microspheres had relatively high specific surface areas of about 50 m2 g-1. The 1 μm sized TiO2 nanorod microspheres were fabricated as a scattering overlayer in DSSCs, leading to a remarkable improvement in the power conversion efficiency: 8.22% of the bi-layer DSSCs versus 7.00% for the reference cell made of a single-layer film prepared from nanocrystalline TiO2. Such improvement was mainly attributed to the enhanced light harvesting and dye loading brought by the effective scattering centers.TiO2 microspheres assembled by single crystalline rutile TiO2 nanorods were synthesized by one-pot solvothermal treatment at 180 °C based on an aqueous-organic mixture solution containing n-hexane, distilled water, titanium n-butoxide and hydrochloric acid. The spheres had a radiative structure from the center, and their diameters were controlled in the range from 1 to 5 μm by adjusting the volume of the reactant water. Nitrogen adsorption-desorption isotherms showed that all the as-prepared microspheres had relatively high specific surface areas of about 50 m2 g-1. The 1 μm sized TiO2 nanorod microspheres were fabricated as a scattering overlayer in DSSCs, leading to a remarkable improvement in the power conversion efficiency: 8.22% of the bi-layer DSSCs versus 7.00% for the reference cell made of a single-layer film prepared from nanocrystalline TiO2. Such improvement was mainly attributed to the enhanced light harvesting and dye loading brought by the effective scattering

  20. Instability of Hydrogenated TiO2

    SciTech Connect

    Nandasiri, Manjula I.; Shutthanandan, V.; Manandhar, Sandeep; Schwarz, Ashleigh M.; Oxenford, Lucas S.; Kennedy, John V.; Thevuthasan, Suntharampillai; Henderson, Michael A.

    2015-11-06

    Hydrogenated TiO2 (H-TiO2) is toted as a viable visible light photocatalyst. We report a systematic study on the thermal stability of H-implanted TiO2 using X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), Rutherford backscattering spectrometry (RBS) and nuclear reaction analysis (NRA). Protons (40 keV) implanted at a ~2 atom % level within a ~120 nm wide profile of rutile TiO2(110) were situated ~300 nm below the surface. NRA revealed that this H-profile broadened preferentially toward the surface after annealing at 373 K, dissipated out of the crystal into vacuum at 473 K, and was absent within the beam sampling depth (~800 nm) at 523 K. Photoemission showed that the surface was reduced in concert with these changes. Similar anneals had no effect on pristine TiO2(110). The facile bulk diffusivity of H in rutile, as well as its activity toward interfacial reduction, significantly limits the utilization of H-TiO2 as a photocatalyst. This work was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle. The research was performed using the Environmental Molecular Sciences Laboratory (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. Electrochemical immobilization of Cs in single-crystalline SYNROC

    NASA Astrophysics Data System (ADS)

    Abe, Hideki; Satoh, Akira; Nishida, Kenji; Abe, Eiji; Naka, Takashi; Imai, Motoharu; Kitazawa, Hideaki

    2006-05-01

    The development of a disposal technique for the radiotoxic 137Cs in nuclear wastes is one of the most urgent issues in nuclear fuel technology. An effective disposal method of 137Cs is to immobilize it in a synthetic rock (SYNROC) material: cesium titanate hollandite, 137Cs xTi 8O 16 ( I4/ m, a=10.2866(3) Å, c=2.9669(1) Å). Practical applications of 137Cs xTi 8O 16 have been restricted so far because the conventional synthetic method requires strong chemical reducers and reaction temperatures higher than 1250 °C. In this report, we present a milder preparation method of Cs xTi 8O 16 by electrolysis of a mixture of Cs 2MoO 4 and TiO 2 in ambient atmosphere at 900 °C. The Cs content in the resultant single-crystalline Cs 1.35Ti 8O 16 is competitive with the highest value in polycrystalline Cs 1.36±0.03Ti 8O 16 prepared by the conventional synthetic method. The electrochemical preparation of Cs 1.35Ti 8O 16 is a promising way to immobilize a high quantity of 137Cs ions in a stable form of single-crystalline SYNROC.

  2. {116} faceted anatase single-crystalline nanosheet arrays: facile synthesis and enhanced electrochemical performances

    NASA Astrophysics Data System (ADS)

    Li, Feng; Li, Xiaoning; Peng, Ranran; Zhai, Xiaofang; Yang, Shangfeng; Fu, Zhengping; Lu, Yalin

    2014-10-01

    Single-crystalline anatase TiO2 nanosheet arrays were synthesized on a transparent conductive fluorine-doped tin oxide (FTO) substrate with a unique one-step alcohol-thermal process. The nanosheets were nearly vertically grown on the FTO substrate along their <11&cmb.macr;0> zone, and they were dominated by {116} facets. The as-fabricated {116} faceted single-crystalline anatase nanosheet arrays exhibit a much higher reduction capacity and a much better electrochemical reversibility than both {001} faceted anatase single-crystalline nanosheet arrays and P25 film. The results indicate a promising application potential for the new material in the photoelectrochemical field.Single-crystalline anatase TiO2 nanosheet arrays were synthesized on a transparent conductive fluorine-doped tin oxide (FTO) substrate with a unique one-step alcohol-thermal process. The nanosheets were nearly vertically grown on the FTO substrate along their <11&cmb.macr;0> zone, and they were dominated by {116} facets. The as-fabricated {116} faceted single-crystalline anatase nanosheet arrays exhibit a much higher reduction capacity and a much better electrochemical reversibility than both {001} faceted anatase single-crystalline nanosheet arrays and P25 film. The results indicate a promising application potential for the new material in the photoelectrochemical field. Electronic supplementary information (ESI) available: Photo of the large area STNA-116, FESEM images of STNA-001 and STNA-116 with a series of growth time, the enlarged XRD pattern, the simulated SAED pattern, the reflectance spectra, the cyclic voltammograms of P25 on the FTO substrate. See DOI: 10.1039/c4nr04248d

  3. A maskless synthesis of TiO2-nanofiber-based hierarchical structures for solid-state dye-sensitized solar cells with improved performance

    PubMed Central

    2014-01-01

    TiO2 hierarchical nanostructures with secondary growth have been successfully synthesized on electrospun nanofibers via surfactant-free hydrothermal route. The effect of hydrothermal reaction time on the secondary nanostructures has been studied. The synthesized nanostructures comprise electrospun nanofibers which are polycrystalline with anatase phase and have single crystalline, rutile TiO2 nanorod-like structures growing on them. These secondary nanostructures have a preferential growth direction [110]. UV–vis spectroscopy measurements point to better dye loading capability and incident photon to current conversion efficiency spectra show enhanced light harvesting of the synthesized hierarchical structures. Concomitantly, the dye molecules act as spacers between the conduction band electrons of TiO2 and holes in the hole transporting medium, i.e., spiro-OMeTAD and thus enhance open circuit voltage. The charge transport and recombination effects are characterized by electrochemical impedance spectroscopy measurements. As a result of improved light harvesting, dye loading, and reduced recombination losses, the hierarchical nanofibers yield 2.14% electrochemical conversion efficiency which is 50% higher than the efficiency obtained by plain nanofibers. PMID:24410851

  4. Remarkable Charge Separation and Photocatalytic Efficiency Enhancement through Interconnection of TiO2 Nanoparticles by Hydrothermal Treatment.

    PubMed

    Ide, Yusuke; Inami, Nozomu; Hattori, Hideya; Saito, Kanji; Sohmiya, Minoru; Tsunoji, Nao; Komaguchi, Kenji; Sano, Tsuneji; Bando, Yoshio; Golberg, Dmitri; Sugahara, Yoshiyuki

    2016-03-01

    Although tremendous effort has been directed to synthesizing advanced TiO2 , it remains difficult to obtain TiO2 exhibiting a photocatalytic efficiency higher than that of P25, a benchmark photocatalyst. P25 is composed of anatase, rutile, and amorphous TiO2 particles, and photoexcited electron transfer and subsequent charge separation at the anatase-rutile particle interfaces explain its high photocatalytic efficiency. Herein, we report on a facile and rational hydrothermal treatment of P25 to selectively convert the amorphous component into crystalline TiO2 , which is deposited between the original anatase and rutile particles to increase the particle interfaces and thus enhance charge separation. This process produces a new TiO2 exhibiting a considerably enhanced photocatalytic efficiency. This method of synthesizing this TiO2 , inspired by a recently burgeoning zeolite design, promises to make TiO2 applications more feasible and effective.

  5. Size-tunable TiO2 nanorod microspheres synthesised via a one-pot solvothermal method and used as the scattering layer for dye-sensitized solar cells.

    PubMed

    Rui, Yichuan; Li, Yaogang; Zhang, Qinghong; Wang, Hongzhi

    2013-12-21

    TiO2 microspheres assembled by single crystalline rutile TiO2 nanorods were synthesized by one-pot solvothermal treatment at 180 °C based on an aqueous-organic mixture solution containing n-hexane, distilled water, titanium n-butoxide and hydrochloric acid. The spheres had a radiative structure from the center, and their diameters were controlled in the range from 1 to 5 μm by adjusting the volume of the reactant water. Nitrogen adsorption-desorption isotherms showed that all the as-prepared microspheres had relatively high specific surface areas of about 50 m(2) g(-1). The 1 μm sized TiO2 nanorod microspheres were fabricated as a scattering overlayer in DSSCs, leading to a remarkable improvement in the power conversion efficiency: 8.22% of the bi-layer DSSCs versus 7.00% for the reference cell made of a single-layer film prepared from nanocrystalline TiO2. Such improvement was mainly attributed to the enhanced light harvesting and dye loading brought by the effective scattering centers.

  6. Acetaldehyde Photochemistry on TiO2(110)

    SciTech Connect

    Zehr, Robert T.; Henderson, Michael A.

    2008-07-01

    The ultraviolet (UV) photon induced decomposition of acetaldehyde adsorbed on the oxidized rutile TiO2(110) surface was studied with photon stimulated desorption (PSD) and thermal programmed desorption (TPD). Acetaldehyde desorbs molecularly from TiO2(110) with minor decomposition channels yielding butene on the reduced TiO2 surface and acetate on the oxidized TiO2 surface. Acetaldehyde adsorbed on oxidized TiO2(110) undergoes a facile thermal reaction to form a photoactive acetaldehyde-oxygen complex. UV irradiation of the acetaldehyde-oxygen complex initiated photofragmentation of the complex resulting in the ejection of methyl radical into gas phase and conversion of the surface bound fragment to formate.

  7. Effect of TiO2 blocking layer on TiO2 nanorod arrays based dye sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Sivakumar, R.; Paulraj, M.

    2016-05-01

    Highly ordered rutile titanium dioxide nanorod (TNR) arrays (1.2 to 6.2 μm thickness) were grown on TiO2 blocking layer chemically deposited on fluorine doped tin oxide (FTO) substrate and were used as photo-electrodes to fabricate dye sensitized solar cells (DSSC's). Homogeneous layer of TiO2 on FTO was achieved by using aqueous peroxo- titanium complex (PTC) solutions via chemical bath deposition. Structural and morphological properties of the prepared samples were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM) measurements. TNR arrays (6.2 μm) with TiO2 blocking layer showed higher energy conversion efficiency (1.46%) than that without TiO2 blocking layer. The reason can be ascertained to the suppression of electron-hole recombination at the semiconductor/electrolyte interface by the effect of TiO2 blocking layer.

  8. Dramatic activity of mixed-phase TiO2 photocatalyst synthesized by hydrothermal method

    NASA Astrophysics Data System (ADS)

    Li, Huiquan; Xu, Bolian; Fan, Yining

    2013-02-01

    The mixed-phase TiO2 photocatalysts with different anatase/rutile/brookite ratios and high specific surface area (157-218 m2/g) were prepared by hydrothermal method at 100 °C and the effect of rutile content in TiO2 on the BET surface area, light absorption and separation efficiency of photogenerated charge carriers was studied and correlated to the photocatalytic activity of TiO2. Rutile content increased from 0% to 100% by increasing the amount of TiCl4 in aqueous phase and the initial pH value of reaction solution played an important role in the phase composition of TiO2. The photocatalytic mechanism of mixed-phase TiO2 was discussed.

  9. Photocatalytic degradation of rhodamine B by anchored TiO2 nanowires.

    PubMed

    Wang, Chih-Chieh; Yu, Chung-Yi; Kei, Chi-Chung; Perng, Tsong-Pyng

    2011-01-01

    Rutile TiO2 nanowires anchored on silica were fabricated by annealing TiO2 nanoparticles dispersed on silicon or quartz substrate by means of a polystyrene nanosphere monolayer template at 1000 degrees C for 1 h without any catalyst. The diameter and length of the nanowires were 30-80 nm and 1-3 microm, respectively. The growth direction of the nanowires is [112]. The photocatalytic activities of TiO2 nanoparticles and anchored nanowires were evaluated. TiO2 nanowires had higher photocatalytic activity for rhodamine B than TiO2 nanoparticles.

  10. A comparative study of doped and un-doped sol-gel TiO2 and P25 TiO2 (photo)electrodes.

    PubMed

    Pooarporn, Y; Worayingyong, A; Wörner, M; Songsiriritthigul, P; Braun, A M

    2007-01-01

    Doped and undoped titanium dioxide films have been deposited on indium tin oxide glass using the sol-gel technique. The percentage of rutile in the prepared TiO2, calcined at 823 K and determined by X-ray diffraction, was 23% compared to 24% of rutile in P25-TiO2. Cerium doped TiO2 showed mainly the anatase phase, as characterised by both X-ray diffraction and Raman spectroscopy. The electrochemical and photoelectrochemical properties of the films were studied by cyclic voltammetry and electrochemical impedance spectroscopy. The (photo)electrochemical characteristics of the different films are reported and discussed.

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

    NASA Astrophysics Data System (ADS)

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

    2014-10-01

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

  12. Study of the interaction of formic acid, formaldehyde and formamide with the bulk terminated (1 × 1) and reconstructed (2 × 1) surfaces of rutile TiO2(011)

    NASA Astrophysics Data System (ADS)

    Muir, J. M. R.; Idriss, H.

    2013-01-01

    The nature of interactions of formaldehyde (HCHO), formamide (NH2CHO) and formic acid (HCOOH) is studied for the bulk terminated TiO2 (011) (1 × 1) surface and its most stable real surface structure the “brookite-like” (2 × 1) reconstruction; denoted (011)R. On the (011) (1 × 1) strong bridging adsorptions are seen for formic acid (1.71 eV) and formamide (1.57 eV) whereas the formaldehyde adsorbs in an η2 (C,O) structure (1.31 eV). On the (011)R there is a marked decrease in binding with only weak monodentate structures seen for formic acid (0.38, 0.27 eV) and formamide (0.44, 0.29 eV) and an η1 (O) adsorption seen for formaldehyde (0.23 eV). The reasons for this weak adsorption are examined. The arrangement of surface O atoms in the (011)R forces longer Tisbnd Oadsorbate bonds resulting in weak adsorption energy. Charge transfer to the surface is also reduced and in the case of bridging adsorptions the destabilising effect of the surface O atoms is considerable. The crystal field of the titanium surface atoms is examined and the (011) (1 × 1) Ti is found to have a higher proportion of states in the conduction band available to bind to the adsorbate when compared to their counterparts of the (011)R surface.

  13. Structural, Optical and Thermal Investigations of TiO2 and S-Doped TiO2 Nanoparticles

    NASA Astrophysics Data System (ADS)

    Bhatnagar, Divyanshu; Kumar, Ashavani

    2011-12-01

    Titanium dioxide (TiO2) and sulfur doped titanium dioxide (S-doped TiO2) nanoparticles are synthesized by Coprecipitation technique using titanium trichloride (TiCl3) as precursor, ammonium hydroxide (NH4OH) as solvent and sodium sulfite as source of sulfur. The X-ray diffraction (xrd) pattern reveals that TiO2 Nanoparticles are in anatase phase and anatase content decreases with increasing S-doping. The Differential Scanning Calorimetry (DSC) analysis elucidates the metastable anatase phase changes to stable rutile phase at 746 °C temperature. The UV/Vis study predicts larger band gap of TiO2 Nanoparticles as compare to bulk and blue shift with increasing S-doping.

  14. TiO2 (B) nanosheets mediate phase selective synthesis of TiO2 nanostructured photocatalyst

    NASA Astrophysics Data System (ADS)

    Wang, Yuxi; Wang, Changhua; Zhang, Xintong; Sun, Panpan; Kong, Lina; Wei, Yongan; Zheng, Han; Liu, Yichun

    2014-02-01

    Phase selective synthesis is particularly valuable in revealing performance of photocatalyst existing as several polymorphic phases. In this work, we develop a general soft chemical route that used a TiO2 (B) nanosheet as a precursor to synthesize TiO2 nanostructures of desired phase. Benefiting from the structural similarity and ultrathin thickness feature, TiO2 (B) nanosheet precursor can readily transform to pure phase of anatase, rutile and brookite as well as mixed phase of brookite/anatase. A possible dissolution-recrystallization mechanism is proposed for the phase transition of TiO2 (B) nanosheets to other phases. Photocatalytic activity tests demonstrated that the brookite/anatase mixture had the highest activity in degrading acetaldehyde under UV light irradiation, due to the synergistic effect of high crystallinity, large surface area and mixed phase structure.

  15. Pure single crystallographic form of TiO2 nanoparticles: Preparation and characterization

    NASA Astrophysics Data System (ADS)

    Bhatt, Piyush J.; Tomar, Laxmi J.; Desai, Rahul K.; Chakrabarty, Bishwajit S.

    2015-06-01

    TiO2 nanoparticles in three pure crystallographic forms (anatase, rutile and Brookite) have been prepared by hydrothermal and precipitation method. XRD analysis showed that the prepared nanoparticles using hydrothermal method for 2h and 24h were pure Brookite and pure anatase respectively. Pure rutile phase of TiO2 nanoparticles has been obtained by precipitation method. The average crystallite size for anatase, rutile and Brookite was found to be 14.71 nm, 12.88 nm and 5.27 nm respectively. This nano size of crystals has produced lattice strain in material, and this strain varies with size and structure. The UV-Visible absorption analysis showed that the energy gaps for anatase, rutile and Brookite are 3.32 eV, 2.45 eV and 2.60 eV respectively. Refractive index of all the samples has been changed compared to the bulk TiO2.

  16. Environment-friendly biomimetic synthesis of TiO2 nanomaterials for photocatalytic application

    NASA Astrophysics Data System (ADS)

    Bao, Shu-Juan; Lei, Chao; Xu, Mao-Wen; Cai, Chang-Jun; Jia, Dian-Zeng

    2012-05-01

    We have demonstrated an environment-friendly biomimetic synthesis method for the preparation of TiO2 nanomaterials with different crystal phases and morphologies. This is the first time that it has been found that the crystal phase of TiO2 can be controlled just by using different biotemplates, and cannot be changed by calcination up to 750 °C. In our experiment, anatase TiO2 was obtained by using yeast and albumen templates, while rutile TiO2 was formed by using dandelion pollen as the template.

  17. Nitrogen doped TiO2 nano-particles: Phase control by solution combustion method

    NASA Astrophysics Data System (ADS)

    Bapna, Komal; Choudhary, R. J.; Phase, D. M.; Shastri, Sheetal; Prasad, R.; Ahuja, B. L.

    2016-05-01

    N-doped TiO2 nano powders were prepared by sol-gel solution combustion method. The influence of different fuels (urea and citric acid) used in obtaining N-TiO2 nano particles in similar conditions (heat treatment, amount of precursors) has been investigated. The growth of different phases of TiO2 (anatase and rutile) is strongly affected by the ligands and the dehydration reaction. Reduction in the band gap of TiO2 and features observed in the XPS spectra confirm the incorporation of N into TiO2 matrix.

  18. A Single-Crystalline Mesoporous Quartz Superlattice.

    PubMed

    Matsuno, Takamichi; Kuroda, Yoshiyuki; Kitahara, Masaki; Shimojima, Atsushi; Wada, Hiroaki; Kuroda, Kazuyuki

    2016-05-10

    There has been significant interest in the crystallization of nanostructured silica into α-quartz because of its physicochemical properties. We demonstrate a single-crystalline mesoporous quartz superlattice, a silica polymorph with unprecedentedly ordered hierarchical structures on both the several tens of nanometers scale and the atomic one. The mesoporous quartz superlattice consists of periodically arranged α-quartz nanospheres whose crystalline axes are mostly oriented in an assembly. The superlattice is prepared by thermal crystallization of amorphous silica nanospheres constituting a colloidal crystal. We found that the deposition of a strong flux of Li(+) only on the surface of silica nanospheres is effective for crystallization.

  19. Controlled synthesis of single-crystalline graphene

    SciTech Connect

    Xueshen, Wang Jinjin, Li Qing, Zhong; Yuan, Zhong; Mengke, Zhao; Yonggang, Liu

    2014-03-15

    This paper reports the controlled synthesis of single-crystalline graphene on the back side of copper foil using CH{sub 4} as the precursor. The influence of growth time and the pressure ratio of CH{sub 4}/H{sub 2} on the structure of graphene are examined. An optimized polymer-assisted method is used to transfer the synthesized graphene onto a SiO{sub 2}/Si substrate. Scanning electron microscopy and Raman spectroscopy are used to characterize the graphene.

  20. Searching for new TiO2 crystal phases with better photoactivity

    NASA Astrophysics Data System (ADS)

    Shang, Cheng; Zhao, Wei-Na; Liu, Zhi-Pan

    2015-04-01

    Using the recently developed stochastic surface walking global optimization method, this work explores the potential energy surface of TiO2 crystals aiming to search for likely phases with higher photocatalytic activity. Five new phases of TiO2 are identified and the lowest energy phase transition pathways connecting to the most abundant phases (rutile and anatase) are determined. Theory shows that a high-pressure phase, α-PbO2-like form (TiO2II) acts as the key intermediate in between rutile and anatase. The phase transition of anatase to rutile belongs to the diffusionless Martensitic phase transition, occurring through a set of habit planes, rutile(101)//TiO2II(001), and TiO2II(100)//anatase(112). With regard to the photocatalytic activity, three pure phases (#110, pyrite and fluorite) are found to possess the band gap narrower than rutile, but they are unstable at the low-pressure condition. Instead, a mixed anatase-TiO2II phase is found to have good stability and narrower band gap than both parent phases. Because of the phase separation, the mixed phase is also expected to improve the photocatalytic performance by reducing the probability of the electron-hole pair recombination.

  1. Electronic and optical properties of TiO2 and its polymorphs by Z-scan method

    NASA Astrophysics Data System (ADS)

    Divya, S.; V, P. N. Nampoori; P, Radhakrishnan; A, Mujeeb

    2014-08-01

    TiO2 is a material which has attracted considerable attention from the scientific community for its innumerable properties. TiO2 is known to exist in nature in three different crystalline structures: rutile, anatase, and brookite. Anatase and rutile TiO2 films have been widely characterized for their potential applications in solar cells, self-cleaning coatings, and photocatalysis. In the present report, the third-order nonlinear susceptibilities of TiO2 and its polymorphs, anatase, and rutile, prepared by the sol—gel technique followed by heat treatment are investigated using the Z-scan technique at a wavelength of 532 nm with a duration of 7 ns. Imaginary and real values of χ(3) for amorphous, anatase, and rutile are also calculated and found to be 5 × 10-19 m2/V2, 27 × 10-19 m2/V2, 19 × 10-19 m2/V2, respectively. It is found that the values of the optical constants of amorphous TiO2 after heat treatment vary considerably. It is assumed that this could be due to the variation in the electronic structure of TiO2 synchronous with the formation of its polymorphs, anatase, and rutile. Amorphous TiO2 is marked by the localization of the tail states near the band gap, whereas its crystalline counterparts are characterized by completely delocalized tail states.

  2. BIOLOGICAL RESPONSE TO NANO-SCALE TIO2: ROLE OF PARTICLE DOSE, SHAPE AND RETENTION

    PubMed Central

    Silva, Rona M.; TeeSy, Christel; Franzi, Lisa; Weir, Alex; Westerhoff, Paul; Evans, James E.; Pinkerton, Kent E.

    2015-01-01

    TiO2 is one of the most widely used nanomaterials, valued for its highly refractive, photocatalytic and pigmenting properties. TiO2 is also classified by the International Agency for Research on Cancer (IARC) as a possible human carcinogen. The objectives of this study were to establish a lowest observed effect level (LOEL) for nano-scale TiO2, determine TiO2 uptake in the lungs, and estimate toxicity based on physico-chemical properties and retention in the lungs. In vivo lung toxicity of nano-scale TiO2 using varying forms of well-characterized, highly-dispersed TiO2 was assessed. Anatase/rutile P25 spheres (TiO2-P25), pure anatase spheres (TiO2-A), and anatase nanobelts (TiO2-NB) were tested. To determine the effects of dose and particle characteristics, male Sprague-Dawley rats were given TiO2 (0, 20, 70, or 200 µg) via intratracheal instillation. Broncho-alveolar lavage fluid (BALF) and lung tissue were obtained for analysis 1 and 7 days post exposure. Despite abundant TiO2 inclusions in all exposed animals, only TiO2-NB elicited any significant degree of inflammation seen in BALF at the 1-day time-point. This inflammation resolved by 7 days; although, TiO2 particles had not cleared from alveolar macrophages recovered from the lung. Histological examination showed TiO2-NB caused cellular changes at day 1 which were still evident at day 7. We conclude TiO2-NB is the most inflammatory with a lowest observable effect level of 200 µg at 1 day post instillation. PMID:24156719

  3. Heterostructured TiO2 Nanorod@Nanobowl Arrays for Efficient Photoelectrochemical Water Splitting.

    PubMed

    Wang, Wenhui; Dong, Jingya; Ye, Xiaozhou; Li, Yang; Ma, Yurong; Qi, Limin

    2016-03-01

    Heterostructured TiO2 nanorod@nanobowl (NR@NB) arrays consisting of rutile TiO2 nanorods grown on the inner surface of arrayed anatase TiO2 nanobowls are designed and fabricated as a new type of photoanodes for photoelectrochemical (PEC) water splitting. The unique heterostructures with a hierarchical architecture are readily fabricated by interfacial nanosphere lithography followed by hydrothermal growth. Owing to the two-dimensionally arrayed structure of anatase nanobowls and the nearly radial alignment of rutile nanorods, the TiO2 NR@NB arrays provide multiple scattering centers and hence exhibit an enhanced light harvesting ability. Meanwhile, the large surface area of the NR@NB arrays enhances the contact with the electrolyte while the nanorods offer direct pathways for fast electron transfer. Moreover, the rutile/anatase phase junction in the NR@NB heterostructure improves charge separation because of the facilitated electron transfer. Accordingly, the PEC measurements of the TiO2 NR@NB arrays on the fluoride-doped tin oxide (FTO) substrate show significantly enhanced photocatalytic properties for water splitting. Under AM1.5G solar light irradiation, the unmodified TiO2 NR@NB array photoelectrode yields a photocurrent density of 1.24 mA cm(-2) at 1.23 V with respect to the reversible hydrogen electrode, which is almost two times higher than that of the TiO2 nanorods grown directly on the FTO substrate. PMID:26779803

  4. Heterostructured TiO2 Nanorod@Nanobowl Arrays for Efficient Photoelectrochemical Water Splitting.

    PubMed

    Wang, Wenhui; Dong, Jingya; Ye, Xiaozhou; Li, Yang; Ma, Yurong; Qi, Limin

    2016-03-01

    Heterostructured TiO2 nanorod@nanobowl (NR@NB) arrays consisting of rutile TiO2 nanorods grown on the inner surface of arrayed anatase TiO2 nanobowls are designed and fabricated as a new type of photoanodes for photoelectrochemical (PEC) water splitting. The unique heterostructures with a hierarchical architecture are readily fabricated by interfacial nanosphere lithography followed by hydrothermal growth. Owing to the two-dimensionally arrayed structure of anatase nanobowls and the nearly radial alignment of rutile nanorods, the TiO2 NR@NB arrays provide multiple scattering centers and hence exhibit an enhanced light harvesting ability. Meanwhile, the large surface area of the NR@NB arrays enhances the contact with the electrolyte while the nanorods offer direct pathways for fast electron transfer. Moreover, the rutile/anatase phase junction in the NR@NB heterostructure improves charge separation because of the facilitated electron transfer. Accordingly, the PEC measurements of the TiO2 NR@NB arrays on the fluoride-doped tin oxide (FTO) substrate show significantly enhanced photocatalytic properties for water splitting. Under AM1.5G solar light irradiation, the unmodified TiO2 NR@NB array photoelectrode yields a photocurrent density of 1.24 mA cm(-2) at 1.23 V with respect to the reversible hydrogen electrode, which is almost two times higher than that of the TiO2 nanorods grown directly on the FTO substrate.

  5. Photocatalytic activity of TiO2 nanomaterials for methylene blue dye degradation

    NASA Astrophysics Data System (ADS)

    Lee, Deuk Yong; Son, Siwon; Jeon, Min-Seok; Lee, Myung-Hyun; Kim, Bae-Yeon

    2016-04-01

    TiO2 nanomaterials were prepared by a sol-gel derived electrospinning, calcination from 500°C to 650°C, and subsequent mechanical grinding to investigate the effect of calcination temperature on crystal structure, crystallinity, and photocatalytic activity of methylene blue (MB). XRD results indicated that TiO2 nanorods calcined at 500°C is composed of anatase TiO2 only. However, mixed crystals of anatase and rutile were observed for TiO2 calcined above 550°C. Higher MB degradation was found for the TiO2 nanorods calcined at 550°C probably due to the mixed crystals and larger surface area. However, the improved photocatalytic activity was achieved for TiO2 nanotube due to the synergic combinations of mixed crystals, larger specific surface area, and light trapping effect.

  6. Directed synthesis of hierarchical nanostructured TiO2 catalysts and their morphology-dependent photocatalysis for phenol degradation.

    PubMed

    Liu, Lu; Liu, Huajie; Zhao, Ya-Ping; Wang, Yuqiu; Duan, Yueqin; Gao, Guandao; Ge, Ming; Chen, Wei

    2008-04-01

    Nanostructured TiO2 with different hierarchical morphologies were synthesized via a warmly hydrothermal route. The properties of the products were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, N2 adsorption, UV-vis spectroscopy, etc. Two of the products, TiO2 1D nanorods (one-dimensional rutile TiO2 nanorods) and TiO2 3D0D microspheres (three-dimensional anatase TiO2 nanoparticle-assembled microspheres) exhibited superior photocatalytic effects on phenol degradation under UV illumination, compared with TiO2 3D1D microspheres (three-dimensional rutile TiO2 nanorods-assembled microspheres). Moreover, TiO2 3D0D was superior to TiO2 1D, as indicated by a 30% higher mineralization of dissolved phenol. Dihydroxybenze, 4,4'-dihydroxybiphenyl, benzoquinone, maleic anhydride, etc. were identified as the degradation intermediates. The excellent catalytic effect was attributed to the structural features of TiO2 1D nanorods and TiO2 3D0D microspheres, that is, a larger amount of surface active sites and a higher band gap energy resulted in more efficient decomposition of organic contaminants. PMID:18504963

  7. Directed synthesis of hierarchical nanostructured TiO2 catalysts and their morphology-dependent photocatalysis for phenol degradation.

    PubMed

    Liu, Lu; Liu, Huajie; Zhao, Ya-Ping; Wang, Yuqiu; Duan, Yueqin; Gao, Guandao; Ge, Ming; Chen, Wei

    2008-04-01

    Nanostructured TiO2 with different hierarchical morphologies were synthesized via a warmly hydrothermal route. The properties of the products were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, N2 adsorption, UV-vis spectroscopy, etc. Two of the products, TiO2 1D nanorods (one-dimensional rutile TiO2 nanorods) and TiO2 3D0D microspheres (three-dimensional anatase TiO2 nanoparticle-assembled microspheres) exhibited superior photocatalytic effects on phenol degradation under UV illumination, compared with TiO2 3D1D microspheres (three-dimensional rutile TiO2 nanorods-assembled microspheres). Moreover, TiO2 3D0D was superior to TiO2 1D, as indicated by a 30% higher mineralization of dissolved phenol. Dihydroxybenze, 4,4'-dihydroxybiphenyl, benzoquinone, maleic anhydride, etc. were identified as the degradation intermediates. The excellent catalytic effect was attributed to the structural features of TiO2 1D nanorods and TiO2 3D0D microspheres, that is, a larger amount of surface active sites and a higher band gap energy resulted in more efficient decomposition of organic contaminants.

  8. Hierarchical Oriented Anatase TiO2 Nanostructure arrays on Flexible Substrate for Efficient Dye-sensitized Solar Cells

    PubMed Central

    Wu, Wu-Qiang; Rao, Hua-Shang; Xu, Yang-Fan; Wang, Yu-Fen; Su, Cheng-Yong; Kuang, Dai-Bin

    2013-01-01

    The vertically oriented anatase single crystalline TiO2 nanostructure arrays (TNAs) consisting of TiO2 truncated octahedrons with exposed {001} facets or hierarchical TiO2 nanotubes (HNTs) consisting of numerous nanocrystals on Ti-foil substrate were synthesized via a two-step hydrothermal growth process. The first step hydrothermal reaction of Ti foil and NaOH leads to the formation of H-titanate nanowire arrays, which is further performed the second step hydrothermal reaction to obtain the oriented anatase single crystalline TiO2 nanostructures such as TiO2 nanoarrays assembly with truncated octahedral TiO2 nanocrystals in the presence of NH4F aqueous or hierarchical TiO2 nanotubes with walls made of nanocrystals in the presence of pure water. Subsequently, these TiO2 nanostructures were utilized to produce dye-sensitized solar cells in a backside illumination pattern, yielding a significant high power conversion efficiency (PCE) of 4.66% (TNAs, JSC = 7.46 mA cm−2, VOC = 839 mV, FF = 0.75) and 5.84% (HNTs, JSC = 10.02 mA cm−2, VOC = 817 mV, FF = 0.72), respectively. PMID:23715529

  9. Photocatalytic antibacterial performance of TiO2 and Ag-doped TiO2 against S. aureus. P. aeruginosa and E. coli.

    PubMed

    Gupta, Kiran; Singh, R P; Pandey, Ashutosh; Pandey, Anjana

    2013-01-01

    This paper reports the structural and optical properties and comparative photocatalytic activity of TiO2 and Ag-doped TiO2 nanoparticles against different bacterial strains under visible-light irradiation. The TiO2 and Ag-doped TiO2 photocatalysts were synthesized by acid catalyzed sol-gel technique and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), UV-vis spectroscopy and photoluminescence (PL). The XRD pattern revealed that the annealed sample of TiO2 has both anatase and rutile phases while only an anatase phase was found in Ag-doped TiO2 nanoparticles. The decreased band-gap energy of Ag-doped TiO2 nanoparticles in comparison to TiO2 nanoparticles was investigated by UV-vis spectroscopy. The rate of recombination and transfer behaviour of the photoexcited electron-hole pairs in the semiconductors was recorded by photoluminescence. The antimicrobial activity of TiO2 and Ag-doped TiO2 nanoparticles (3% and 7%) was investigated against both gram positive (Staphylococcus aureus) and gram negative (Pseudomonas aeruginosa, Escherichia coli) bacteria. As a result, the viability of all three microorganisms was reduced to zero at 60 mg/30 mL culture in the case of both (3% and 7% doping) concentrations of Ag-doped TiO2 nanoparticles. Annealed TiO2 showed zero viability at 80 mg/30 mL whereas doped Ag-TiO2 7% showed zero viability at 40 mg/30 mL culture in the case of P. aeruginosa only.

  10. Photocatalytic Properties of TiO2 Porous Network Film.

    PubMed

    Yu, Lianqing; Zhi, Qianqian; Huang, Chengxing; Zhang, Yaping; Dong, Kaituo; Neppolian, B

    2015-09-01

    Three-dimensional porous network TiO2 film (PW-film) and nanoparticles film were synthesized on surface of the Ti foil by a facile method to investigate both the photoelectrochemical and photocatalytic properties. The prepared samples were characterized by scanning electron microscopy (SEM), transmission electron microscope (TEM) and X-ray diffraction spectroscopy (XRD) techniques. Methylene blue was used as a target molecule to estimate the photocatalytic activity of the films. Results revealed that the hydrothermal temperature and time have great influence on the crystal type and film morphology of TiO2 catalysts. A higher hydrothermal temperature is benefit for the formation of anatase phase of TiO2 nanotubes with PW-film, which had a large number of nodes. After investigation of the photoelectrochemical properties, a maximum photoconversion efficiency of 4.79% is observed for nanoparticles film with rutile phase of TiO2 under UV light illumination, which was incredible 2 times higher than that of the PW-film with anatase phase. It was shown that the morphology of TiO2 film contributes more significant effect on photocatalytic and photoelectric performance than its crystal type. PMID:26716214

  11. Photocatalytic Properties of TiO2 Porous Network Film.

    PubMed

    Yu, Lianqing; Zhi, Qianqian; Huang, Chengxing; Zhang, Yaping; Dong, Kaituo; Neppolian, B

    2015-09-01

    Three-dimensional porous network TiO2 film (PW-film) and nanoparticles film were synthesized on surface of the Ti foil by a facile method to investigate both the photoelectrochemical and photocatalytic properties. The prepared samples were characterized by scanning electron microscopy (SEM), transmission electron microscope (TEM) and X-ray diffraction spectroscopy (XRD) techniques. Methylene blue was used as a target molecule to estimate the photocatalytic activity of the films. Results revealed that the hydrothermal temperature and time have great influence on the crystal type and film morphology of TiO2 catalysts. A higher hydrothermal temperature is benefit for the formation of anatase phase of TiO2 nanotubes with PW-film, which had a large number of nodes. After investigation of the photoelectrochemical properties, a maximum photoconversion efficiency of 4.79% is observed for nanoparticles film with rutile phase of TiO2 under UV light illumination, which was incredible 2 times higher than that of the PW-film with anatase phase. It was shown that the morphology of TiO2 film contributes more significant effect on photocatalytic and photoelectric performance than its crystal type.

  12. Does photocatalytic activity of TiO2 nanoparticles correspond to photo-cytotoxicity? Cellular uptake of TiO2 nanoparticles is important in their photo-cytotoxicity.

    PubMed

    Horie, Masanori; Sugino, Sakiko; Kato, Haruhisa; Tabei, Yosuke; Nakamura, Ayako; Yoshida, Yasukazu

    2016-05-01

    Titanium dioxide (TiO2) nanoparticles are important industrial nano-objects with wide applications, including as photocatalysts and sunscreen components. Recently, the phototoxicity of TiO2 nanoparticles has been a concern. However, phototoxicity caused by photocatalytic activity may differ between anatase and rutile nanoparticles. In the present study, we compared the phototoxicity of anatase and rutile nanoparticles. Human keratinocyte HaCaT cells were treated with stable TiO2 nanoparticle suspensions. Without UVA irradiation, TiO2 nanoparticles did not affect mitochondrial activity or cell membranes. However, exposure to rutile nanoparticle suspensions inhibited cell growth and induced HO-1 gene expression without UVA irradiation. These effects may be explained by the hydrophobic surface of rutile nanoparticles. Next, TiO2-exposed cells were irradiated with UVA for 4 h and effects of TiO2 nanoparticles on cells were examined. The rutile nanoparticles did not show any cellular effects after UVA irradiation. However, the anatase nanoparticles caused strong phototoxicity. Decreased mitochondrial activity, cell membrane damage and the induction of oxidative stress were observed in the cells exposed to anatase nanoparticles with UVA irradiation. Cellular uptake of the nanoparticles was observed in both anatase- and rutile-exposed cells. These results suggest that internalized anatase nanoparticles are important for phototoxicity. Additionally, the exposure of a 3D skin model to TiO2 nanoparticles did not result in significant toxicity. In conclusion, rutile nanoparticles used in sunscreen did not exhibit phototoxic activity. Despite the strong phototoxic activity of anatase nanoparticles in cell cultures, they demonstrated no phototoxicity using a 3D skin model. PMID:27142467

  13. Modification of dense TiO2 particles using polyethylene glycol template: Synthesis, characterization, and photocatalytic activity

    NASA Astrophysics Data System (ADS)

    Dostanić, J.; Lončarević, D.; Radosavljević-Mihajlović, A.; Jovanović, D. M.

    2015-12-01

    In this study, an effort has been made to prepare TiO2 materials by sol-gel technique using polyethylene glycol (PEG) as pore directing agent. Different PEG amounts were used during samples preparation in order to investigate the change in intrinsic material properties. The photocatalytic activity of prepared catalysts was estimated by measuring the decomposition of arylazo pyridone dye. The optimum template amount was determined, resulting in catalyst with enhanced textural properties, optimal anatase/rutile ratio and hence improved photocatalytic properties. Specific surface area and anatase/rutile ratio were found to be the main contributing factors to the catalyst activity. A synergistic effect between anatase and rutile TiO2 has been observed, since the presence of relatively inactive rutile phase enhanced the photoactivity of mixed TiO2.

  14. Preparation of TiO2 Nanocrystallite Powders Coated with 9 mol% ZnO for Cosmetic Applications in Sunscreens

    PubMed Central

    Ko, Horng-Huey; Chen, Hui-Ting; Yen, Feng-Ling; Lu, Wan-Chen; Kuo, Chih-Wei; Wang, Moo-Chin

    2012-01-01

    The preparation of TiO2 nanocrystallite powders coated with and without 9 mol% ZnO has been studied for cosmetic applications in sunscreens by a co-precipitation process using TiCl4 and Zn(NO3)2·6H2O as starting materials. XRD results show that the phases of anatase TiO2 and rutile TiO2 coexist for precursor powders without added ZnO (T-0Z) and calcined at 523 to 973 K for 2 h. When the T-0Z precursor powders are calcined at 1273 K for 2 h, only the rutile TiO2 appears. In addition, when the TiO2 precursor powders contain 9 mol% ZnO (T-9Z) are calcined at 873 to 973 K for 2 h, the crystallized samples are composed of the major phase of rutile TiO2 and the minor phases of anatase TiO2 and Zn2Ti3O8. The analyses of UV/VIS/NIR spectra reveal that the absorption of the T-9Z precursor powders after being calcined has a red-shift effect in the UV range with increasing calcination temperature. Therefore, the TiO2 nanocrystallite powders coated with 9 mol% ZnO can be used as the attenuate agent in the UV-A region for cosmetic applications in sunscreens. PMID:22408415

  15. A simple hydrothermal preparation of TiO 2 nanomaterials using concentrated hydrochloric acid

    NASA Astrophysics Data System (ADS)

    Nguyen Phan, Thuy-Duong; Pham, Hai-Dinh; Viet Cuong, Tran; Jung Kim, Eui; Kim, Sunwook; Woo Shin, Eun

    2009-12-01

    A TiO 2 nanostructure was synthesized via a simple method using only concentrated hydrochloric acid as the morphological/crystallographic controlling agent. Microscopy images showed that the texture of the TiO 2 powder could be easily engineered and tuned by tailoring the HCl volume, creating cuboid, flower, cauliflower, and ball-shaped particles. Three-dimensional TiO 2 microparticles resulted from the self-assembly of nanostructured sub-units including nanocubes, nanoprisms, and nanorods. The crystalline anatase and rutile phases were also identified depending on the acidic medium. HCl played a key role in orchestrating the structures and morphologies of the TiO 2 nanoscale materials. The phase transformation and morphological changes were strongly related to the crystal growth mechanism of the TiO 2 nanostructure.

  16. Enhanced photocatalytic activity in anodized WO3-loaded TiO2 nanotubes

    NASA Astrophysics Data System (ADS)

    Nazari, M.; Golestani-Fard, F.; Bayati, R.; Eftekhari-Yekta, B.

    2015-04-01

    In this work, TiO2 and WO3-grafted TiO2 nanotubes were grown via anodizing of titanium substrates in tungstate containing electrolytes. The samples were characterized in detail by XRD, XPS, SEM, EDX, and UV-Vis spectrophotometry techniques. Besides, photocatalytic characteristics were evaluated through measuring the degradation rate of 4-chlorophenol to establish a correlation between structure and photochemical properties. We were able to control morphology and growth mode of nanotubes from a tubular to a worm-like structure by changing the electrolyte composition. The samples possessed an anatase-rutile matrix where the anatase/rutile ratio was found to increase with the concentration of tungstate in the electrolyte. We attributed this observation to change in electrical conductivity of the electrolyte and the heat generated on the substrates. It was unambiguously revealed that a composite of WO3 and TiO2 forms and, in parallel, tungsten is doped into the crystalline lattice of TiO2. The maximum photocatalytic reaction rate constant for TiO2 and WO3-TiO2 samples was determined to be 0.0131 and 0.0174 min-1 respectively. The grafting TiO2 nanotubes with WO3 enhances the photocatalytic activity mainly due to the hindrance of charge carrier recombination and the formation of a more acidic surface. We established a correlation between structure, stoichiometry, and photocatalytic characteristics of nanotubes.

  17. A comparative study of TiO2 nanoparticles synthesized in premixed and diffusion flames

    NASA Astrophysics Data System (ADS)

    Ma, Hsiao-Kang; Yang, Hsiung-An

    2010-12-01

    Previous studies have been shown that synthesis of titania (TiO2) crystalline phase purity could be effectively controlled by the oxygen concentration through titanium tetra-isopropoxide (TTIP) via premixed flame from a Bunsen burner. In this study, a modified Hencken burner was used to synthesize smaller TiO2 nanoparticles via short diffusion flames. The frequency of collisions among particles would decrease and reduce TiO2 nanoparticle size in a short diffusion flame height. The crystalline structure of the synthesized nanoparticles was characterized by X-ray diffraction (XRD), transmission electron microscope (TEM), Barrett-Joyner-Halenda (BJH) and Brunauer-Emmett-Teller (BET) measurements. The characteristic properties of TiO2 nanoparticles synthesized from a modified Hencken burner were compared with the results from a Bunsen burner and commercial TiO2 (Degussa P25). The results showed that the average particle size of 6.63 nm from BET method was produced by a modified Hencken burner which was smaller than the TiO2 in a Bunsen burner and commercial TiO2. Moreover, the rutile content of TiO2 nanoparticles increased as the particle collecting height increased. Also, the size of TiO2 nanoparticles was highly dependent on the TTIP loading and the collecting height in the flame.

  18. Improvement of solar energy conversion with Nb-incorporated TiO2 hierarchical microspheres.

    PubMed

    Hoang, Son; Ngo, Thong Q; Berglund, Sean P; Fullon, Raymond R; Ekerdt, John G; Mullins, C Buddie

    2013-07-22

    Niobium-modified TiO2 hierarchical spherical micrometer-size particles, which consist of many nanowires, are synthesized by solvothermal synthesis and studied as photoelectrodes for water photo-oxidation and dye-sensitized solar cell (DSSC) applications. Incorporation of Nb leads to a rutile-to-anatase TiO2 phase transition in the TiO2 hierarchical spheres (HSs), with the anatase percentage increasing from 0% for the pristine TiO2 HSs to 47.6% for the 1.82 at.% Nb-incorporated TiO2 sample. Incorporation of Nb leads to significant improvements in water photo-oxidation with the photocurrents reaching 70.5 μA cm(-2) at 1.23 V versus the reversible hydrogen electrode, compared with 28.3 μA cm(-2) for the pristine TiO2 sample. The photoconversion efficiency of Nb:TiO2 HS-based DSSCs reaches 6.09±0.15% at 0.25 at.% Nb, significantly higher than that for the pristine TiO2 HS cells (3.99±0.02%). In addition, the incident-photon-to-current efficiency spectra for DSSCs show that employing TiO2 and Nb:TiO2 HSs provides better light harvesting, especially of long-wavelength photons, than anatase TiO2 nanoparticle-based DSSCs. PMID:23512241

  19. Controllable Synthesis and Tunable Photocatalytic Properties of Ti3+-doped TiO2

    PubMed Central

    Ren, Ren; Wen, Zhenhai; Cui, Shumao; Hou, Yang; Guo, Xiaoru; Chen, Junhong

    2015-01-01

    Photocatalysts show great potential in environmental remediation and water splitting using either artificial or natural light. Titanium dioxide (TiO2)-based photocatalysts are studied most frequently because they are stable, non-toxic, readily available, and highly efficient. However, the relatively wide band gap of TiO2 significantly limits its use under visible light or solar light. We herein report a facile route for controllable synthesis of Ti3+-doped TiO2 with tunable photocatalytic properties using a hydrothermal method with varying amounts of reductant, i.e., sodium borohydride (NaBH4). The resulting TiO2 showed color changes from light yellow, light grey, to dark grey with the increasing amount of NaBH4. The present method can controllably and effectively reduce Ti4+ on the surface of TiO2 and induce partial transformation of anatase TiO2 to rutile TiO2, with the evolution of nanoparticles into hierarchical structures attributable to a high pressure and strong alkali environment in the synthesis atmosphere; in this way, the photocatalytic activity of Ti3+-doped TiO2 under visible-light can be tuned. The as-developed strategy may open up a new avenue for designing and functionalizing TiO2 materials for enhancing visible light absorption, narrowing band gap, and improving photocatalytic activity. PMID:26044406

  20. Controllable Synthesis and Tunable Photocatalytic Properties of Ti(3+)-doped TiO2.

    PubMed

    Ren, Ren; Wen, Zhenhai; Cui, Shumao; Hou, Yang; Guo, Xiaoru; Chen, Junhong

    2015-06-05

    Photocatalysts show great potential in environmental remediation and water splitting using either artificial or natural light. Titanium dioxide (TiO2)-based photocatalysts are studied most frequently because they are stable, non-toxic, readily available, and highly efficient. However, the relatively wide band gap of TiO2 significantly limits its use under visible light or solar light. We herein report a facile route for controllable synthesis of Ti(3+)-doped TiO2 with tunable photocatalytic properties using a hydrothermal method with varying amounts of reductant, i.e., sodium borohydride (NaBH4). The resulting TiO2 showed color changes from light yellow, light grey, to dark grey with the increasing amount of NaBH4. The present method can controllably and effectively reduce Ti(4+) on the surface of TiO2 and induce partial transformation of anatase TiO2 to rutile TiO2, with the evolution of nanoparticles into hierarchical structures attributable to a high pressure and strong alkali environment in the synthesis atmosphere; in this way, the photocatalytic activity of Ti(3+)-doped TiO2 under visible-light can be tuned. The as-developed strategy may open up a new avenue for designing and functionalizing TiO2 materials for enhancing visible light absorption, narrowing band gap, and improving photocatalytic activity.

  1. Near-infrared electroluminescence from light-emitting devices based on Nd-doped TiO2/p+-Si heterostructures

    NASA Astrophysics Data System (ADS)

    Yang, Yang; Lv, Chunyan; Zhu, Chen; Li, Si; Ma, Xiangyang; Yang, Deren

    2014-05-01

    We report on near-infrared (NIR) electroluminescence (EL) from the light-emitting devices based on Nd-doped TiO2/p+-Si heterostructures. NIR emissions peaking at ˜910, 1090, and 1370 nm, originated from intra-4f transitions in Nd3+ ions, can be activated by a forward bias voltage as low as ˜5 V. Such NIR EL is triggered by the energy transferred from TiO2 host to Nd3+ ions. It is found that the coexistence of anatase and rutile phases in the TiO2 host enables the device to exhibit pronounced Nd-related EL without concurrent emission from the TiO2 host itself, quite other than the case of existing only anatase phase in TiO2 host. We tentatively suggest that the anatase/rutile interface states play important role in the energy transfer from TiO2 host to Nd3+ ions.

  2. Photocatalytical Antibacterial Activity of Mixed-Phase TiO2 Nanocomposite Thin Films against Aggregatibacter actinomycetemcomitans.

    PubMed

    Yeniyol, Sinem; Mutlu, Ilven; He, Zhiming; Yüksel, Behiye; Boylan, Robert Joseph; Ürgen, Mustafa; Karabuda, Zihni Cüneyt; Basegmez, Cansu; Ricci, John Lawrence

    2015-01-01

    Mixed-phase TiO2 nanocomposite thin films consisting of anatase and rutile prepared on commercially pure Ti sheets via the electrochemical anodization and annealing treatments were investigated in terms of their photocatalytic activity for antibacterial use around dental implants. The resulting films were characterized by scanning electron microscopy (SEM), and X-ray diffraction (XRD). The topology was assessed by White Light Optical Profiling (WLOP) in the Vertical Scanning Interferometer (VSI) mode. Representative height descriptive parameters of roughness R a and R z were calculated. The photocatalytic activity of the resulting TiO2 films was evaluated by the photodegradation of Rhodamine B (RhB) dye solution. The antibacterial ability of the photocatalyst was examined by Aggregatibacter actinomycetemcomitans suspensions in a colony-forming assay. XRD showed that anatase/rutile mixed-phase TiO2 thin films were predominantly in anatase and rutile that were 54.6 wt% and 41.9 wt%, respectively. Craters (2-5 µm) and protruding hills (10-50 µm) on Ti substrates were produced after electrochemical anodization with higher R a and R z surface roughness values. Anatase/rutile mixed-phase TiO2 thin films showed 26% photocatalytic decolorization toward RhB dye solution. The number of colonizing bacteria on anatase/rutile mixed-phase TiO2 thin films was decreased significantly in vitro. The photocatalyst was effective against A. actinomycetemcomitans colonization. PMID:26576430

  3. Photocatalytical Antibacterial Activity of Mixed-Phase TiO2 Nanocomposite Thin Films against Aggregatibacter actinomycetemcomitans

    PubMed Central

    Yeniyol, Sinem; Mutlu, Ilven; He, Zhiming; Yüksel, Behiye; Boylan, Robert Joseph; Ürgen, Mustafa; Karabuda, Zihni Cüneyt; Basegmez, Cansu; Ricci, John Lawrence

    2015-01-01

    Mixed-phase TiO2 nanocomposite thin films consisting of anatase and rutile prepared on commercially pure Ti sheets via the electrochemical anodization and annealing treatments were investigated in terms of their photocatalytic activity for antibacterial use around dental implants. The resulting films were characterized by scanning electron microscopy (SEM), and X-ray diffraction (XRD). The topology was assessed by White Light Optical Profiling (WLOP) in the Vertical Scanning Interferometer (VSI) mode. Representative height descriptive parameters of roughness Ra and Rz were calculated. The photocatalytic activity of the resulting TiO2 films was evaluated by the photodegradation of Rhodamine B (RhB) dye solution. The antibacterial ability of the photocatalyst was examined by  Aggregatibacter actinomycetemcomitans suspensions in a colony-forming assay. XRD showed that anatase/rutile mixed-phase TiO2 thin films were predominantly in anatase and rutile that were 54.6 wt% and 41.9 wt%, respectively. Craters (2–5 µm) and protruding hills (10–50 µm) on Ti substrates were produced after electrochemical anodization with higher Ra and Rz surface roughness values. Anatase/rutile mixed-phase TiO2 thin films showed 26% photocatalytic decolorization toward RhB dye solution. The number of colonizing bacteria on anatase/rutile mixed-phase TiO2 thin films was decreased significantly in vitro. The photocatalyst was effective against A. actinomycetemcomitans colonization. PMID:26576430

  4. Vapor-phase hydrothermal transformation of HTiOF3 intermediates into {001} faceted anatase single-crystalline nanosheets.

    PubMed

    Liu, Porun; Wang, Yun; Zhang, Haimin; An, Taicheng; Yang, Huagui; Tang, Zhiyong; Cai, Weiping; Zhao, Huijun

    2012-12-01

    For the first time, a facile, one-pot hydrofluoric acid vapor-phase hydrothermal (HF-VPH) method is demonstrated to directly grow single-crystalline anatase TiO(2) nanosheets with 98.2% of exposed {001} faceted surfaces on the Ti substrate via a distinctive two-stage formation mechanism. The first stage produces a new intermediate crystal (orthorhombic HTiOF(3) ) that is transformed into anatase TiO(2) nanosheets during the second stage. The findings reveal that the HF-VPH reaction environment is unique and differs remarkably from that of liquid-phase hydrothermal processes. The uniqueness of the HF-VPH conditions can be readily used to effectively control the nanostructure growth. PMID:22903795

  5. Photocatalytic performance of nitrogen, osmium co-doped TiO2 for removal of eosin yellow in water under simulated solar radiation.

    PubMed

    Kuvarega, Alex T; Krause, Rui W M; Mamba, Bhekie B

    2013-07-01

    Nitrogen, osmium co-doped TiO2 photocatalysts were prepared by a modified sol-gel method using ammonia as the nitrogen source and osmium tetroxide as the source of osmium. The role of rutile phase OsO2 in enhancing the photocatalytic activity of rutile TiO2 towards the degradation of Eosin Yellow was investigated. The materials were characterised by various techniques that include FTIR, Raman, XRD, SEM, EDS, TEM, TGA and DRUV-Vis. The amorphous, oven dried sample was transformed to the anatase and then the rutile phase with increasing calcination temperature. DRUV-Vis analysis revealed a red shift in absorption with increasing calcination temperature, confirmed by a decrease in the band gap of the material. The photocatalytic activity of N, Os co-doped TiO2 was evaluated using eosin yellow degradation and activity increased with increase in calcination temperature under simulated solar irradiation. The rutile phase of the co-doped TiO2 was found to be more effective in degrading the dye (k(a) = 1.84 x 10(-2) min(-1)) compared to the anatase co-doped phase (k(a) = 9.90 x 10(-3) min(-1)). The enhanced photocatalytic activity was ascribed to the synergistic effects of rutile TiO2 and rutile OsO2 in the N, Os co-doped TiO2. PMID:23901525

  6. Photocatalytic performance of nitrogen, osmium co-doped TiO2 for removal of eosin yellow in water under simulated solar radiation.

    PubMed

    Kuvarega, Alex T; Krause, Rui W M; Mamba, Bhekie B

    2013-07-01

    Nitrogen, osmium co-doped TiO2 photocatalysts were prepared by a modified sol-gel method using ammonia as the nitrogen source and osmium tetroxide as the source of osmium. The role of rutile phase OsO2 in enhancing the photocatalytic activity of rutile TiO2 towards the degradation of Eosin Yellow was investigated. The materials were characterised by various techniques that include FTIR, Raman, XRD, SEM, EDS, TEM, TGA and DRUV-Vis. The amorphous, oven dried sample was transformed to the anatase and then the rutile phase with increasing calcination temperature. DRUV-Vis analysis revealed a red shift in absorption with increasing calcination temperature, confirmed by a decrease in the band gap of the material. The photocatalytic activity of N, Os co-doped TiO2 was evaluated using eosin yellow degradation and activity increased with increase in calcination temperature under simulated solar irradiation. The rutile phase of the co-doped TiO2 was found to be more effective in degrading the dye (k(a) = 1.84 x 10(-2) min(-1)) compared to the anatase co-doped phase (k(a) = 9.90 x 10(-3) min(-1)). The enhanced photocatalytic activity was ascribed to the synergistic effects of rutile TiO2 and rutile OsO2 in the N, Os co-doped TiO2.

  7. Solar-light photocatalytic disinfection using crystalline/amorphous low energy bandgap reduced TiO2

    NASA Astrophysics Data System (ADS)

    Kim, Youngmin; Hwang, Hee Min; Wang, Luyang; Kim, Ikjoon; Yoon, Yeoheung; Lee, Hyoyoung

    2016-04-01

    A generation of reactive oxygen species (ROS) from TiO2 under solar light has been long sought since the ROS can disinfect organic pollutants. We found that newly developed crystalline/amorphous reduced TiO2 (rTiO2) that has low energy bandgap can effectively generate ROS under solar light and successfully remove a bloom of algae. The preparation of rTiO2 is a one-pot and mass productive solution-process reduction using lithium-ethylene diamine (Li-EDA) at room temperature. Interestingly only the rutile phase of TiO2 crystal was reduced, while the anatase phase even in case of both anatase/rutile phased TiO2 was not reduced. Only reduced TiO2 materials can generate ROS under solar light, which was confirmed by electron spin resonance. Among the three different types of Li-EDA treated TiO2 (anatase, rutile and both phased TiO2), the both phased rTiO2 showed the best performance to produce ROS. The generated ROS effectively removed the common green algae Chlamydomonas. This is the first report on algae degradation under solar light, proving the feasibility of commercially available products for disinfection.

  8. Solar-light photocatalytic disinfection using crystalline/amorphous low energy bandgap reduced TiO2

    PubMed Central

    Kim, Youngmin; Hwang, Hee Min; Wang, Luyang; Kim, Ikjoon; Yoon, Yeoheung; Lee, Hyoyoung

    2016-01-01

    A generation of reactive oxygen species (ROS) from TiO2 under solar light has been long sought since the ROS can disinfect organic pollutants. We found that newly developed crystalline/amorphous reduced TiO2 (rTiO2) that has low energy bandgap can effectively generate ROS under solar light and successfully remove a bloom of algae. The preparation of rTiO2 is a one-pot and mass productive solution-process reduction using lithium-ethylene diamine (Li-EDA) at room temperature. Interestingly only the rutile phase of TiO2 crystal was reduced, while the anatase phase even in case of both anatase/rutile phased TiO2 was not reduced. Only reduced TiO2 materials can generate ROS under solar light, which was confirmed by electron spin resonance. Among the three different types of Li-EDA treated TiO2 (anatase, rutile and both phased TiO2), the both phased rTiO2 showed the best performance to produce ROS. The generated ROS effectively removed the common green algae Chlamydomonas. This is the first report on algae degradation under solar light, proving the feasibility of commercially available products for disinfection. PMID:27121120

  9. Solar-light photocatalytic disinfection using crystalline/amorphous low energy bandgap reduced TiO2.

    PubMed

    Kim, Youngmin; Hwang, Hee Min; Wang, Luyang; Kim, Ikjoon; Yoon, Yeoheung; Lee, Hyoyoung

    2016-04-28

    A generation of reactive oxygen species (ROS) from TiO2 under solar light has been long sought since the ROS can disinfect organic pollutants. We found that newly developed crystalline/amorphous reduced TiO2 (rTiO2) that has low energy bandgap can effectively generate ROS under solar light and successfully remove a bloom of algae. The preparation of rTiO2 is a one-pot and mass productive solution-process reduction using lithium-ethylene diamine (Li-EDA) at room temperature. Interestingly only the rutile phase of TiO2 crystal was reduced, while the anatase phase even in case of both anatase/rutile phased TiO2 was not reduced. Only reduced TiO2 materials can generate ROS under solar light, which was confirmed by electron spin resonance. Among the three different types of Li-EDA treated TiO2 (anatase, rutile and both phased TiO2), the both phased rTiO2 showed the best performance to produce ROS. The generated ROS effectively removed the common green algae Chlamydomonas. This is the first report on algae degradation under solar light, proving the feasibility of commercially available products for disinfection.

  10. Solar-light photocatalytic disinfection using crystalline/amorphous low energy bandgap reduced TiO2.

    PubMed

    Kim, Youngmin; Hwang, Hee Min; Wang, Luyang; Kim, Ikjoon; Yoon, Yeoheung; Lee, Hyoyoung

    2016-01-01

    A generation of reactive oxygen species (ROS) from TiO2 under solar light has been long sought since the ROS can disinfect organic pollutants. We found that newly developed crystalline/amorphous reduced TiO2 (rTiO2) that has low energy bandgap can effectively generate ROS under solar light and successfully remove a bloom of algae. The preparation of rTiO2 is a one-pot and mass productive solution-process reduction using lithium-ethylene diamine (Li-EDA) at room temperature. Interestingly only the rutile phase of TiO2 crystal was reduced, while the anatase phase even in case of both anatase/rutile phased TiO2 was not reduced. Only reduced TiO2 materials can generate ROS under solar light, which was confirmed by electron spin resonance. Among the three different types of Li-EDA treated TiO2 (anatase, rutile and both phased TiO2), the both phased rTiO2 showed the best performance to produce ROS. The generated ROS effectively removed the common green algae Chlamydomonas. This is the first report on algae degradation under solar light, proving the feasibility of commercially available products for disinfection. PMID:27121120

  11. Hydrogen plasma reduced black TiO2sbnd B nanowires for enhanced photoelectrochemical water-splitting

    NASA Astrophysics Data System (ADS)

    Tian, Zhangliu; Cui, Huolei; Zhu, Guilian; Zhao, Wenli; Xu, JiJian; Shao, Feng; He, Jianqiao; Huang, Fuqiang

    2016-09-01

    Black TiO2 with various nanostructures and phase constitutions have been reported to exhibit excellent photocatalytic and photoelectrochemical (PEC) performance. Here, we report the fabrication of black nanostructured TiO2sbnd B through hydrogen plasma assisted reduction and its enhanced PEC properties for the first time. Both the obtained TiO2sbnd B and black TiO2sbnd B are single crystalline nanowires, while the black TiO2sbnd B samples exhibit much stronger visible and infrared light absorption. The optimal black TiO2sbnd B sample obtained by hydrogen plasma treatment at 425 °C yields a photocurrent density of 0.85 mA cm-2, a rather low onset potential of -0.937 VAg/AgCl and a high applied bias photon-to-current efficiency (ABPE) of 0.363%, which is far superior to the TiO2sbnd B (0.15 mA cm-2 photocurrent, -0.917 VAg/AgCl onset potential and 0.138% ABPE). The significantly enhanced PEC performance of the black TiO2sbnd B is ascribed to the introduction of moderate surface oxygen vacancies. These results indicate that the black TiO2sbnd B is a promising material for PEC application and solar energy utilization.

  12. Lithium insertion in nanostructured TiO(2)(B) architectures.

    PubMed

    Dylla, Anthony G; Henkelman, Graeme; Stevenson, Keith J

    2013-05-21

    Electric vehicles and grid storage devices have potentialto become feasible alternatives to current technology, but only if scientists can develop energy storage materials that offer high capacity and high rate capabilities. Chemists have studied anatase, rutile, brookite and TiO2(B) (bronze) in both bulk and nanostructured forms as potential Li-ion battery anodes. In most cases, the specific capacity and rate of lithiation and delithiation increases as the materials are nanostructured. Scientists have explained these enhancements in terms of higher surface areas, shorter Li(+) diffusion paths and different surface energies for nanostructured materials allowing for more facile lithiation and delithiation. Of the most studied polymorphs, nanostructured TiO2(B) has the highest capacity with promising high rate capabilities. TiO2(B) is able to accommodate 1 Li(+) per Ti, giving a capacity of 335 mAh/g for nanotubular and nanoparticulate TiO2(B). The TiO2(B) polymorph, discovered in 1980 by Marchand and co-workers, has been the focus of many recent studies regarding high power and high capacity anode materials with potential applications for electric vehicles and grid storage. This is due to the material's stability over multiple cycles, safer lithiation potential relative to graphite, reasonable capacity, high rate capability, nontoxicity, and low cost (Bruce, P. G.; Scrosati, B.; Tarascon, J.-M. Nanomaterials for Rechargeable Lithium Batteries. Angew. Chem., Int. Ed.2008, 47, 2930-2946). One of the most interesting properties of TiO2(B) is that both bulk and nanostructured forms lithiate and delithiate through a surface redox or pseudocapacitive charging mechanism, giving rise to stable high rate charge/discharge capabilities in the case of nanostructured TiO2(B). When other polymorphs of TiO2 are nanostructured, they still mainly intercalate lithium through a bulk diffusion-controlled mechanism. TiO2(B) has a unique open crystal structure and low energy Li

  13. 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.

  14. Structural and optical properties of terbium in TiO 2 matrix

    NASA Astrophysics Data System (ADS)

    Domaradzki, Jaroslaw; Prociow, Eugeniusz L.; Kaczmarek, Danuta; Borkowska, Agnieszka; Berlicki, Tadeusz; Prociow, Krystyna

    2009-07-01

    TiO 2 thin films doped with different concentration of Tb have been prepared and study of terbium photoluminescence in TiO 2 host has been presented. Thin films were deposited on silicon and SiO 2 substrates by magnetron sputtering of Ti-Tb mosaic target in oxygen atmosphere. XRD examinations show nanocrystalline nature of prepared thin films with TiO 2-anatase and -rutile phases depending on concentration of Tb. Optical transmission study has shown the red shift of the fundamental absorption edge of TiO 2 with the increase of terbium content in the thin film. Also, the transparency decreased with increasing in amount of Tb. Photoluminescence (PL) spectra, measured upon UV excitation at 302 nm at room temperature, show a dominating green luminescence corresponding to 5D 4- 7F 5 transition at 545 nm for TiO 2-rutile thin film with 2.6 at.% of Tb. The superposition of PL peaks from Tb and TiO 2 host matrix was also observed at 491 nm.

  15. The adsorption and photo-degradation of oxalic acid at the TiO2 surface.

    NASA Astrophysics Data System (ADS)

    Mendive, Cecilia; Blesa, Miguel; Bahnemann, Detlef

    2006-03-01

    Oxalic acid is the simplest model compound to study the heterogeneous photocatalytic oxidation of pollutants on TiO2 containing more than one carboxylate group. We have carried out a study of a system of an oxalic acid solution in contact with a thin film of TiO2 particles employing ATR - FTIR in combination with quantum chemical calculations. Thus, possible adsorption structures have been identified and molecular dynamic simulations have been used to compare their predictions with the experimental data. It was found that the adsorption of oxalic acid on TiO2 in the dark can be explained in terms of two surface complexation modes for the anatase phase and only one surface complexation mode for the rutile phase. We have found that under illumination one of the complexes on the anatase phase preferably undergoes photo-degradation. At the same time water molecules are desorbed from the TiO2 surface by a thermal mechanism induced by the absorption of photons. Both processes favor the adsorption of more molecules of oxalic acid at the TiO2 surface which is thus enriched in the second complexation mode. A similar mechanism was found to occur on the rutile phase. The only complexation mode appears not to be photo-sensitive but the TiO2 surface is enriched in oxalic acid under illumination due to the replacement of photo-desorbed water molecules.

  16. Design of Novel Visible Light Active Photocatalyst Materials: Surface Modified TiO2.

    PubMed

    Nolan, Michael; Iwaszuk, Anna; Lucid, Aoife K; Carey, John J; Fronzi, Marco

    2016-07-01

    Work on the design of new TiO2 based photocatalysts is described. The key concept is the formation of composite structures through the modification of anatase and rutile TiO2 with molecular-sized nanoclusters of metal oxides. Density functional theory (DFT) level simulations are compared with experimental work synthesizing and characterizing surface modified TiO2 . DFT calculations are used to show that nanoclusters of metal oxides such as TiO2 , SnO/SnO2 , PbO/PbO2 , ZnO and CuO are stable when adsorbed at rutile and anatase surfaces, and can lead to a significant red shift in the absorption edge which will induce visible light absorption; this is the first requirement for a useful photocatalyst. The origin of the red shift and the fate of excited electrons and holes are determined. For p-block metal oxides the oxidation state of Sn and Pb can be used to modify the magnitude of the red shift and its mechanism. Comparisons of recent experimental studies of surface modified TiO2 that validate our DFT simulations are described. These nanocluster-modified TiO2 structures form the basis of a new class of photocatalysts which will be useful in oxidation reactions and with a correct choice of nanocluster modified can be applied to other reactions. PMID:26833714

  17. Enhancement of spectral response of visible light absorption of TiO2 synthesis by femtosecond laser ablation

    NASA Astrophysics Data System (ADS)

    Mahmood, Abdul Salam; Venkatakrishnan, Krishnan; Alubaidy, M.; Tan, Bo

    2011-05-01

    In this study, we report a simple, precise, and nano-scale fabrication technique for oxide nanosphere structure rutile (TiO2) using couple hundred of femtosecond laser irradiation at MHz pulse repetition frequency in air at atmospheric pressure. Measured reflectance's through Spectroradiometer show that their couplings of incident electromagnetic irradiations are improved greatly over the broad band wavelength range. Lower reflectance intensity obtained with long dwell time is due to generate bulk quantity of TiO2 oxide nanoparticle agglomerate by fusion, and form interweaving fibrous structures that show certain degree of assembly. The X-ray diffraction test confirmed that the oxide titanium metallic nanostructure is a rutile phase (TiO2). The growth of TiO2 nanostructure is highly recommended for the applications of dye-sensitized solar cells and photovoltaic applications.

  18. Influence of TiO2 Nanorod Arrays on the Bilayered Photoanode for Dye-Sensitized Solar Cells

    NASA Astrophysics Data System (ADS)

    Cao, Ya; Li, Zhen; Wang, Yang; Zhang, Tao; Li, Yinchang; Liu, Xueqin; Li, Fei

    2016-10-01

    A TiO2 bilayered structure consisting of TiO2 nanoparticles (TiO2NP) as an overlayer and single-crystal rutile TiO2 nanorods (TiO2 NRs) as an underlayer on a transparent conductive fluorine-doped tin oxide substrate was designed as the photoanode of dye-sensitized solar cells (DSSCs) through a facile hydrothermal treatment followed by a doctor-blade method. DSSCs based on the hierarchical TiO2 nano-architecture photoelectrode shows a power conversion efficiency of 7.39% because the relatively large specific surface area of TiO2NP increased the dye absorption, and oriented one-dimensional TiO2 NRs enhanced the light harvesting capability, accelerating interfacial electron transport. In particular, we observed the growth morphology of the TiO2 nanorod arrays in the bilayered photoanode and the influence of the whole solar cell. The result indicated that the TiO2 NRs layer clearly impacted the photoelectron chemical properties, while the vertical and intensive nanorod arrays significantly increased their performance.

  19. Comparison of Au and TiO2 based catalysts for the synthesis of chalcogenide nanowires

    NASA Astrophysics Data System (ADS)

    Schönherr, P.; Prabhakaran, D.; Jones, W.; Dimitratos, N.; Bowker, M.; Hesjedal, T.

    2014-06-01

    We present a comparative study of TiO2-based and Au catalysts for the physical vapor deposition of (Bi1-xSbx)2Se3 topological insulator nanowires. The standard Au nanoparticle catalyst was compared to five TiO2 nanoparticle based catalysts (anatase, rutile, P-25, high surface area anatase, and TiO2 supported Au particles). The use of Au nanoparticles seriously harms the properties of nanowires, thereby limiting their application. In contrast, TiO2 based catalysts lead to the residue-free growth of nanowires with a higher degree of crystallinity. Homogeneous nanowire ensembles are achieved with the mixed phase P-25 catalyst, and a possible growth mechanism is proposed.

  20. Phase stability frustration on ultra-nanosized anatase TiO2

    PubMed Central

    Patra, Snehangshu; Davoisne, Carine; Bouyanfif, Houssny; Foix, Dominique; Sauvage, Frédéric

    2015-01-01

    This work sheds light on the exceptional robustness of anatase TiO2 when it is downsized to an extreme value of 4 nm. Since at this size the surface contribution to the volume becomes predominant, it turns out that the material becomes significantly resistant against particles coarsening with temperature, entailing a significant delay in the anatase to rutile phase transition, prolonging up to 1000 °C in air. A noticeable alteration of the phase stability diagram with lithium insertion is also experienced. Lithium insertion in such nanocrystalline anatase TiO2 converts into a complete solid solution until almost Li1TiO2, a composition at which the tetragonal to orthorhombic transition takes place without the formation of the emblematic and unwished rock salt Li1TiO2 phase. Consequently, excellent reversibility in the electrochemical process is experienced in the whole portion of lithium content. PMID:26042388

  1. Mesoporous TiO2 single crystals: facile shape-, size-, and phase-controlled growth and efficient photocatalytic performance.

    PubMed

    Zheng, Xiaoli; Kuang, Qin; Yan, Keyou; Qiu, Yongcai; Qiu, Jianhang; Yang, Shihe

    2013-11-13

    In this work, we have succeeded in preparing rutile and anatase TiO2 mesoporous single crystals with diverse morphologies in a controllable fashion by a simple silica-templated hydrothermal method. A simple in-template crystal growth process was put forward, which involved heterogeneous crystal nucleation and oriented growth within the template, a sheer spectator, and an excluded volume, i.e., crystal growth by faithful negative replication of the silica template. A series of mesoporous single-crystal structures, including rutile mesoporous TiO2 nanorods with tunable sizes and anatase mesoporous TiO2 nanosheets with dominant {001} facets, have been synthesized to demonstrate the versatility of the strategy. The morphology, size, and phase of the TiO2 mesoporous single crystals can be tuned easily by varying the external conditions such as the hydrohalic acid condition, seed density, and temperature rather than by the silica template, which merely serves for faithful negative replication but without interfering in the crystallization process. To demonstrate the application value of such TiO2 mesoporous single crystals, photocatalytic activity was tested. The resultant TiO2 mesoporous single crystals exhibited remarkable photocatalytic performance on hydrogen evolution and degradation of methyl orange due to their increased surface area, single-crystal nature, and the exposure of reactive crystal facets coupled with the three-dimensionally connected mesoporous architecture. It was found that {110} facets of rutile mesoporous single crystals can be considered essentially as reductive sites with a key role in the photoreduction, while {001} facets of anatase mesoporous single crystals provided oxidation sites in the oxidative process. Such shape- and size-controlled rutile and anatase mesoporous TiO2 single crystals hold great promise for building energy conversion devices, and the simple solution-based hydrothermal method is extendable to the synthesis of other

  2. Bilayer hollow/spindle-like anatase TiO2 photoanode for high efficiency dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Wang, Guanxi; Zhu, Xunjin; Yu, Jiaguo

    2015-03-01

    Derived from a hollow TiO2 nanoparticle (HNP) as underlayer and a TiO2 spindle (SP) as light scattering overlayer, a new bilayer single-crystalline photoanode (HNP/SP) is fabricated for dye-sensitized solar cell (DSSC) application. The prepared bilayer TiO2 photoanode and two comparative HNP/HNP and SP/SP ones are fully characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, UV-vis absorption spectroscopy and N2 adsorption-desorption isotherms. An overall photoelectric conversion efficiency of 8.65% has been achieved for HNP/SP DSSC, which is 25% higher than that of HNP/HNP DSSC, and also far superior to that of SP/SP or conventional P25 DSSC. The improved photovoltaic performance of HNP/SP DSSC is attributed to the synergic effects, i.e. the single-crystalline bilayer structure favoring for rapid interfacial electron transport, the relatively large specific surface area of HNP for effective dye adsorption, and the 1D geometry of single-crystalline TiO2 spindles for direct electron transport pathway and strong light scattering effect.

  3. Facile preparation and enhanced microwave absorption properties of core-shell composite spheres composited of Ni cores and TiO2 shells.

    PubMed

    Zhao, Biao; Shao, Gang; Fan, Bingbing; Zhao, Wanyu; Xie, Yajun; Zhang, Rui

    2015-04-14

    Core-shell microspheres with Ni cores and two phases of TiO2 (anatase, rutile) shells have been successfully synthesized. The crystal structure, morphology and microwave absorption properties of the as-prepared composites were analyzed by X-ray diffraction, field-emission scanning electron microscopy, energy dispersive X-ray spectroscopy, transmission electron microscopy, and vector network analysis. The core-shell rutile TiO2-coated Ni exhibits better antioxidation ability than that of pure Ni due to the presence of the rutile TiO2 shell, which is confirmed by the thermal gravimetric analysis (TGA). In comparison with bare Ni, these two composites show better microwave absorption properties. The minimum reflection loss (RL) is -38.0 dB at 11.1 GHz with a thickness of only 1.8 mm for the Ni@TiO2 (rutile) composite. The enhanced absorption capability arises from the efficient complementarities between the magnetic loss and dielectric loss, multiple interfacial polarization, high thermal conductivity of rutile TiO2 and microwave attenuation constant. These results show that the thin high-efficiency rutile TiO2-coated Ni composite is a great potential microwave absorbing material for practical applications. PMID:25745675

  4. Preparation of hollow TiO2 nanoparticles through TiO2 deposition on polystyrene latex particles and characterizations of their structure and photocatalytic activity

    PubMed Central

    2012-01-01

    In a mixed solvent of water and ethanol, polystyrene/titanium dioxide (PSt/TiO2) composite particles of core-shell structure were prepared by hydrolysis of tetrabutyl titanate in the presence of cationic PSt particles or anionic PSt particles surface-treated using γ-aminopropyl triethoxysilane. Hollow TiO2 particles were obtained through calcination of the PSt/TiO2 core-shell particles to burn off the PSt core or through dissolution of the core by tetrahydrofuran (THF). An alternative process constituted of preheating the PSt/TiO2 particles at 200°C to allow partial crystallization followed by calcination or PSt dissolution by THF. The outcome TiO2 particles thus prepared were examined by TEM, and hollow TiO2 particles were observed. The crystalline phase structure and phase transformation were characterized, which revealed that preheating before the removal of the PSt core was useful to achieve the desired hollow TiO2 particles, and the calcination process was beneficial to the formation of anatase and rutile structures. The tests of TiO2 particles as catalyst in the photodegradation of Rhodamine B demonstrated that a much higher catalytic activity was observed with the TiO2 hollow particles prepared through calcination combined with preheating. PMID:23176612

  5. Hydrogen donor in anatase TiO2

    NASA Astrophysics Data System (ADS)

    Lavrov, E. V.

    2016-01-01

    An IR absorption study of hydrogen-related defects in natural single-crystalline anatase TiO2 has been carried out. A complex with IR absorption lines at 3412 and 3417 cm-1 is shown to act as a donor with ionization energy of tens of meV. The two lines are identified as stretching local vibrational modes of the O-H bonds of the donor in the neutral and positive charge states, respectively. The defect is unstable against annealing at approximately 300 ∘C and a storage at room temperature on the time scale of a few weeks. These findings suggest that interstitial hydrogen is a plausible model of this defect.

  6. Whiter, brighter, and more stable cellulose paper coated with TiO2 /SiO2 core/shell nanoparticles using a layer-by-layer approach.

    PubMed

    Cheng, Fei; Lorch, Mark; Sajedin, Seyed Mani; Kelly, Stephen M; Kornherr, Andreas

    2013-08-01

    To inhibit the photocatalytic degradation of organic material supports induced by small titania (TiO2 ) nanoparticles, four kinds of TiO2 nanoparticles, that is, commercial P25-TiO2 , commercial rutile phase TiO2 , rutile TiO2 nanorods and rutile TiO2 spheres, prepared from TiCl4 , were coated with a thin, but dense, coating of silica (SiO2 ) using a conventional sol-gel technique to form TiO2 /SiO2 core/shell nanoparticles. These core/shell particles were deposited and fixed as a very thin coating onto the surface of cellulose paper samples by a wet-chemistry polyelectrolyte layer-by-layer approach. The TiO2 /SiO2 nanocoated paper samples exhibit higher whiteness and brightness and greater stability to UV-bleaching than comparable samples of blank paper. There are many potential applications for this green chemistry approach to protect cellulosic fibres from UV-bleaching in sunlight and to improve their whiteness and brightness.

  7. Nanometer-size alpha-PbO(2)-type TiO(2) in garnet: A thermobarometer for ultrahigh-pressure metamorphism

    PubMed

    Hwang; Shen; Chu; Yui

    2000-04-14

    A high-pressure phase of titanium dioxide (TiO(2)) with an alpha-PbO(2)-type structure has been identified in garnet of diamondiferous quartzofeldspathic rocks from the Saxonian Erzgebirge, Germany. Analytical electron microscopy indicates that this alpha-PbO(2)-type TiO(2) occurred as an epitaxial nanometer-thick slab between twinned rutile bicrystals. Given a V-shaped curve for the equilibrium phase boundary of alpha-PbO(2)-type TiO(2) to rutile, the stabilization pressure of alpha-PbO(2)-type TiO(2) should be 4 to 5 gigapascals at 900 degrees to 1000 degrees C. This suggests a burial of continental crustal rocks to depths of at least 130 kilometers. The alpha-PbO(2)-type TiO(2) may be a useful pressure and temperature indicator in the diamond stability field.

  8. Room-temperature ferromagnetism in the mixtures of the TiO2 and Co3O4 powders

    NASA Astrophysics Data System (ADS)

    Serrano, A.; Pinel, E. Fernandez; Quesada, A.; Lorite, I.; Plaza, M.; Pérez, L.; Jiménez-Villacorta, F.; de La Venta, J.; Martín-González, M. S.; Costa-Krämer, J. L.; Fernandez, J. F.; Llopis, J.; García, M. A.

    2009-04-01

    We report here the observation of ferromagnetism (FM) at 300 K in mixtures of TiO2 and Co3O4 powders despite the antiferromagnetic and diamagnetic characters of both oxides, respectively. The ferromagnetic behavior is found in the early stages of reaction and only for TiO2 in anatase structure; no FM is found for identical samples prepared with rutile- TiO2 . Optical spectroscopy and x-ray absorption spectra confirm a surface reduction of octahedral Co+3→Co+2 in the mixtures which is in the origin of the observed magnetism.

  9. Band gap enhancement of glancing angle deposited TiO2 nanowire array

    NASA Astrophysics Data System (ADS)

    Chinnamuthu, P.; Mondal, A.; Singh, N. K.; Dhar, J. C.; Chattopadhyay, K. K.; Bhattacharya, Sekhar

    2012-09-01

    Vertically oriented TiO2 nanowire (NW) arrays were fabricated by glancing angle deposition technique. Field emission-scanning electron microscopy shows the formation of two different diameters ˜80 nm and ˜40 nm TiO2 NW for 120 and 460 rpm azimuthal rotation of the substrate. The x-ray diffraction and Raman scattering depicted the presence of rutile and anatase phase TiO2. The overall Raman scattering intensity decreased with nanowire diameter. The role of phonon confinement in anatase and rutile peaks has been discussed. The red (7.9 cm-1 of anatase Eg) and blue (7.4 cm-1 of rutile Eg, 7.8 cm-1 of rutile A1g) shifts of Raman frequencies were observed. UV-vis absorption measurements show the main band absorption at 3.42 eV, 3.48 eV, and ˜3.51 eV for thin film and NW prepared at 120 and 460 rpm, respectively. Three fold enhance photon absorption and intense light emission were observed for NW assembly. The photoluminescence emission from the NW assembly revealed blue shift in main band transition due to quantum confinement in NW structures.

  10. Structure and Formation Mechanism of Black TiO2 Nanoparticles

    DOE PAGESBeta

    Tian, Mengkun; Mahjouri-Samani, Masoud; Eres, Gyula; Sachan, Ritesh; Yoon, Mina; Chisholm, Matthew F.; Wang, Kai; Puretzky, Alexander A.; Rouleau, Christopher M.; Geohegan, David B.; et al

    2015-10-27

    The remarkable properties of black TiO2 are due to its disordered surface shell surrounding a crystalline core. However, the chemical composition and the atomic and electronic structure of the disordered shell and its relationship to the core remain poorly understood. Using advanced transmission electron microscopy methods, we show that the outermost layer of black TiO2 nanoparticles consists of a disordered Ti2O3 shell. The measurements show a transition region that connects the disordered Ti2O3 shell to the perfect rutile core consisting first of four to five monolayers of defective rutile, containing clearly visible Ti interstitial atoms, followed by an ordered reconstructionmore » layer of Ti interstitial atoms. Our data suggest that this reconstructed layer presents a template on which the disordered Ti2O3 layers form by interstitial diffusion of Ti ions. In contrast to recent reports that attribute TiO2 band-gap narrowing to the synergistic action of oxygen vacancies and surface disorder of nonspecific origin, our results point to Ti2O3, which is a narrow-band-gap semiconductor. In conclusion, as a stoichiometric compound of the lower oxidation state Ti3+ it is expected to be a more robust atomic structure than oxygen-deficient TiO2 for preserving and stabilizing Ti3+ surface species that are the key to the enhanced photocatalytic activity of black TiO2.« less

  11. Colloidal TiO2 nanocrystals prepared from peroxotitanium complex solutions: phase evolution from different precursors.

    PubMed

    Seok, Sang Il; Vithal, Muga; Chang, Jeong Ah

    2010-06-01

    We report the preparation of nanocrystalline anatase and rutile TiO(2) from aqueous peroxotitanium complex (PTC) solutions and their characterization by powder X-ray diffraction (XRD), infrared spectroscopy, and Raman spectroscopy. The phase evolution of TiO(2) prepared using PTC derived from different precursors, i.e., TiCl(4) and titanium tetraisopropoxide (TTIP), is related to the nature of the intermediate steps. Phase-pure nanoanatase was formed in PTC solution derived from TiCl(4), while a mixture of minor anatase and dominant rutile were prepared from PTC when TTIP was used as precursor. On the other hand, in the case of calcining PTC powders in air, a pure anatase phase of TiO(2) was obtained, regardless of the precursor used. Thus, the formation and attachment of hydrated TiO(6) units or TiO(2)·xH(2)O under a different environment, especially pH, plays a critical role in determining the phase during the crystallization of TiO(2). PMID:20227087

  12. Efficient Photocatalytic Activities of TiO2 Hollow Fibers with Mixed Phases and Mesoporous Walls.

    PubMed

    Hou, Huilin; Shang, Minghui; Wang, Lin; Li, Wenge; Tang, Bin; Yang, Weiyou

    2015-01-01

    Currently, Degussa P25, with the typical mixed phases of anatase and rutile TiO2, is widely applied as the commercial photocatalysts. However, there are still some of obstacles for the P25 nanoparticles with totally high photocatalytic activities, especially for the catalytic stability due to their inevitable aggregation of the nanoparticles when used as the photocatalysts. In the present work, we reported the exploration of a novel TiO2 photocatalyst, which could offer an ideal platform for synergetic combination of the mixed-phase composition, hollow architecture and mesoporous walls for the desired excellent photocatalytic efficiency and robust stability. The mesoporous TiO2 hollow nanofibers were fabricated via a facile single capillary electrospinning technique, in which the foaming agents were used for creating mesopores throughout the walls of the hollow fibers. The obtained hollow fibers exhibit a high purity and possess the mixed phases of 94.6% anatase and 5.4% rutile TiO2. As compared to P25, the as-fabricated mesoporous TiO2 hollow fibers exhibited much higher efficient photocatalytic activities and stabilities toward the hydrogen evolution with a rate of ~499.1 μmol g(-1)·h(-1) and ~99.5% degradation Rhodamine B (RhB) in 60 min, suggesting their promising application in efficient photocatalysts. PMID:26470013

  13. Efficient Photocatalytic Activities of TiO2 Hollow Fibers with Mixed Phases and Mesoporous Walls

    PubMed Central

    Hou, Huilin; Shang, Minghui; Wang, Lin; Li, Wenge; Tang, Bin; Yang, Weiyou

    2015-01-01

    Currently, Degussa P25, with the typical mixed phases of anatase and rutile TiO2, is widely applied as the commercial photocatalysts. However, there are still some of obstacles for the P25 nanoparticles with totally high photocatalytic activities, especially for the catalytic stability due to their inevitable aggregation of the nanoparticles when used as the photocatalysts. In the present work, we reported the exploration of a novel TiO2 photocatalyst, which could offer an ideal platform for synergetic combination of the mixed-phase composition, hollow architecture and mesoporous walls for the desired excellent photocatalytic efficiency and robust stability. The mesoporous TiO2 hollow nanofibers were fabricated via a facile single capillary electrospinning technique, in which the foaming agents were used for creating mesopores throughout the walls of the hollow fibers. The obtained hollow fibers exhibit a high purity and possess the mixed phases of 94.6% anatase and 5.4% rutile TiO2. As compared to P25, the as-fabricated mesoporous TiO2 hollow fibers exhibited much higher efficient photocatalytic activities and stabilities toward the hydrogen evolution with a rate of ~499.1 μmol g−1·h−1 and ~99.5% degradation Rhodamine B (RhB) in 60 min, suggesting their promising application in efficient photocatalysts. PMID:26470013

  14. TiO2 hierarchical nanostructures: Hydrothermal fabrication and application in dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Liang, Jia; Zhang, Gengmin; Yang, Jin; Sun, Wentao; Shi, Mingji

    2015-01-01

    Arrays of TiO2 hierarchical nanostructures that consisted of rutile nanorods and anatase branches were hydrothermally fabricated and employed as photoanodes in dye-sensitized solar cells (DSSCs). Each hierarchical nanostructure array was attained in two steps. First, a primary nanorod array was synthesized in aqueous solutions of hydrochloric acid (HCl) and tetrabutyl titanate (C16H36O4Ti); subsequently, secondary branches were grown on the nanorods in aqueous solutions of ammonium hexafluorotitanate ((NH4)2TiF6) and boric acid (H3BO3). The secondary anatase branches filled part of the space among the primary rutile nanorods and gave rise to a larger surface area. Light-harvesting capability of the DSSCs with TiO2 hierarchical nanostructures as photoanodes was appreciably improved because more dye molecules could be loaded on the photoanodes and more light could be scattered inside the DSSCs. Therefore, the conversion efficiencies of the DSSCs were doubled by replacing the photoanode of primary TiO2 nanorod array with the photoanodes of TiO2 hierarchical nanostructure arrays. Furthermore, in order to reach a compromise between the photoanode surface area and the inter-nanorod space volume, the growth time of the secondary TiO2 anatase branches was optimized.

  15. Structure and Formation Mechanism of Black TiO2 Nanoparticles.

    PubMed

    Tian, Mengkun; Mahjouri-Samani, Masoud; Eres, Gyula; Sachan, Ritesh; Yoon, Mina; Chisholm, Matthew F; Wang, Kai; Puretzky, Alexander A; Rouleau, Christopher M; Geohegan, David B; Duscher, Gerd

    2015-10-27

    The remarkable properties of black TiO2 are due to its disordered surface shell surrounding a crystalline core. However, the chemical composition and the atomic and electronic structure of the disordered shell and its relationship to the core remain poorly understood. Using advanced transmission electron microscopy methods, we show that the outermost layer of black TiO2 nanoparticles consists of a disordered Ti2O3 shell. The measurements show a transition region that connects the disordered Ti2O3 shell to the perfect rutile core consisting first of four to five monolayers of defective rutile, containing clearly visible Ti interstitial atoms, followed by an ordered reconstruction layer of Ti interstitial atoms. Our data suggest that this reconstructed layer presents a template on which the disordered Ti2O3 layers form by interstitial diffusion of Ti ions. In contrast to recent reports that attribute TiO2 band-gap narrowing to the synergistic action of oxygen vacancies and surface disorder of nonspecific origin, our results point to Ti2O3, which is a narrow-band-gap semiconductor. As a stoichiometric compound of the lower oxidation state Ti(3+) it is expected to be a more robust atomic structure than oxygen-deficient TiO2 for preserving and stabilizing Ti(3+) surface species that are the key to the enhanced photocatalytic activity of black TiO2.

  16. Low Frequency Ultrasonication of Degussa P25 TiO2 and Its Superior Photocatalytic Properties.

    PubMed

    Vijayarangamuthu, K; Han, EunJi; Jeon, Ki-Joon

    2016-05-01

    We report the simple and effective method for enhancing the photocatalytic properties of Degussa P25 TiO2 by low frequency ultrasonication. The improvement in the crystallinity of ultrasonicated TiO2 was confirmed by the X-ray diffraction and Raman spectroscopy studies. Further, the X-ray photoelectron spectroscopy was utilized to study the changes in chemical nature and band edge due to the effect of ultrasonication and H2O2 solvent. The transmission electron microscope (TEM) was used to analysis the surface distortion. The Moire fringes in TEM were examined to understand the partial transformation of amorphous to crystalline anatase structure and overlapping of rutile over anatase crystal. The photocatalytic results indicated improvement in the degradation of methylene blue dye. The degradation efficiency was estimated to be 86% for ultrasonicated TiO2, which is higher as compared to 40% of P25. The rate constant values revealed four times superior degradation property of ultrasonicated TiO2. The improvement in the photocatalytic efficiency was correlated to the formation of rutile/anatase TiO2 aggregation and its consequences on electron-hole recombination. PMID:27483763

  17. Efficient Photocatalytic Activities of TiO2 Hollow Fibers with Mixed Phases and Mesoporous Walls

    NASA Astrophysics Data System (ADS)

    Hou, Huilin; Shang, Minghui; Wang, Lin; Li, Wenge; Tang, Bin; Yang, Weiyou

    2015-10-01

    Currently, Degussa P25, with the typical mixed phases of anatase and rutile TiO2, is widely applied as the commercial photocatalysts. However, there are still some of obstacles for the P25 nanoparticles with totally high photocatalytic activities, especially for the catalytic stability due to their inevitable aggregation of the nanoparticles when used as the photocatalysts. In the present work, we reported the exploration of a novel TiO2 photocatalyst, which could offer an ideal platform for synergetic combination of the mixed-phase composition, hollow architecture and mesoporous walls for the desired excellent photocatalytic efficiency and robust stability. The mesoporous TiO2 hollow nanofibers were fabricated via a facile single capillary electrospinning technique, in which the foaming agents were used for creating mesopores throughout the walls of the hollow fibers. The obtained hollow fibers exhibit a high purity and possess the mixed phases of 94.6% anatase and 5.4% rutile TiO2. As compared to P25, the as-fabricated mesoporous TiO2 hollow fibers exhibited much higher efficient photocatalytic activities and stabilities toward the hydrogen evolution with a rate of ~499.1 μmol g-1·h-1 and ~99.5% degradation Rhodamine B (RhB) in 60 min, suggesting their promising application in efficient photocatalysts.

  18. Effect of crystalline structure of TiO 2 substrates on initial growth of atomic layer deposited Ru thin films

    NASA Astrophysics Data System (ADS)

    Kim, Seong Keun; Han, Sora; Han, Jeong Hwan; Hwang, Cheol Seong

    2011-02-01

    Ru thin films were grown on polymorphic TiO2 thin film substrates at 230 and 250 °C by atomic layer deposition using 2,4-(dimethylpentadienyl)(ethylcyclopentadienyl)Ru and an O2 gas. While the Ru films grown on amorphous and rutile TiO2 substrates showed a relatively long incubation cycle number of approximately 350 and 100 at 230 and 250 °C, respectively, the Ru films grown on anatase TiO2 substrates exhibited a significantly shorter incubation delay which was attributed to the catalytic activity of anatase TiO2. This difference in the incubation cycle affected the surface morphology of the Ru films on different TiO2 substrates.

  19. Tricrystalline TiO2 with enhanced photocatalytic activity and durability for removing volatile organic compounds from indoor air.

    PubMed

    Chen, Kunyang; Zhu, Lizhong; Yang, Kun

    2015-06-01

    It is important to develop efficient and economic techniques for removing volatile organic compounds (VOCs) in indoor air. Heterogeneous TiO2-based semiconductors are a promising technology for achieving this goal. Anatase/brookite/rutile tricrystalline TiO2 with mesoporous structure was synthesized by a low-temperature hydrothermal route in the presence of HNO3. The obtained samples were characterized by X-ray diffraction and N2 adsorption-desorption isotherm. The photocatalytic activity was evaluated by photocatalytic decomposition of toluene in air under UV light illumination. The results show that tricrystalline TiO2 exhibited higher photocatalytic activity and durability toward gaseous toluene than bicrystalline TiO2, due to the synergistic effects of high surface area, uniform mesoporous structure and junctions among mixed phases. The tricrystalline TiO2 prepared at RHNO3=0.8, containing 80.7% anatase, 15.6% brookite and 3.7% rutile, exhibited the highest photocatalytic activity, about 3.85-fold higher than that of P25. The high activity did not significantly degrade even after five reuse cycles. In conclusion, it is expected that our study regarding gas-phase degradation of toluene over tricrystalline TiO2 will enrich the chemistry of the TiO2-based materials as photocatalysts for environmental remediation and stimulate further research interest on this intriguing topic.

  20. Synthesis of Nanoscale TiO2 and Study of the Effect of Their Crystal Structure on Single Cell Response

    PubMed Central

    Ismagilov, Z. R.; Shikina, N. V.; Mazurkova, N. A.; Tsikoza, L. T.; Tuzikov, F. V.; Ushakov, V. A.; Ishchenko, A. V.; Rudina, N. A.; Korneev, D. V.; Ryabchikova, E. I.

    2012-01-01

    To study the effect of nanoscale titanium dioxide (TiO2) on cell responses, we synthesized four modifications of the TiO2 (amorphous, anatase, brookite, and rutile) capable of keeping their physicochemical characteristics in a cell culture medium. The modifications of nanoscale TiO2 were obtained by hydrolysis of TiCl4 and Ti(i-OC3H7)4 (TIP) upon variation of the synthesis conditions; their textural, morphological, structural, and dispersion characteristics were examined by a set of physicochemical methods: XRD, BET, SAXS, DLS, AFM, SEM, and HR-TEM. The effect of synthesis conditions (nature of precursor, pH, temperature, and addition of a complexing agent) on the structural-dispersion properties of TiO2 nanoparticles was studied. The hydrolysis methods providing the preparation of amorphous, anatase, brookite, and rutile modifications of TiO2 nanoparticles 3–5 nm in size were selected. Examination of different forms of TiO2 nanoparticles interaction with MDCK cells by transmission electron microscopy of ultrathin sections revealed different cell responses after treatment with different crystalline modifications and amorphous form of TiO2. The obtained results allowed us to conclude that direct contact of the nanoparticles with cell plasma membrane is the primary and critical step of their interaction and defines a subsequent response of the cell. PMID:22623903

  1. Tricrystalline TiO2 with enhanced photocatalytic activity and durability for removing volatile organic compounds from indoor air.

    PubMed

    Chen, Kunyang; Zhu, Lizhong; Yang, Kun

    2015-06-01

    It is important to develop efficient and economic techniques for removing volatile organic compounds (VOCs) in indoor air. Heterogeneous TiO2-based semiconductors are a promising technology for achieving this goal. Anatase/brookite/rutile tricrystalline TiO2 with mesoporous structure was synthesized by a low-temperature hydrothermal route in the presence of HNO3. The obtained samples were characterized by X-ray diffraction and N2 adsorption-desorption isotherm. The photocatalytic activity was evaluated by photocatalytic decomposition of toluene in air under UV light illumination. The results show that tricrystalline TiO2 exhibited higher photocatalytic activity and durability toward gaseous toluene than bicrystalline TiO2, due to the synergistic effects of high surface area, uniform mesoporous structure and junctions among mixed phases. The tricrystalline TiO2 prepared at RHNO3=0.8, containing 80.7% anatase, 15.6% brookite and 3.7% rutile, exhibited the highest photocatalytic activity, about 3.85-fold higher than that of P25. The high activity did not significantly degrade even after five reuse cycles. In conclusion, it is expected that our study regarding gas-phase degradation of toluene over tricrystalline TiO2 will enrich the chemistry of the TiO2-based materials as photocatalysts for environmental remediation and stimulate further research interest on this intriguing topic. PMID:26040745

  2. Novel TiO2/C nanocomposites: synthesis, characterization, and application as a photocatalyst for the degradation of organic pollutants.

    PubMed

    da Costa, Elias; Zamora, Patricio P; Zarbin, Aldo J G

    2012-02-15

    Novel TiO(2)/carbon nanocomposites were prepared through the pyrolysis of TiO(2)/poly(furfuryl alcohol) hybrid materials, which were obtained by the sol-gel method, starting from titanium tetraisopropoxide (TTIP) and furfuryl alcohol (FA) precursors. Six different TiO(2)/C samples were prepared based on different TiO(2) nanoparticle sizes and TiO(2)/FA ratios. All of the samples were characterized using X-ray diffraction, infrared, and Raman spectroscopy. The results indicated effective FA polymerization onto the TiO(2) (anatase) nanoparticles, polymer conversion to disordered carbon following the pyrolysis, and a simultaneous TiO(2) anatase-rutile phase transition. The resulting TiO(2)/carbon composites were used as photocatalysts in the advanced oxidative process (AOP) for the degradation of reactive organic dyes in aqueous solution. The results indicate excellent photocatalytic performance (degradation of 99% of the dye after 60 min) with several advantages over traditional TiO(2)-based photocatalysts. PMID:22056275

  3. Nanostructured TiO2 films for dye-sensitized solar cells prepared by the sol-gel method.

    PubMed

    Jin, Young Sam; Kim, Kyung Hwan; Park, Sang Joon; Yoon, Hyon Hee; Choi, Hyung Wook

    2011-12-01

    TiO2 films were prepared on glass substrates using the sol-gel process for a dye-sensitized solar cell application. The TiO2 sol was prepared using hydrolysis/polycondensation. Titanium (IV) Tetra Isopropoxide (TTIP) was used as precursor and Nitric acid (HNO3) was used as a catalyst for the peptization. The crystal structure and morphology of the prepared materials were characterized by XRD, and an SEM. The observations confirmed the nanocrystalline nature of the TiO2. The reaction parameters, such as the catalyst concentrations, the calcination time, and the calcination temperature were varied during the synthesis in order to achieve nanosize TiO2 particles. The prepared TiO2 particles were coated onto FTO glass using a screen printing technique. The prepared TiO2 films were characterized by UV-vis. The TiO2 particles calcinated at low temperatures showed an anatase phase they grew into a rutile phase when the calcination temperature increased. The size and structure of the TiO2 particles were adjusted to specific surface areas. It was found that the conversion efficiency of the DSSC was highly affected by the properties of the TiO2 particles. PMID:22409037

  4. Nanostructured TiO2 films for dye-sensitized solar cells prepared by the sol-gel method.

    PubMed

    Jin, Young Sam; Kim, Kyung Hwan; Park, Sang Joon; Yoon, Hyon Hee; Choi, Hyung Wook

    2011-12-01

    TiO2 films were prepared on glass substrates using the sol-gel process for a dye-sensitized solar cell application. The TiO2 sol was prepared using hydrolysis/polycondensation. Titanium (IV) Tetra Isopropoxide (TTIP) was used as precursor and Nitric acid (HNO3) was used as a catalyst for the peptization. The crystal structure and morphology of the prepared materials were characterized by XRD, and an SEM. The observations confirmed the nanocrystalline nature of the TiO2. The reaction parameters, such as the catalyst concentrations, the calcination time, and the calcination temperature were varied during the synthesis in order to achieve nanosize TiO2 particles. The prepared TiO2 particles were coated onto FTO glass using a screen printing technique. The prepared TiO2 films were characterized by UV-vis. The TiO2 particles calcinated at low temperatures showed an anatase phase they grew into a rutile phase when the calcination temperature increased. The size and structure of the TiO2 particles were adjusted to specific surface areas. It was found that the conversion efficiency of the DSSC was highly affected by the properties of the TiO2 particles.

  5. A single crystalline InP nanowire photodetector

    NASA Astrophysics Data System (ADS)

    Yan, Xin; Li, Bang; Wu, Yao; Zhang, Xia; Ren, Xiaomin

    2016-08-01

    Single crystalline nanowires are critical for achieving high-responsivity, high-speed, and low-noise nanoscale photodetectors. Here, we report a metal-semiconductor-metal photodetector based on a single crystalline InP nanowire. The nanowires are grown by a self-catalyzed method and exhibit stacking-fault-free zinc blende crystal structure. The nanowire exhibits a typical n-type semiconductor property and shows a low room temperature dark current of several hundred pA at moderate biases. A photoresponsivity of 6.8 A/W is obtained at a laser power density of 0.2 mW/cm2. This work demonstrates that single crystalline InP nanowires are good candidates for future optoelectronic device applications.

  6. Raman spectroscopy of ball-milled TiO 2

    NASA Astrophysics Data System (ADS)

    Gajović, A.; Stubičar, M.; Ivanda, M.; Furić, K.

    2001-05-01

    Raman spectroscopy was applied to study structural and dimensional changes during high-energy ball milling of TiO 2 anatase. Milling was performed for up to 10 h using two different sets of grinding tools (wolfram carbide (WC) and agate). The diminution of the TiO 2 particle to nanometric size was monitoring by low-frequency Raman spectroscopy. The nanometric sizes were confirmed by transmission electron microscopy (TEM). After short milling time by WC the bands of high-pressure TiO 2 II phase (α-PbO 2 structure) were detected in Raman spectrum. Prolonged milling time was needed for transformation to rutil. When milling was performed by agate, the time necessary for both phase transitions was longer, presumably because of lower ball-to-powder weight ratio. The low-frequency Raman band of the prolonged milled samples was broad, which suggests the wide dispersion in nano-particle dimensions. The position of the low-frequency band in longer-milled samples indicated dimensions smaller than 20 nm, since the diameter of the particle is inversely proportional to the low-frequency mode of the spherical particles. These results were in agreement with the TEM results.

  7. Unexpected adsorption of oxygen on TiO2 nanotube arrays: influence of crystal structure.

    PubMed

    Funk, S; Hokkanen, B; Burghaus, U; Ghicov, A; Schmuki, P

    2007-04-01

    We present kinetics data of O2, n/iso-butane, CO2, and CO adsorbed at ultrahigh vacuum conditions on TiO2 nanotube (TiNTs) arrays produced by electrochemical anodization; amorphous and polycrystalline (anatase and mixed anatase/rutile) TiNTs have been studied addressing structure-activity relationships. Oxygen distinctly interacts with the TiNTs, whereas this process is not observed on fully oxidized TiO2 single crystals. Both molecularly and atomically bonded oxygen have been observed. Variations in the binding energies of alkanes were also detected.

  8. Preparation of TiO2 nanocrystallites by oxidation of Ti-Au111 surface alloy.

    PubMed

    Potapenko, Denis V; Osgood, Richard M

    2009-06-01

    Ti-Au surface alloy oxidation is used to form nanocrystals of TiO(2) on Au(111). In situ scanning tunneling microscopy (STM) studies show that the approach yields arrays of 8-11 nm wide crystals with relatively narrow size dispersion and uniform crystallography. STM imaging shows that their crystallographic form is rutile with a triangular or hexagonal geometry. Scanning tunneling spectroscopy indicates that the crystals have a well-developed band gap, comparable to that in bulk TiO(2).

  9. Single-crystalline monolayer and multilayer graphene nano switches

    SciTech Connect

    Li, Peng; Cui, Tianhong; Jing, Gaoshan; Zhang, Bo; Sando, Shota

    2014-03-17

    Growth of monolayer, bi-layer, and tri-layer single-crystalline graphene (SCG) using chemical vapor deposition method is reported. SCG's mechanical properties and single-crystalline nature were characterized and verified by atomic force microscope and Raman spectroscopy. Electro-mechanical switches based on mono- and bi-layer SCG were fabricated, and the superb properties of SCG enable the switches to operate at pull-in voltage as low as 1 V, and high switching speed about 100 ns. These devices exhibit lifetime without a breakdown of over 5000 cycles, far more durable than any other graphene nanoelectromechanical system switches reported.

  10. Electron-irradiation induced changes in the phases and photocatalytic activity of TiO2 nanoparticles

    NASA Astrophysics Data System (ADS)

    Sapnar, K. B.; Dhole, S. D.; Bhoraskar, V. N.

    2012-04-01

    Samples of TiO2 nanoparticles, with mixed anatase and rutile phases, were irradiated with 6.5 MeV electrons at fluences, 1.5, 2.0, 2.5, 3.0, and 3.5 × 1015 e cm-2 and characterized by several methods. With increasing electron fluence, a continuous decrease in the average particle size from ˜80 nm to around 30 nm were observed along with a decrease in the rutile and the anatase phases of TiO2, but at different rates, and growth of the TiO2 brookite phase at slow rate. The photocatalytic activities of different electron irradiated TiO2 samples, in the photodegradation of methylene blue, were studied by recording UV-Vis absorption spectra of the respective solutions. On electron irradiation, even though the rutile phase in the TiO2 was decreasing, the photocatalytic activity of the nanoparticles increased continuously with fluence up to ˜3.0 × 1015 e cm-2, but decreased at 3.5 × 1015 e cm-2. The energy levels introduced by the brookite phase and the electron induced defects in TiO2 could have effectively reduced the electron-hole recombination rate in the absence of the rutile phase. The observed enhancement in the photocatalytic activity of the irradiated TiO2 is attributed to the formation of small size particles, the introduction of the oxygen related vacancies and other defects, the growth of the brookite phase, and increased absorption of radiation over the ultraviolet and visible range.

  11. Effect of TiO2 Nanoparticles on Tensile Strength of Dental Acrylic Resins.

    PubMed

    Shirkavand, Saeed; Moslehifard, Elnaz

    2014-01-01

    Background and aims. Adding further fillers to dental resins may enhance their physical characteristics. The aim of this study was to evaluate the tensile strength of heat-curing acrylic resin reinforced by TiO2nanoparticles added into the resin matrix. Materials and methods. Commercially available TiO2 nanoparticles were obtained and characterized using X-ray diffrac-tion (XRD) and scanning electron microscopy (SEM) to determine their crystalline structure, particle size and morphology. TiO2-acrylic resin nanocomposite was prepared by mixing 0.5, 1 and 2 (wt%) of surface modified TiO2 nanoparticles in an amalgamator providing three groups of samples. Before curing, the obtained paste was packed into steel molds. After cur-ing, the specimens were removed from the molds. The tensile strength test samples were prepared according to ISO 1567. Results. Two crystalline phases were found in TiO2 nanoparticles including: (i) anatase as the major one, and (ii) rutile. The average particle size calculated according to the Scherrer equation was 20.4 nm, showing a normal size distribution. According to SEM images, the nanocomposite with 1wt% TiO2 nanoparticles had a better distribution compared to other groups. In addition, the group by 1wt% TiO2 exhibited higher tensile strength with a significant difference compared to other groups. ANOVA showed significant differences between the contents of TiO2 particles in acrylic resin (F = 22.19; P < 0.001). Conclusion. A considerable increase in tensile strength was observed with titania NPs reinforcement agents in 1wt% by weight. Further increase of TiO2 nanoparticles decreased the tensile strength.

  12. Photodegradation of phenanthrene by N-doped TiO2 photocatalyst.

    PubMed

    Sirisaksoontorn, Weekit; Thachepan, Surachai; Songsasen, Apisit

    2009-07-15

    The photodegradation of phenanthrene has been catalyzed by nanostructures of TiO2 doped with nitrogen, N-doped TiO2. The N-doped TiO2 was prepared from the sol-gel reaction of Titanium(IV) bis(ethyl acetoacetato)diisopropoxide with 25% ammonia solution. The N-doped TiO2 was calcined at various temperatures from 300 to 700 degrees C. X-ray diffraction (XRD) results showed that N-doped TiO2 remained amorphous at 300 degrees C but anatase-to-rutile transformation started at 400 degrees C and was complete at 700 degrees C. The average particle size calculated from Scherrer's equation was in the range of 9-51 nm with surface area (S(BET)) of 253.7-4.8 m2/g. X-ray photoelectron spectroscopy (XPS) results confirmed the incorporation of nitrogen atoms (Ti-N bond) in the N-doped catalyst. Moreover, the percentage of nitrogen determined by Elemental analysis was 0.236% of N-doped calcined at 400 degrees C. UV-Vis reflection spectra indicated that N-doped TiO2 calcined at 400 degrees C shifted to the higher absorption edge in the range of visible light. N-doped TiO2 calcined at 400 degrees C successfully catalyzed the photodegradation of phenanthrene (80% conversion) whereas N-doped TiO2 calcined at 500 degrees C and P25 TiO2 failed as catalysts.

  13. Effect of TiO2 Nanoparticles on Tensile Strength of Dental Acrylic Resins

    PubMed Central

    Shirkavand, Saeed; Moslehifard, Elnaz

    2014-01-01

    Background and aims. Adding further fillers to dental resins may enhance their physical characteristics. The aim of this study was to evaluate the tensile strength of heat-curing acrylic resin reinforced by TiO2nanoparticles added into the resin matrix. Materials and methods. Commercially available TiO2 nanoparticles were obtained and characterized using X-ray diffrac-tion (XRD) and scanning electron microscopy (SEM) to determine their crystalline structure, particle size and morphology. TiO2-acrylic resin nanocomposite was prepared by mixing 0.5, 1 and 2 (wt%) of surface modified TiO2 nanoparticles in an amalgamator providing three groups of samples. Before curing, the obtained paste was packed into steel molds. After cur-ing, the specimens were removed from the molds. The tensile strength test samples were prepared according to ISO 1567. Results. Two crystalline phases were found in TiO2 nanoparticles including: (i) anatase as the major one, and (ii) rutile. The average particle size calculated according to the Scherrer equation was 20.4 nm, showing a normal size distribution. According to SEM images, the nanocomposite with 1wt% TiO2 nanoparticles had a better distribution compared to other groups. In addition, the group by 1wt% TiO2 exhibited higher tensile strength with a significant difference compared to other groups. ANOVA showed significant differences between the contents of TiO2 particles in acrylic resin (F = 22.19; P < 0.001). Conclusion. A considerable increase in tensile strength was observed with titania NPs reinforcement agents in 1wt% by weight. Further increase of TiO2 nanoparticles decreased the tensile strength. PMID:25587380

  14. Efficient Electrochemical Reduction of Nitrobenzene by Defect-Engineered TiO2-x Single Crystals.

    PubMed

    Liu, Chang; Zhang, Ai-Yong; Pei, Dan-Ni; Yu, Han-Qing

    2016-05-17

    TiO2 is a typical semiconductor and has been extensively used as an effective photocatalyst for environmental pollution control. But it could not be used as an electrochemical reductive catalyst because of its low electric conductivity and electrocatalytic activity. In this work, however, we demonstrate that TiO2 can act as an excellent cathodic electrocatalyst when its crystal shape, exposed facet and oxygen-stoichiometry are finely tailored by the local geometric and electronic structures. The defect-engineered TiO2-x single crystals dominantly exposed by high-energy {001} facets exhibits a high cathodic activity and great stability for electrochemical reduction of nitrobenzene, a typical refractory pollutant with high toxicity in environment. The single crystalline structure, the high-energy {001} facet and the defective oxygen vacancy of the defect-engineered TiO2-x single crystals are found to be mainly responsible for their cathodic superiority. With the findings in this work, a more practical non-Pd cathodic electrocatalyst could be prepared and applied for electrocatalytic reduction of refractory pollutants in water and wastewater, and extend the promising applications of TiO2 in the fields of environmental science. PMID:27128346

  15. Magnetism in single-crystalline CePtSn.

    SciTech Connect

    Bordallo, H. N.; Chang, S.; Lacerda, A. H.; Nakotte, H.; Takabatake, T.; Torikachvili, M. S.

    1999-08-04

    CePtSn exhibits two antiferromagnetic transitions at low temperatures. We report on magnetoresistance and in magnetization studies of single-crystalline CePtSn in magnetic fields up to 18 T. The data were taken to establish the magnetic phase diagrams for CePtSn in fields applied along the principal directions.

  16. Cavity polaritons in an organic single-crystalline rubrene microcavity

    NASA Astrophysics Data System (ADS)

    Tsuchimoto, Yuta; Nagai, Hikaru; Amano, Masamitsu; Bando, Kazuki; Kondo, Hisao

    2014-06-01

    We fabricated a single-crystalline rubrene microcavity using a simple solution technique and observed cavity polaritons in the microcavity at room temperature (RT). Large Rabi splitting energies were obtained from dispersion of the cavity polaritons. Furthermore, photoluminescence from the cavity polaritons was observed at RT. The findings will be of importance for the application of cavity polaritons.

  17. Effect of the crystalline constitution of TiO2 substrates on the growth of ultrathin Mo layer

    NASA Astrophysics Data System (ADS)

    Noirfalise, X.; Renaux, F.; Cossement, D.; Sebaihi, Noham; Lazzaroni, Roberto; Snyders, R.

    2012-11-01

    Metallic molybdenum was deposited by magnetron sputtering on amorphous and (110) rutile TiO2 substrates. An interfacial reaction between the deposited Mo and the TiO2 substrates generating Ti3 +, Ti2 + oxidation states is evidenced by X-ray photoelectron spectroscopy. Our XPS data suggest, as compared to the (110) rutile substrate, a higher reactivity of the amorphous TiO2 leading to a stronger Mo oxidation. In both cases, this reaction, leads to the formation of MoOx nanostructures at the interfaces. The growth mechanism of the Mo deposit as a function of the crystalline constitution of the TiO2 substrate was analyzed by processing the XPS data using the Quases ® software. The data reveal a layer-by-layer growth of the Mo deposit on the (110) rutile substrate and a Stranski-Krastanov growth on the amorphous one. We explain these different growth modes based on the TiO2 surface reactivity and electronic structure using the Cabrera-Mott theory. This explanation is supported by Time-of-Flight Secondary Ion Mass spectrometry profiling.

  18. Exposure to TiO2 nanoparticles increases Staphylococcusaureusinfection of HeLa cells

    NASA Astrophysics Data System (ADS)

    Xu, Yan; Wei, Ming-Tzo; Walker, Stephen. G.; Wang, Hong Zhan; Gondon, Chris; Brink, Peter; Guterman, Shoshana; Zawacki, Emma; Applebaum, Eliana; Rafailovich, Miriam; Ou-Yang, H. Daniel; Mironava, Tatsiana

    TiO2 is one of the most common nanoparticles in industry from food additives to energy generation. Even though TiO2 is also used as an anti-bacterial agent in combination with UV, we found that, in the absence of UV, exposure of HeLa cells to TiO2 nanoparticles largely increased their risk of bacterial invasion. HeLa cells cultured with low dosage rutile and anatase TiO2 nanoparticles (0.1 mg/ml) for 24 hrs prior to exposure to bacteria had 350% and 250% respectively more bacteria infected per cell. The increase was attributed to increased LDH leakage, and changes in the mechanical response of the cell membrane. On the other hand, macrophages exposed to TiO2 particles ingested 40% fewer bacteria, further increasing the risk of infection. In combination, these two factors raise serious concerns regarding the impact of exposure to TiO2 nanoparticles on the ability of organisms to resist bacterial infection.

  19. Phenol degradation by TiO2 photocatalysts combined with different pulsed discharge systems.

    PubMed

    Zhang, Yi; Lu, Jiani; Wang, Xiaoping; Xin, Qing; Cong, Yanqing; Wang, Qi; Li, Chunjuan

    2013-11-01

    Films of TiO2 nanotubes distributed over the inner surface of a discharge reactor cylinder (CTD) or adhered to a stainless steel electrode surface (PTD) in a discharge reactor were compared with a single-discharge (SD) system to investigate their efficiencies in phenol degradation. Morphology studies indicated that the TiO2 film was destroyed in the PTD system, but that there was no change in the CTD system after discharge. X-ray diffraction results revealed that the anatase phase of the original sample was preserved in the CTD system, but that an anatase-to-rutile phase transformation occurred in the PTD system after discharge. The highest efficiencies of phenol degradation and total organic carbon (TOC) mineralization were observed in the CTD system, and there was no decrease in phenol degradation efficiency upon reuse of a TiO2 film, indicating high catalysis activity and stability of the TiO2 photocatalysts in the combined treatment. TiO2 photocatalysts favored the formation of hydrogen peroxide and disfavored the formation of ozone. A greater degree of oxidation of intermediates and higher energy efficiency in phenol oxidation were observed with the TiO2-plasma systems, especially in the CTD system, compared to those with the SD system.

  20. ZnFe2O4-TiO2 Nanoparticles within Mesoporous MCM-41

    PubMed Central

    Tang, Aidong; Deng, Yuehua; Jin, Jiao; Yang, Huaming

    2012-01-01

    A novel nanocomposite ZnFe2O4-TiO2/MCM-41 (ZTM) was synthesized by a sol-gel method and characterized through X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), N2 adsorption-desorption, Raman spectroscopy, and ultraviolet visible (UV-vis) spectrophotometry. The results confirmed the incorporation of ZnFe2O4-TiO2 nanoparticles inside the pores of the mesoporous MCM-41 host without destroying its integrity. ZnFe2O4 nanoparticles can inhibit the transformation of anatase into rutile phase of TiO2. Incorporation of ZnFe2O4-TiO2 within MCM-41 avoided the agglomeration of nanoparticles and reduced the band gap energy of TiO2 to enhance its visible light photocatalytic activity. UV-vis absorption edges of ZTM nanocomposites redshifted with the increase of Zn/Ti molar ratio. The nanocomposite approach could be a potential choice for enhancing the photoactivity of TiO2, indicating an interesting application in the photodegradation and photoelectric fields. PMID:22919325

  1. ZnFe2O4-TiO2 nanoparticles within mesoporous MCM-41.

    PubMed

    Tang, Aidong; Deng, Yuehua; Jin, Jiao; Yang, Huaming

    2012-01-01

    A novel nanocomposite ZnFe(2)O(4)-TiO(2)/MCM-41 (ZTM) was synthesized by a sol-gel method and characterized through X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), N(2) adsorption-desorption, Raman spectroscopy, and ultraviolet visible (UV-vis) spectrophotometry. The results confirmed the incorporation of ZnFe(2)O(4)-TiO(2) nanoparticles inside the pores of the mesoporous MCM-41 host without destroying its integrity. ZnFe(2)O(4) nanoparticles can inhibit the transformation of anatase into rutile phase of TiO(2). Incorporation of ZnFe(2)O(4)-TiO(2) within MCM-41 avoided the agglomeration of nanoparticles and reduced the band gap energy of TiO(2) to enhance its visible light photocatalytic activity. UV-vis absorption edges of ZTM nanocomposites redshifted with the increase of Zn/Ti molar ratio. The nanocomposite approach could be a potential choice for enhancing the photoactivity of TiO(2), indicating an interesting application in the photodegradation and photoelectric fields.

  2. Synthesis and visible light photoactivity of anatase Ag, and garlic loaded TiO2 nanocrystalline catalyst

    EPA Science Inventory

    An excellent visible light activated Ag and S doped TiO2 nanocatalyst was prepared by using AgNO3 and garlic (Allium sativum) as Ag+ and sulfur sources, respectively. The catalyst resisted the change from anatase to rutile phase even at calcination at 700 oC. The photocatalytic e...

  3. Electronic structure and room temperature ferromagnetism of C doped TiO2

    NASA Astrophysics Data System (ADS)

    Ablat, Abduleziz; Wu, Rong; Mamat, Mamatrishat; Ghupur, Yasin; Aimidula, Aimierding; Bake, Muhammad Ali; Gholam, Turghunjan; Wang, Jiaou; Qian, Haijie; Wu, Rui; Ibrahim, Kurash

    2016-10-01

    C-doped TiO2 nanoparticles were successfully synthesized using a simple hydrothermal synthesis method. After this preparation, a portion of the samples were annealed separately in air on the one hand, and in argon on the other, and another portion remained untreated. The results of X-ray diffraction show that the untreated samples primarily display anatase and rutile structures. However, after annealing, the samples displayed the rutile structure only. The Ti K-edge and L-edge Near Edge X-ray Absorption Fine Structure analyses clearly show that C atoms were successfully incorporated into the TiO2 host lattice. All doped samples exhibit ferromagnetism at room temperature. The saturation magnetization (Ms) and coercive fields (Hc) tend to decrease after the samples are annealed in argon and in air. The maximum Ms of the untreated samples was approximately 0.038 emu/g.

  4. Growth of TiO2 with thermal and plasma enhanced atomic layer deposition.

    PubMed

    Tallarida, Massimo; Friedrich, Daniel; Städter, Matthias; Michling, Marcel; Schmeisser, Dieter

    2011-09-01

    We show a comparative study of the TiO2 ALD with TTIP and either O2 or O2-plasma on Si/SiO2 substrates. In particular we compare the surface morphology and crystalline phase by means of Atomic Force Microscopy (AFM), X-ray Photoelectron Spectroscopy (XPS) and X-ray Absorption Spectroscopy (XAS) for different O2-plasma procedures upon changing the time between cycles and the N2-purging pressure. The AFM images show that already these parameters may induce structural changes in the TiO2 films grown by ALD, with the formation of crystallites with average lateral width varying between 15 and 80 nm. By means of XAS we also found that the crystallites have mixed anatase and rutile crystalline phases and that smaller crystallites have a greater rutile component than the larger ones. PMID:22097528

  5. Morphological and phase evolution of TiO 2 nanocrystals prepared from peroxotitanate complex aqueous solution: Influence of acetic acid

    NASA Astrophysics Data System (ADS)

    Chang, Jeong Ah; Vithal, Muga; Baek, In Chan; Seok, Sang Il

    2009-04-01

    Nanosized anatase and rutile TiO 2 having different shape, phase and size have been prepared from aqueous solutions of peroxo titanium complex starting from titanium(IV) isopropoxide (TTIP), acetic acid and hydrogen peroxide (H 2O 2) in water/isopropanol media by a facile sol-gel process. The TiO 2 nanocrystals are characterized by powder X-ray diffraction (XRD), Raman spectroscopy, FT-IR spectroscopy, TEM, high resolution transmission electron microscopy (HRTEM) and selected area electron diffraction (SAED) techniques. The influence of pH and the sequence of addition of reaction contents on the phase and morphology of TiO 2 are studied. The reasons for the observation of only anatase and/or mixture of anatase and rutile are given.

  6. Osteoconductivity and Hydrophilicity of TiO(2) Coatings on Ti Substrates Prepared by Different Oxidizing Processes.

    PubMed

    Yamamoto, Dai; Kawai, Ikki; Kuroda, Kensuke; Ichino, Ryoichi; Okido, Masazumi; Seki, Azusa

    2012-01-01

    Various techniques for forming TiO(2) coatings on Ti have been investigated for the improvement of the osteoconductivity of Ti implants. However, it is not clear how the oxidizing process affects this osteoconductivity. In this study, TiO(2) coatings were prepared using the following three processes: anodizing in 0.1 M H(3)PO(4) or 0.1 M NaOH aqueous solution; thermal oxidation at 673 K for 2 h in air; and a two-step process of anodizing followed by thermal oxidation. The oxide coatings were evaluated using SEM, XRD, and XPS. The water contact angle on the TiO(2) coatings was measured as a surface property. The osteoconductivity of these samples was evaluated by measuring the contact ratio of formed hard tissue on the implanted samples (defined as the R(B-I) value) after 14 d implantation in rats' tibias. Anatase was formed by anodizing and rutile by thermal oxidation, but the difference in the TiO(2) crystal structure did not influence the osteoconductivity. Anodized TiO(2) coatings were hydrophilic, but thermally oxidized TiO(2) coatings were less hydrophilic than anodized TiO(2) coatings because they lacked in surface OH groups. The TiO(2) coating process using anodizing without thermal oxidation gave effective improvement of the osteoconductivity of Ti samples.

  7. Synthesis and Modification of Zn-doped TiO2 Nanoparticles for the Photocatalytic Degradation of Tetracycline.

    PubMed

    Pang, Shuo; Huang, Ji-Guo; Su, Yun; Geng, Bo; Lei, Su-Yuan; Huang, Yu-Ting; Lyu, Cong; Liu, Xing-Juan

    2016-09-01

    The synthesis of Zn-doped TiO2 nanoparticles by solgel method was investigated in this study, as well as its modification by H2 O2 . The catalyst was characterized by transmission electron microscopy, X-ray diffraction, Brunauer-Emmett-Teller, UV-visible reflectance spectra and X-ray photoelectron spectroscopy (XPS). The results indicated that doping Zn into TiO2 nanoparticles could inhibit the transformation from anatase phase to rutile phase. Zn existed as the second valence oxidation state in the Zn-doped TiO2 . Zn-doped TiO2 that was synthesized by 5% Zn doping at 450°C exhibited the best photocatalytic activity. Then, the H2 O2 modification further enhanced the photocatalytic activity. Zn doping and H2 O2 modifying narrowed the band gap and efficiently increased the optical absorption in visible region. The optimal degradation rate of tetracycline by Zn-doped TiO2 and H2 O2 modified Zn-doped TiO2 was 85.27% and 88.14%. Peroxide groups were detected in XPS analysis of H2 O2 modified Zn-doped TiO2 , favoring the adsorption of visible light. Furthermore, Zn-doped TiO2 modified by H2 O2 had relatively good reusability, exhibiting a potential practical application for tetracycline's photocatalytic degradation.

  8. Toxicity of TiO2 Nanoparticles to Escherichia coli: Effects of Particle Size, Crystal Phase and Water Chemistry

    PubMed Central

    Lin, Xiuchun; Li, Jingyi; Ma, Si; Liu, Gesheng; Yang, Kun; Tong, Meiping; Lin, Daohui

    2014-01-01

    Controversial and inconsistent results on the eco-toxicity of TiO2 nanoparticles (NPs) are commonly found in recorded studies and more experimental works are therefore warranted to elucidate the nanotoxicity and its underlying precise mechanisms. Toxicities of five types of TiO2 NPs with different particle sizes (10∼50 nm) and crystal phases were investigated using Escherichia coli as a test organism. The effect of water chemistry on the nanotoxicity was also examined. The antibacterial effects of TiO2 NPs as revealed by dose-effect experiments decreased with increasing particle size and rutile content of the TiO2 NPs. More bacteria could survive at higher solution pH (5.0–10.0) and ionic strength (50–200 mg L−1 NaCl) as affected by the anatase TiO2 NPs. The TiO2 NPs with anatase crystal structure and smaller particle size produced higher content of intracellular reactive oxygen species and malondialdehyde, in line with their greater antibacterial effect. Transmission electron microscopic observations showed the concentration buildup of the anatase TiO2 NPs especially those with smaller particle sizes on the cell surfaces, leading to membrane damage and internalization. These research results will shed new light on the understanding of ecological effects of TiO2 NPs. PMID:25310452

  9. The provenance of rutile.

    USGS Publications Warehouse

    Force, E.R.

    1980-01-01

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

  10. Metal oxide nanocluster-modified TiO2 as solar activated photocatalyst materials

    NASA Astrophysics Data System (ADS)

    Fronzi, Marco; Iwaszuk, Anna; Lucid, Aoife; Nolan, Michael

    2016-02-01

    In this review we describe our work on new TiO2 based photocatalysts. The key concept in our work is to form new composite structures by the modification of rutile and anatase TiO2 with nanoclusters of metal oxides and our density functional theory (DFT) level simulations are validated by experimental work synthesizing and characterizing surface-modified TiO2. We use DFT to show that nanoclusters of different metal oxides, TiO2, SnO/SnO2, PbO/PbO2, NiO and CuO can be adsorbed at rutile and anatase surfaces and can induce red shifts in the absorption edge to enable visible light absorption which is the first key requirement for a practical photocatalyst. We furthermore determine the origin of the red shift and discuss the factors influencing this shift and the fate of excited electrons and holes. For p-block metal oxides we show how the oxidation state of Sn and Pb can be used to tune both the magnitude of the red shift and also its mechanism. Finally, aiming to make our models more realistic, we present some new results on the stability of water at rutile and anatase surfaces and the effect of water on oxygen vacancy formation and on nanocluster modification. These nanocluster-modified TiO2 structures form the basis of a new class of photocatalysts which will be useful in oxidation reactions and with the suitable choice of nanocluster modifier can be applied to CO2 reduction.

  11. 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.

  12. Structural, electronic, and dynamical properties of Pca21-TiO2 by first principles

    NASA Astrophysics Data System (ADS)

    Abbasnejad, M.; Mohammadizadeh, M. R.; Maezono, R.

    2012-03-01

    First-principles calculations of the structural, electronic, and mechanical properties of the modified fluorite structure of TiO2 with Pca21 symmetry are obtained using the plane-wave pseudopotential density functional theory. The results indicate that Pca21-TiO2 is a semiconductor with an indirect band gap. The calculated static dielectric constants are larger than those of anatase and brookite, but they are much smaller than those of rutile. The calculated bulk modulus using the equation of state is in good agreement with that calculated from elastic constants. The calculated bulk modulus is in agreement with a recent theoretical and experimental report, which confirms that the experimentally claimed structure (cubic fluorite phase) can be Pca21-TiO2.

  13. Raman spectral analysis of TiO2 thin films doped with rare-earth samarium.

    PubMed

    Yang, Chang-Hu; Ma, Zhong-Quan

    2012-08-01

    TiO(2) thin films doped with rare-earth samarium were prepared on a quartz plate by the sol-gel/spin-coating technique. The samples were annealed at 700 °C to 1100 °C, and the Raman spectra of the samples were obtained. Analyses of Raman spectra show that samarium doping can inhibit the anatase-rutile phase transition. Samarium doping can refine grains of TiO(2) thin films and increase the internal stress, thereby preventing lattice vibration. Nanocrystalline TiO(2) thin films obviously show the phonon confinement effect, i.e., the blueshift of characteristic Raman peak and full width at half-height increase, and the peak shapes asymmetrically broaden with a decrease in the grain sizes of the samples.

  14. Phase transformations in nanocrystalline TiO 2 milled in different milling atmospheres

    NASA Astrophysics Data System (ADS)

    Pan, Xiaoyan; Ma, Xueming

    2004-11-01

    The structural evolution of nanocrystalline TiO 2 milled in different milling atmospheres was studied by X-ray diffraction (XRD), Raman spectroscopy and X-ray photoelectron spectroscopy. Rietveld refinements of the XRD data showed that high-energy ball milling induced the transformations from anatase to srilankite and rutile at room temperature and ambient pressure. The milling atmospheres with different oxygen partial pressures had an influence on the transformation kinetics of anatase. When the nanocrystalline TiO 2 powders were, respectively, milled in oxygen, air and nitrogen atmospheres, the transformation rates of anatases in turn increased with a decrease in oxygen partial pressure of the milling atmosphere, due to the reducing concentration of oxygen vacancies in the milled TiO 2 lattice.

  15. DFT study of coverage-depended adsorption of NH3 on TiO2-B (100) surface.

    PubMed

    Guo, Xiao-Jing; Liu, Weijia; Fang, Wei; Cai, Lu; Zhu, Yudan; Lu, Linghong; Lu, Xiaohua

    2012-12-28

    A previous study showed that TiO(2)-B (100) surface is very unique. It is characterised by high activity and a loose structure. In this study, we studied the adsorption of ammonia on TiO(2)-B (100) surface at coverages ranging from 1/6 ML to 1 ML using ab initio density functional calculations. We also investigated the adsorption of an isolated ammonia molecule on TiO(2)-B (001) surface to compare the different activities of TiO(2)-B (100) and (001) surfaces towards NH(3). The results showed that the TiO(2)-B (100) surface is more reactive towards NH(3) molecule than TiO(2)-B (001) surface, and the Lewis acid site on TiO(2)-B (100) surface is more acidic. The decrease rate of the average molecular adsorption energy of NH(3) with coverage on TiO(2)-B (100) surface is substantially lower than that on a rutile (011) surface above 1/2 ML coverage due to the open structure of TiO(2)-B (100) surface. The average molecular adsorption energy shows a linear dependence on the coverage of y = 111.0 - 36.3x on TiO(2)-B (100) surface. The possibility of NH(3) molecule onto the Ti(5c) site is nearly equal to forming a dimer with adsorbed NH(3) on TiO(2)-B (100) surface at 5/6 ML coverage. PMID:22955312

  16. Photocatalytic degradation of acetaminophen in modified TiO2 under visible irradiation.

    PubMed

    Dalida, Maria Lourdes P; Amer, Kristine Marfe S; Su, Chia-Chi; Lu, Ming-Chun

    2014-01-01

    This study investigated the photocatalytic degradation of acetaminophen (ACT) in synthetic titanium dioxide (TiO2) solution under a visible light (λ >440 nm). The TiO2 photocatalyst used in this study was synthesized via sol-gel method and doped with potassium aluminum sulfate (KAl(SO4)2) and sodium aluminate (NaAlO2). The influence of some parameters on the degradation of acetaminophen was examined, such as initial pH, photocatalyst dosage, and initial ACT concentration. The optimal operational conditions were also determined. Results showed that synthetic TiO2 catalysts presented mainly as anatase phase and no rutile phase was observed. The results of photocatalytic degradation showed that LED alone degraded negligible amount of ACT but with the presence of TiO2/KAl(SO4)2, 95% removal of 0.10-mM acetaminophen in 540-min irradiation time was achieved. The synthetic TiO2/KAl(SO4)2 presented better photocatalytic degradation of acetaminophen than commercially available Degussa P-25. The weak crystallinity of synthesized TiO2/NaAlO2 photocatalyst showed low photocatalytic degradation than TiO2/KAl(SO4)2. The optimal operational conditions were obtained in pH 6.9 with a dose of 1.0 g/L TiO2/KAl(SO4)2 at 30 °C. Kinetic study illustrated that photocatalytic degradation of acetaminophen fits well in the pseudo-first order model. Competitive reactions from intermediates affected the degradation rate of ACT, and were more obvious as the initial ACT concentration increased.

  17. A first-principles study of the dielectric properties of TiO2 polymorphs

    NASA Astrophysics Data System (ADS)

    Thilagam, A.; Simpson, D. J.; Gerson, A. R.

    2011-01-01

    We present an analysis of the dielectric properties of the three polymorphs of TiO2 (rutile, anatase and brookite phases), using ab initio time-dependent density functional perturbation theory based on the Vignale-Kohn functional. We implement this functional, which incorporates many-body effects, using the periodic program BAND. The improved result for the density of states spectra for brookite is suggestive of increased titanium ion Jahn-Teller effects for this phase. The imaginary and real components of the frequency-dependent dielectric functions show notable dielectric anisotropies, with implications for excitonic interactions, for all three common phases of TiO2. Comparison of the electron energy-loss spectrum for undoped and doped rutile and anatase reveals the critical role of collective charge excitations in photocatalytic mechanisms. The correlation between plasmon peaks present at lower energies and decreased photocatalytic activity due to substitutional aluminum doping in combination with oxygen vacancies in rutile and anatase is highlighted. Moreover, there is clear correlation between dielectric properties and the microstructure of the TiO2 polymorphs as suggested via the framework of the Born effective charge and Hirshfeld charge distribution schemes.

  18. Microstructure and Transport properties of epitaxial VO2 thin films on TiO2 substrates

    NASA Astrophysics Data System (ADS)

    Lu, Jiwei

    2008-10-01

    Vanadium oxides are paradigms of strongly correlated oxides and have attracted attention because of the metal insulator transitions (MIT) that several of the oxides and sub-oxides exhibit. In particular, VO2 has a metal--semiconductor transition at 340 K. This transition in VO2 combines the properties of a pure Mott Hubbard electronic transition with those of a Peierls structural transition. The Mott transition is responsible for the extreme speed of the optical switching that has been observed (faster than 100 fs). Understanding this transition and how to control it remains a challenge for both theory and experimental physics. We used a novel deposition technique, Reactive Bias Target Ion Beam Deposition, to grow 40 nm epitaxial VO2 thin films on rutile TiO2 substrates with various crystal orientations. X-ray diffraction (XRD) was used to explore the epitaxy of VO2 and we found that all VO2 thin films on TiO2 substrates showed tetragonal symmetry at room temperature due to the constrain from rutile substrates. We also characterized the metal-insulator transition of VO2 films as the function of the crystal orientation of rutile TiO2. We also characterized the anisotropy of VO2 thin films. In collaboration with Kevin West and Stuart Wolf, University of Virginia.

  19. Theoretical investigations of Ni- and Cu-doped TiO2

    NASA Astrophysics Data System (ADS)

    Esakki muthuraju, M.; Mahesh, R.; Sreekanth, T.; Venugopal Reddy, P.

    2014-03-01

    The electronic, magnetic and optical properties of rutile Ti1-xTMxO2 (where TM: Ni, Cu and x = 0.25) have been investigated by the density functional theory with the plane wave self consistent field method. For the calculation of exchange correlation potential, the local density approximation along with Hubbard correction (LDA +U) was used. Electronic, magnetic and optical properties were calculated using 12 atoms supercell of rutile TiO2 with one Ti atom replaced by a dopant transition metal atom. The band structure of doped rutile phase indicates the reduction of band gap leading to improvement in the photocatalytic properties of TiO2 as well as enhancement in its magnetic properties. The observed magnetism is explained on the basis of spin polarization of d states of Ti with dopants. Optical calculations by full potential, linear augmented plane wave plus local orbital (FP-LAPW+lo) method with ELK code established the presence of optical transitions in the visible light region. These theoretical calculations gave a meaningful information and excellent prediction to develop TiO2 for spintronics applications and photocatalytic applications in the visible region.

  20. Hydrothermal growth of TiO2 nanorod arrays and in situ conversion to nanotube arrays for highly efficient quantum dot-sensitized solar cells.

    PubMed

    Huang, Hui; Pan, Lei; Lim, Chiew Keat; Gong, Hua; Guo, Jun; Tse, Man Siu; Tan, Ooi Kiang

    2013-09-23

    TiO2 nanorod (NR) and nanotube (NT) arrays grown on transparent conductive substrates are attractive electrode for solar cells. In this paper, TiO2 NR arrays are hydrothermally grown on FTO substrate, and are in situ converted into NT arrays by hydrothermally etching. The TiO2 NR arrays are reported as single crystalline, but the TiO2 NR arrays are demonstrated to be polycrystalline with a bundle of 2-5 nm single crystalline nanocolumns grown along [001] throughout the whole NR from bottom to top. TiO2 NRs can be converted to NTs by hydrothermal selective etching of the (001) core and remaining the inert sidewall of (110) face. A growth mechanism of the NR and NT arrays is proposed. Quantum dot-sensitized solar cells (QDSCs) are fabricated by coating CdSe QDs on to the TiO2 arrays. After conversion from NRs to NTs, more QDs can be filled in the NTs and the energy conversion efficiency of the QDSCs almost double.

  1. Photocatalytic Activity of W-Doped TiO2 Nanofibers for Methylene Blue Dye Degradation.

    PubMed

    Song, Yo-Seung; Cho, Nam-Ihn; Lee, Myung-Hyun; Kim, Bae-Yeon; Lee, Deuk Yong

    2016-02-01

    Photocatalytic degradation of methylene blue (MB) in water was examined using W-doped TiO2 nanofibers prepared by a sol-gel derived electrospinning and subsequent calcination for 4 h at 550 degrees C. Different concentrations of W dopant in the range of 0 to 8 mol% were synthesized to evaluate the effect of W concentration on the photocatalytic activity of TiO2. XRD results indicated that the undoped TiO2 is composed of anatase and rutile phases. The rutile phase was transformed to anatase phase completely with the W doping. Among W-TiO2 catalysts, the 2 mol% W-TiO2 catalyst showed the highest MB degradation rate. The degradation kinetic constant increased from 1.04 x 10(-3) min(-1) to 3.54 x 10(-3) min(-1) with the increase of W doping from 0 to 2 mol%, but decreased down to 1.77 x 10(-3) min(-1) when the W content was 8 mol%. It can be concluded that the degradation of MB under UV radiation was more efficient with W-TiO2 catalysts than with pure TiO2-

  2. Photocatalytic Activity of W-Doped TiO2 Nanofibers for Methylene Blue Dye Degradation.

    PubMed

    Song, Yo-Seung; Cho, Nam-Ihn; Lee, Myung-Hyun; Kim, Bae-Yeon; Lee, Deuk Yong

    2016-02-01

    Photocatalytic degradation of methylene blue (MB) in water was examined using W-doped TiO2 nanofibers prepared by a sol-gel derived electrospinning and subsequent calcination for 4 h at 550 degrees C. Different concentrations of W dopant in the range of 0 to 8 mol% were synthesized to evaluate the effect of W concentration on the photocatalytic activity of TiO2. XRD results indicated that the undoped TiO2 is composed of anatase and rutile phases. The rutile phase was transformed to anatase phase completely with the W doping. Among W-TiO2 catalysts, the 2 mol% W-TiO2 catalyst showed the highest MB degradation rate. The degradation kinetic constant increased from 1.04 x 10(-3) min(-1) to 3.54 x 10(-3) min(-1) with the increase of W doping from 0 to 2 mol%, but decreased down to 1.77 x 10(-3) min(-1) when the W content was 8 mol%. It can be concluded that the degradation of MB under UV radiation was more efficient with W-TiO2 catalysts than with pure TiO2- PMID:27433681

  3. Influences of TiO2 phase structures on the structures and photocatalytic hydrogen production of CuOx/TiO2 photocatalysts

    NASA Astrophysics Data System (ADS)

    Liu, Yuanxu; Wang, Zhonglei; Huang, Weixin

    2016-12-01

    CuOx/TiO2 photocatalysts employing TiO2 with different phase structures as well as P25 as supports were prepared, and their structures and activity for photocatalytic H2 production in methanol/water solution under simulated solar light were comparatively studied. Structural characterization results demonstrated that the TiO2 phase structure strongly affects the CuOx-TiO2 interaction and copper species in various CuOx/TiO2 photocatalysts. The Cu2O-rutile TiO2 interaction is much stronger than the Cu2O-anatase TiO2 interaction, facilitates the interfacial charge transfer process within the Cu2O-rutile TiO2 heterojunction but disables supported Cu2O to catalyze the hole-participated methanol oxidation. The Cu2O-anatase TiO2 heterojunction with the appropriate Cu2O-anatase TiO2 interaction and thus the balancing efficiencies between the interfacial charge transfer process and hole-participated methanol oxidation is most photocatalytic active, and CuOx/P25 with the largest population of Cu2O-anatase TiO2 heterojunction exhibits the highest photocatalytic H2 production. These results provide novel insights in the applied surface science of CuOx/TiO2 photocatalysts.

  4. A pseudo-single-crystalline germanium film for flexible electronics

    SciTech Connect

    Higashi, H.; Yamada, S.; Kanashima, T.; Hamaya, K.; Kasahara, K.; Park, J.-H.; Miyao, M.; Kudo, K.; Okamoto, H.; Moto, K.; Tsunoda, I.

    2015-01-26

    We demonstrate large-area (∼600 μm), (111)-oriented, and high-crystallinity, i.e., pseudo-single-crystalline, germanium (Ge) films at 275 °C, where the temperature is lower than the softening temperature of a flexible substrate. A modulated gold-induced layer exchange crystallization method with an atomic-layer deposited Al{sub 2}O{sub 3} barrier and amorphous-Ge/Au multilayers is established. From the Raman measurements, we can judge that the crystallinity of the obtained Ge films is higher than those grown by aluminum-induced-crystallization methods. Even on a flexible substrate, the pseudo-single-crystalline Ge films for the circuit with thin-film transistor arrays can be achieved, leading to high-performance flexible electronics based on an inorganic-semiconductor channel.

  5. Freestanding single-crystalline magnetic structures fabricated by ion bombardment

    SciTech Connect

    Schoenherr, P.; Bischof, A.; Boehm, B.; Eib, P.; Grimm, S.; Gross, L.; Allenspach, R.; Alvarado, S. F.

    2015-01-19

    Starting from an ultrathin Fe film grown epitaxially on top of a GaAs(001) substrate, we show that freestanding structures can be created by ion-beam treatment. These structures are single-crystalline blisters and only a few nanometers thick. Anisotropic stress in the rim of a blister induces magnetic domain states magnetized in the direction normal to the blister edge. Experimental evidence is provided that the lateral size can be confined by starting from a nanostructured template.

  6. TiS2 transformation into S-doped and N-doped TiO2 with visible-light catalytic activity

    NASA Astrophysics Data System (ADS)

    Lin, Yu-Chen; Chien, Tzu-En; Lai, Po-Chih; Chiang, Yu-Hsien; Li, Kun-Lin; Lin, Jong-Liang

    2015-12-01

    S-doped rutile has been prepared for the first time by hydrothermal reaction of TiS2 in hydrochloric acid at a low temperature (180 °C), with the S atoms in three states of Tisbnd Ssbnd Ti, Tisbnd Ssbnd O and SO4. TiS2 in nitric acid can also be transformed into TiO2, but with mixed phases of anatase and rutile, containing nitrogen atoms at interstitial sites in the form of Tisbnd Osbnd N or Tisbnd Nsbnd O. The Ssbnd TiO2 catalyst shows a better visible-light reactivity toward adsorbed methylene blue (MB) photodegradation and hydroxylation of terephthalic acid with respect to the Nsbnd TiO2. The possible reasons leading to the high photoactivity of the Ssbnd TiO2 are discussed in terms of the incorporated sulfur states.

  7. Fabrication and characterization of brookite-rich, visible light-active TiO2 films for water splitting

    SciTech Connect

    Pan, Hui; Qiu, Xiaofeng; Ivanov, Ilia N; Meyer III, Harry M; Wang, Wei; Zhu, Wenguang; Paranthaman, Mariappan Parans; Zhang, Zhenyu; Eres, Gyula; Gu, Baohua

    2009-01-01

    We report that mild oxidation of Ti foils in air results in brookite-rich titanium oxide (TiO2) films with similar spectral response to that of dye-sensitized TiO2. X-ray powder diffraction and Raman spectroscopy show that the onset of brookite formation occurs at 500 8C, and the material is characterized by a strong absorption band in the visible spectral range. The first-principle calculations show that enhanced visible light absorption correlates with the presence of Ti interstitials. Photocurrent density measurements of water splitting reveal that the brookite-rich TiO2 exhibits the highest photocatalytic performance among the different forms of TiO2 produced by oxidation of Ti foils. With increasing oxidation temperature transformation to the rutile phase accompanied by declining visible range photoactivity is observed.

  8. Preparation of photoactive nitrogen-doped rutile

    NASA Astrophysics Data System (ADS)

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

    2013-02-01

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

  9. Preparation, testing and characterization of doped TiO2 active in the peroxidation of biomolecules under visible light.

    PubMed

    Bacsa, Revathi; Kiwi, John; Ohno, Teruhisa; Albers, Peter; Nadtochenko, Victor

    2005-03-31

    Doped TiO2 samples using different preparative procedures were synthesized using either urea or thiourea leading to N- or S-doped TiO2. Photocatalytic peroxidation and oxidation (mineralization) of phosphatidylethanolamine (PE) lipid with doped TiO2 were carried out under light irradiation lambda > 410 nm. The formation of conjugated double bonds in PE molecules was followed to detect the formation of peroxy radicals (peroxidation index) under light excitation (lambda > 410 nm) when doped TiO2 was used. The kinetics of CO2 production was monitored during the mineralization of PE. Colored TiO2 powders were studied in detail by different and complementary physicochemical techniques. The band gap energies of colored TiO2 were determined by diffuse reflectance spectroscopy (DRS). The visible absorption shoulder of TiO2 was observed to follow Urbach's law. The variation of the transient decay after 354 nm laser pulse excitation does not correlate with the different N- and S-TiO2 doping levels introduced by the addition of urea or thiourea. This suggests that the states (recombination centers or traps) introduced by the doping are not effective in varying the decay kinetics within the nanosecond and microsecond time scale. Elemental analysis shows comparable amounts of S- and N-doping of TiO2 when thiourea is used as dopant. X-ray diffraction reveals no rutile in S-TiO2 samples heated to 600 degrees C, suggesting that the addition of sulfur precludes rutilization during sample crystallization. X-ray photoelectron spectroscopy (XPS) of the S-TiO2 samples confirms the preferential localization of S on the 20 topmost layers of S-TiO2 upon calcination at 500 degrees C for 2 h.

  10. Theoretical limits of thermoelectric figure of merit in n -type TiO2 polymorphs

    NASA Astrophysics Data System (ADS)

    Bayerl, Dylan; Kioupakis, Emmanouil

    2015-04-01

    We calculate the conduction-band structures and n -type thermoelectric transport properties for the TiO2 polymorphs rutile, anatase, and brookite from first principles within the constant-relaxation-time approximation. Although the Seebeck coefficient is nearly isotropic in all polymorphs, the power factor is anisotropic and takes its largest values along [100] in rutile and anatase and along [010] in brookite. We also identify the free-carrier concentrations and temperatures that maximize the power factor. Our results for the theoretical upper bounds of the figure of merit at high temperature show that optimized rutile exhibits thermoelectric conversion efficiency that is superior to anatase and brookite and can reach values desirable for waste-heat recovery applications.

  11. TiO2 film properties as a function of processing temperature, volume 3

    NASA Technical Reports Server (NTRS)

    Fitzgibbons, E. T.; Sladek, K. J.; Hartwig, W. H.

    1972-01-01

    Thin film TiO2 was produced at 150 C by chemical vapor deposition using hydrolysis of tetraisopropyl titanate. Films were amorphous as grown, but annealing in air caused crystallization, with anatase formed beginning at 350 C and rutile at 700 C. Density and index of refraction increased substantially with increasing anneal temperature, while etch susceptibility in HF and H2SO4 decreased. Comparison with literature data showed two groups of processes. One group yields films having properties that gradually approach those of rutile with increasing process temperature. The other group gives rutile directly at moderate temperatures. Deposition of amorphous film followed by etching and annealing is suggested as a means for pattern definition.

  12. Effect of Nb doping on structural, optical and photocatalytic properties of flame-made TiO2 nanopowder.

    PubMed

    Michalow, Katarzyna A; Flak, Dorota; Heel, Andre; Parlinska-Wojtan, Magdalena; Rekas, Mieczyslaw; Graule, Thomas

    2012-11-01

    TiO(2):Nb nanopowders within a dopant concentration in the range of 0.1-15 at.% were prepared by one-step flame spray synthesis. Effect of niobium doping on structural, optical and photocatalytic properties of titanium dioxide nanopowders was studied. Morphology and structure were investigated by means of Brunauer-Emmett-Teller isotherm, X-ray diffraction and transmission electron microscopy. Diffuse reflectance and the resulting band gap energy were determined by diffuse reflectance spectroscopy. Photocatalytic activity of the investigated nanopowders was revised for the photodecomposition of methylene blue (MB), methyl orange (MO) and 4-chlorophenol under UVA and VIS light irradiation. Commercial TiO(2)-P25 nanopowder was used as a reference. The specific surface area of the powders was ranging from 42.9 m(2)/g for TiO(2):0.1 at.% Nb to 90.0 m(2)/g for TiO(2):15 at.% Nb. TiO(2):Nb particles were nanosized, spherically shaped and polycrystalline. Anatase was the predominant phase in all samples. The anatase-related transition was at 3.31 eV and rutile-related one at 3.14 eV. TiO(2):Nb nanopowders exhibited additional absorption in the visible range. In comparison to TiO(2)-P25, improved photocatalytic activity of TiO(2):Nb was observed for the degradation of MB and MO under both UVA and VIS irradiation, where low doping level (Nb < 1 at.%) was the most effective. Niobium doping affected structural, optical and photocatalytic properties of TiO(2). Low dopant level enhanced photocatalytic performance under UVA and VIS irradiation. Therefore, TiO(2):Nb (Nb < 1 at.%) can be proposed as an efficient selective solar light photocatalyst. PMID:23054731

  13. Bioactive TiO2 fiber films prepared by electrospinning method.

    PubMed

    Chen, S J; Yu, H Y; Yang, B C

    2013-01-01

    Electrospining method was used to prepare bioactive TiO(2) fibers films in this study. The acetic acid/ethanol/tetrabutyl titanate/polyvinylpyrrolidone (PVP) solvent system was used as precursor for the electrospining. The TiO(2) fiber structures (including its fiber diameter, morphology, and phase composition) could be controlled by changing feeding rate, PVP concentration and sinter temperature. The fiber films were subjected to simulated body fluid soaking experiments and MG63 cells culture experiments to study their bioactivity. According to the X-ray diffraction and MTT assay results, the fiber containing with anatase showed better apatite formation ability than that without anatase at the early stage, while cell proliferated on anatase-rutile TiO(2) fiber was better than that on other samples (p < 0.05).Some string beads in the fiber were beneficial for apatite formation, while the cell proliferated best on the fiber film without string beads (p < 0.05). The fiber with a diameter of 200 nm had the best apatite formation ability and osteoblast compatibility (p < 0.05). The results showed that the TiO(2) fiber film structure had great influence on its bioactivity. It indicated that the electronspining method is an effective way to prepare bioactive titania fiber films, and it is possible to control the structure of the films in the spinning process to optimize the bioactivity of TiO(2) fiber.

  14. Synthesis and Characterization of Photocatalytic TiO 2 -ZnFe 2 O 4 Nanoparticles

    DOE PAGESBeta

    Srinivasan, Sesha S.; Wade, Jeremy; Stefanakos, Elias K.

    2006-01-01

    A new coprecipimore » tation/hydrolysis synthesis route is used to create a TiO 2 -ZnFe 2 O 4 nanocomposite that is directed towards extending the photoresponse of TiO 2 from UV to visible wavelengths ( > 400   nm ). The effect of TiO 2 's accelerated anatase-rutile phase transformation due to the presence of the coupled ZnFe 2 O 4 narrow-bandgap semiconductor is evaluated. The transformation's dependence on pH, calcinations temperature, particle size, and ZnFe 2 O 4 concentration has been analyzed using XRD, SEM, and UV-visible spectrometry. The requirements for retaining the highly photoactive anatase phase present in a ZnFe 2 O 4 nanocomposite are outlined. The visible-light-activated photocatalytic activity of the TiO 2 -ZnFe 2 O 4 nanocomposites has been compared to an Aldrich TiO 2 reference catalyst, using a solar-simulated photoreactor for the degradation of phenol.« less

  15. Environmental risk induced by TiO2 dispersions in waters and sediments: a case study.

    PubMed

    Lettino, Antonio; Belviso, Claudia; Cavalcante, Francesco; Fiore, Saverio

    2016-02-01

    A southern Italian area that is characterized by large outcrops of rocks that are rich in titanium oxide (TiO2) phases were investigated to determine the mineralogical risk induced by the natural dispersion of TiO2 minerals. Rock, sediment and surface water samples were collected to determine the physicochemical and mineralogical factors (i.e., size distribution, morphology and alteration) indicative of potential TiO2 toxicity. X-ray diffraction data suggested that titanium oxides were present as rutile and anatase. Scanning electron microscopy images showed elongated TiO2 morphologies; fibres were found as either isolated or embedded/enclosed in flake-like phyllosilicates. The concentration of fibres in stream water ranged from 1.7 to 4.6 million fibres per litre. The highest fibre amounts in the sediments were in the <8-µm fraction, while single fibres were primarily concentrated in the <2-µm fraction. The results indicate that titanium oxide minerals represent a natural source of environmental risk and that the geomineralogical characterization of rich TiO2 areas is indispensable for understanding their geoavailability, dispersion and distribution. PMID:25682128

  16. Element-specific Kikuchi patterns of Rutile.

    PubMed

    Vos, M; Winkelmann, A; Nolze, G

    2015-09-01

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

  17. Influence of Ti nanocrystallization on microstructure, interface bonding, surface energy and blood compatibility of surface TiO 2 films

    NASA Astrophysics Data System (ADS)

    Shao, Honghong; Yu, Chunhang; Xu, Xiaojing; Wang, Ji; Zhai, Rui; Wang, Xiaojing

    2010-12-01

    Recent progress in ultrafine-grained/nano-grained (UFG/NG) titanium permits a consideration for TiO 2 films deposited on nano-grained titanium for antithrombogenic application such as artificial valves and stents. For this paper, the microstructure, interface bonding, surface energy, and blood compatibility features of TiO 2 films deposited by direct current magnetron reactive sputtering technology on NG titanium and coarse-grained (CG) titanium were investigated. The results show that the nanocrystallization of titanium substrate has a significant influence on TiO 2 films. At the same deposition parameters, the content of rutile phase of TiO 2 film was increased from 47% (on the CG titanium substrate) to 72% (on the NG titanium substrate); the adhesion of TiO 2 film was improved from 5.8 N to 17 N; the surface energy was reduced from 6.37 dyn/cm to 3.01 dyn/cm; the clotting time was improved from 18 min to 28 min; the platelets accumulation and pseudopodium of adherent platelets on TiO 2 film on NG titanium were considerably reduced compared to that on CG titanium. The present results demonstrate the possibility of improving the blood compatibility of TiO 2 film through the approach of substrate nanocrystallization. Also it may provide an attractive idea to prepare stents with biological coatings of more outstanding blood compatibility and interface bonding.

  18. Quench-ring assisted flame synthesis of SiO2-TiO2 nanostructured composite.

    PubMed

    Worathanakul, Patcharin; Jiang, Jingkun; Biswas, Pratim; Kongkachuichay, Paisan

    2008-12-01

    A flame aerosol reactor (FLAR) was used to synthesize SiO2-based nanocomposite materials of SiO2-TiO2 in different precursor molar ratios and quench ring positions. Processing conditions were determined that resulted in formation of different crystal phases at different precursor concentration molar ratios. The results showed that the addition of SiO2 inhibited TiO2 phase transformation from anatase to rutile. The different morphology of SiO2-TiO2 nanocomposite was primarily the result of changing the quench ring position. Quenching can stop the growth kinetics, and this was obtained by locating the quench ring at different positions in the particle formation process. At a lower position, a binary mixture of SiO2-TiO2 was obtained in a core-shell structure. The difference in residence time for sintering and coalescence yielded different morphologies of SiO2-TiO2 nanocomposites. The results from FTIR confirmed Si-O-Ti bonding for all samples. The samples of SiO2-TiO2 exhibited better suspension in liquid than pure TiO2 as confirmed by zeta potential measurements.

  19. Visible light Cr(VI) reduction and organic chemical oxidation by TiO2 photocatalysis.

    PubMed

    Sun, Bo; Reddy, Ettireddy P; Smirniotis, Panagiotis G

    2005-08-15

    Here we report the simultaneous Cr(VI) reduction and 4-chlorophenol (4-CP) oxidation in water under visible light (wavelength > 400 nm) using commercial Degussa P25 TiO2. This remarkable observation was attributed to a synergistic effect among TiO2, Cr(VI), and 4-CP. It is well known that TiO2 alone cannot remove either 4-CP or Cr(VI) efficiently under visible light. Moreover, the interaction between Cr(VI) and 4-CP is minimal if not negligible. However, we found that the combination of TiO2, Cr(VI), and 4-CP together can enable efficient Cr(VI) reduction and 4-CP oxidation under visible light. The specific roles of the three ingredients in the synergistic system were studied parametrically. It was found that optimal concentrations of Cr(VI) and TiO2 exist for the Cr(VI) reduction and 4-CP oxidation. Cr(VI) was compared experimentally with other metals such as Cu(ll), Fe(lll), Mn(IV), Ce(IV), and V(V). Among all these metal ions, only Cr(VI) promotes the photocatalytic oxidation of 4-CP. The amount of 4-CP removed was directly related to the initial concentration of Cr(VI). The system was also tested with four other chemicals (aniline, salicylic acid, formic acid, and diethyl phosphoramidate). We found that the same phenomenon occurred for organics containing acid and/or phenolic groups. Cr(VI) was reduced at the same time as the organic chemicals being oxidized during photoreaction under visible light. The synergistic effect was also found with pure anatase TiO2 and rutile TiO2. This study demonstrates a possible economical way for environmental cleanup under visible light.

  20. Photocatalytic properties of TiO2 and TiO2/Pt: a sol-precipitation, sonochemical and hydrothermal approach.

    PubMed

    Žunič, Vojka; Vukomanović, Marija; Škapin, Srečo D; Suvorov, Danilo; Kovač, Janez

    2014-01-01

    In this work we prepared TiO2 nano-powders and TiO2/Pt nano-composites via three synthesis methods (sol-precipitation, sonochemical method, hydrothermal method) starting with the same precursors and media. To evaluate and compare the physical properties of the prepared materials, X-ray diffraction analysis, BET measurements, FTIR spectroscopy, X-ray photoelectron spectroscopy (XPS) and electron microscopy (TEM, HRTEM, SAED) were applied. The results showed changes to the TiO2 phase composition and crystallinity, the specific surface area as well as the platinum's particle shape and size, depending on the method of synthesis. To determine the photocatalytic efficiency of the prepared materials, the photocatalytic discoloration of the methylene blue solution was evaluated using UV-Vis spectroscopy. The important properties required for a high photocatalytic activity, related to the surface characteristics and the phase composition, were determined in terms of the synthesis method. It was concluded that the optimum characteristics were obtained when using the hydrothermal approach, where the TiO2 had two phases, i.e., - anatase and rutile, a Pt-phase in the form of nanoparticles and adsorbed Pt-molecular species, as well as the presence of available free surface hydroxyl groups. Such characteristics had a critical influence on the photocatalytic activity of the final material.

  1. Direct Imaging of Site-Specific Photocatalytic Reactions of O2 on TiO2(110)

    SciTech Connect

    Wang, Zhitao; Deskins, N. Aaron; Lyubinetsky, Igor

    2012-01-01

    Photo-stimulated reactions on TiO2 have attracted much attention due to the variety of potential applications ranging from a hydrogen production by water splitting to environmental remediation through organic pollutant oxidation.[1,2] In the majority of these processes the oxygen plays a crucial role, serving as a simplest oxidizing reagent and/or as an electron scavenger.[3,4] Hence, the physicochemical properties of O2 adsorbed on rutile TiO2(110) (model oxide surface) has been extensively investigated,[7-13] and, in particular, the chemisorbed O2 molecules have been recently imaged by scanning tunneling microscopy (STM).[14-16] While the O2 desorption from rutile TiO2(110) is the most comprehensively studied photoreaction on TiO2 (by traditional ensemble-averaging techniques), details of its mechanism are still far from being understood. On a basis of extensive research of photostimulated desorption (PSD) of O2 from TiO2(110) by ultraviolet (UV) light, Yates and co-workers have developed a hole-mediated desorption model.

  2. Modification mechanism of praseodymium doping for the photocatalytic performance of TiO2: a combined experimental and theoretical study.

    PubMed

    Duan, Zhi-Gang; Zhao, Zong-Yan; Shi, Qing-Nan

    2015-07-15

    Impurity doping is a simple and efficient modification method to improve the photocatalytic performance of wide band gap photocatalysts. However, some basic and important issues about the mechanism of impurity doping modification still need to be further confirmed and explained. In the present work, Pr-doped TiO2 with a mono-phase crystal structure was prepared by a sol-gel method. Then, the crystal structure, binding information, optical absorption, and photocatalytic activity were systematically investigated. The experimental results show that Pr doping could significantly enhance the photocatalytic activity of TiO2, and the effects of modification on rutile TiO2 are more obvious than for anatase TiO2. In order to understand the underlying mechanism, density functional theory was utilized to calculate the crystal structure and electronic structure of pure and Pr-doped TiO2. The differences in electronic structure between anatase and rutile phases lead to the above photocatalytic performance. The experimental measurements and theoretical calculations mutually support each other in the present work. Two points are confirmed: the position of the band edge determines the redox activity of the photocatalyst, and the shallow energy bands induced by impurity doping could improve the photocatalytic performance.

  3. Modification mechanism of praseodymium doping for the photocatalytic performance of TiO2: a combined experimental and theoretical study.

    PubMed

    Duan, Zhi-Gang; Zhao, Zong-Yan; Shi, Qing-Nan

    2015-07-15

    Impurity doping is a simple and efficient modification method to improve the photocatalytic performance of wide band gap photocatalysts. However, some basic and important issues about the mechanism of impurity doping modification still need to be further confirmed and explained. In the present work, Pr-doped TiO2 with a mono-phase crystal structure was prepared by a sol-gel method. Then, the crystal structure, binding information, optical absorption, and photocatalytic activity were systematically investigated. The experimental results show that Pr doping could significantly enhance the photocatalytic activity of TiO2, and the effects of modification on rutile TiO2 are more obvious than for anatase TiO2. In order to understand the underlying mechanism, density functional theory was utilized to calculate the crystal structure and electronic structure of pure and Pr-doped TiO2. The differences in electronic structure between anatase and rutile phases lead to the above photocatalytic performance. The experimental measurements and theoretical calculations mutually support each other in the present work. Two points are confirmed: the position of the band edge determines the redox activity of the photocatalyst, and the shallow energy bands induced by impurity doping could improve the photocatalytic performance. PMID:26130404

  4. A new form of chemisorbed photo- and electro-active atomic H species on the TiO2(110) surface

    NASA Astrophysics Data System (ADS)

    Zhang, Zhen; Yates, John T.

    2016-10-01

    Hydrogen adsorption on TiO2 is of importance in chemical and photochemical reduction processes. Using several surface science methods, we clearly distinguish two kinds of H species on the surface of rutile TiO2(110)-1 × 1. In contrast with the well-studied bridge-bonded OH species (α-H) originating from H2O dissociation on the surface oxygen vacancy site on TiO2(110), atomic H adsorption on the TiO2(110) (denoted as β-H) exhibits special high sensitivity to the electronic excitation of the TiO2(110) by either electrons or UV photons. The formation of molecular H2 gas by photoexcitation of β-H/TiO2(110) surfaces has been observed, which may shed light on the basic understanding of the processes of photocatalytic H2 production by splitting water.

  5. Discrimination of TiO2 polymorphs in sedimentary and metamorphic rocks

    NASA Astrophysics Data System (ADS)

    Triebold, Silke; Luvizotto, George Luiz; Tolosana-Delgado, Raimon; Zack, Thomas; von Eynatten, Hilmar

    2011-04-01

    Investigation by Raman spectroscopy of samples from different geological settings shows that the occurrence of TiO2 polymorphs other than rutile can hardly be predicted, and furthermore, the occurrence of anatase is more widespread than previously thought. Metamorphic pressure and temperature, together with whole rock chemistry, control the occurrence of anatase, whereas variation of mineral assemblage characteristics and/or fluid occurrence or composition takes influence on anatase trace element characteristics and re-equilibration of relict rutiles. Evaluation of trace element contents obtained by electron microprobe in anatase, brookite, and rutile shows that these vary significantly between the three TiO2 phases. Therefore, on the one hand, an appropriation to source rock type according to Nb and Cr contents, but as well application of thermometry on the basis of Zr contents, would lead to erroneous results if no phase specification is done beforehand. For the elements Cr, V, Fe, and Nb, variation between the polymorphs is systematic and can be used for discrimination on the basis of a linear discriminant analysis. Using phase group means and coefficients of linear discriminants obtained from a compilation of analyses from samples with well-defined phase information together with prior probabilities of groupings from a natural sample compilation, one is able to calculate phase grouping probabilities of any TiO2 analysis containing at least the critical elements Cr, V, Fe, and Nb. An application of this calculation shows that for the appropriation to the phase rutile, a correct-classification rate of 99.5% is obtained. Hence, phase specification by trace elements proves to be a valuable tool besides Raman spectroscopy.

  6. An effective method for the preparation of high temperature stable anatase TiO2 photocatalysts

    NASA Astrophysics Data System (ADS)

    Fagan, Rachel; Synnott, Damian W.; McCormack, Declan E.; Pillai, Suresh C.

    2016-05-01

    An efficient, rapid and straightforward method for the preparation of nitrogen and fluorine (N, F) codoped high temperature stable anatase using a microwave pre-treatment is reported. Using a single source, ammonium fluoride (NH4F) for both nitrogen and fluorine, effective doping of the precursor titanium isopropoxide (TTIP) was possible. These samples were characterised for their structural and optical properties using X-ray diffraction (XRD), Fourier Transform IR (FTIR), Raman spectroscopy and UV-vis spectroscopy. In terms of the anatase to rutile transition enhancement using a novel microwave assisted technique, the sample prepared in a composition of 1:8 TiO2: NH4F at 1200 °C was seen to be most effective, having stable anatase present at 57.1% compared to undoped TiO2 being 100% rutile from 900 °C. This method involves the production of ammonium oxofluorotitanates (NH4TiOF3) at low temperatures. The inclusion of these intermediates greatly reduces the particle size growth and delays the anatase to rutile transition. The photocatalytic activity of these materials was studied by analysing the degradation of an organic dye, rhodamine 6G as a model system and the rate constant was calculated by pseudo-first-order kinetics. These results showed that the doped sample (0.0225 min-1) was three times more active than the undoped sample (0.0076 min-1) and over seven times faster than the commercial TiO2 photocatalyst standard Degussa P-25 calcined at 1200 °C (0.0030 min-1). The formation of intermediate compounds, oxofluorotitanates, was identified as the major reason for a delay in the anatase to rutile transition.

  7. Epitaxial growth of homogeneous single-crystalline AlN films on single-crystalline Cu (1 1 1) substrates

    NASA Astrophysics Data System (ADS)

    Wang, Wenliang; Yang, Weijia; Liu, Zuolian; Lin, Yunhao; Zhou, Shizhong; Qian, Huirong; Gao, Fangliang; Yang, Hui; Li, Guoqiang

    2014-03-01

    The homogeneous and crack free single-crystalline AlN thin films have been epitaxially grown on single-crystalline Cu (1 1 1) substrates with an in-plane alignment of AlN [11-20]//Cu [1-10] by pulsed laser deposition (PLD) technology with an integrated laser rastering program. The as-grown AlN films are studied by spectroscopic ellipsometry, field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), polarized light microscopy, high-resolution X-ray diffraction, and high-resolution transmission electron microscopy (HRTEM). The spectroscopic ellipsometry reveals the excellent thickness uniformity of as-grown AlN films on the Cu (1 1 1) substrates with a root-mean-square (RMS) thickness inhomogeneity less than 2.6%. AFM and FESEM measurements indicate that very smooth and flat surface AlN films are obtained with a surface RMS roughness of 2.3 nm. The X-ray reflectivity image illustrates that there is a maximum of 1.2 nm thick interfacial layer existing between the as-grown AlN and Cu (1 1 1) substrates and is confirmed by HRTEM measurement, and reciprocal space mapping shows that almost fully relaxed AlN films are achieved only with a compressive strain of 0.48% within ˜321 nm thick films. This work demonstrates a possibility to obtain homogeneous and crack free single-crystalline AlN films on metallic substrates by PLD with optimized laser rastering program, and brings up a broad prospect for the application of acoustic filters that require abrupt hetero-interfaces between the AlN films and the metallic electrodes.

  8. Epitaxial single crystalline ferrite films for high frequency applications

    SciTech Connect

    Suzuki, Y.; Dover, R.B. van; Korenivski, V.; Werder, D.; Chen, C.H.; Felder, R.J.; Phillips, J.M.

    1996-11-01

    The successful growth of single crystal ferrites in thin film form is an important step towards their future incorporation into integrated circuits operating at microwave frequencies. The authors have successfully grown high quality single crystalline spinel ferrite thin films of (Mn,Zn)Fe{sub 2}O{sub 4} and CoFe{sub 2}O{sub 4} on (100) and (110) SrTiO{sub 3} and MgAl{sub 2}O{sub 4} at low temperature. These ferrite films are buffered with spinel structure layers that are paramagnetic at room temperature. In contrast to ferrite films grown directly on the substrates, ferrite films grown on buffered substrates exhibit excellent crystallinity and bulk saturation magnetization values, thus indicating the importance of lattice match and structural similarity between the film and the immediately underlying layer. X-ray, RBS, AFM and TEM analysis provide a consistent picture of the structural properties of these ferrite films. The authors then use this technique to grow exchange-coupled bilayers of single crystalline CoFe{sub 2}O{sub 4} and (Mn,Zn)Fe{sub 2}O{sub 4}. In these bilayers, they observe strong exchange coupling across the interface that is similar in strength to the exchange coupling in the individual layers.

  9. Synthesis of TiO2 nanoscale rods with MHz femtosecond laser irradiation of single crystal surface and characterisation

    NASA Astrophysics Data System (ADS)

    Sivakumar, M.; Tan, Bo; Venkatakrishnan, Krishnan

    2011-06-01

    Growth of nanoscale rods on single crystal rutile TiO2 surface irradiated by MHz pulse repetition rate femtosecond laser in nitrogen environment without a catalyst or template is reported. The rods are of 100 nm in width to 1 micron length. Microraman analysis of the laser irradiated surface shows only a decrease in the intensity of active modes as compared to untreated surface. The growth of TiO2 nanorods can be explained by a method combining nanoparticles formation due to expulsion of molten material from laser irradiated spot and their subsequent growth by vapor-liquid-solid process.

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

    USGS Publications Warehouse

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

    2006-01-01

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

  11. Contact potential barriers and characterization of Ag-doped composite TiO2 nanotubes

    NASA Astrophysics Data System (ADS)

    Li, Jingling; Chen, Wenzhe; Yu, Hualiang; Wu, Bo; Huang, Wenbo; Wang, Mingxiu; Huang, Shizhen; Lin, Wei; Zhang, Likun; Li, Shiping

    2014-04-01

    Ag-doping TiO2 composite nanotubes (Ag-TNTs) were synthesized by alkaline fusion followed by hydrothermal treatment. The microstructure and morphology of the materials were characterized by XRD, TEM, XPS, SPS (surface photovoltage spectroscopy), FISPS (electric field-induced surface photovoltage spectroscopy) and Raman spectroscopy. First-principles calculations based on density-functional theory (DFT) showed the formation of several impurity levels near the top of the valence band in the band gap (Eg) of rutile TiO2 due to Ag doping. A "double junction" is proposed, involving a Schottky junction and p-n junction (denoted as "Ag-p-n junction") occurring between the Ag particles and the nanotube surface, as well as forming inside TiO2 nanotubes, respectively. The strongly built-in electric field of the junctions promotes the separation of photo-holes and photoelectrons, enhancing the photocatalytic efficiency. XRD results indicated that the composite Ag-TNTs exist as a mixture of anatase and rutile phases. XPS results showed that Ti4+ is the primary state of Ti. Raman spectral analysis of Ag-TNTs revealed the presence of a new peak at 271 cm-1. The red-shift of the absorption light wavelength of Ag-TNTs was 0.16 eV (20 nm) due to a considerable narrowing of Eg by the existing impurity levels.

  12. Ferroelectric Polarization-Enhanced Photoelectrochemical Water Splitting in TiO2-BaTiO3 Core-Shell Nanowire Photoanodes.

    PubMed

    Yang, Weiguang; Yu, Yanhao; Starr, Matthew B; Yin, Xin; Li, Zhaodong; Kvit, Alexander; Wang, Shifa; Zhao, Ping; Wang, Xudong

    2015-11-11

    The performances of heterojunction-based electronic devices are extremely sensitive to the interfacial electronic band structure. Here we report a largely enhanced performance of photoelectrochemical (PEC) photoanodes by ferroelectric polarization-endowed band engineering on the basis of TiO2/BaTiO3 core/shell nanowires (NWs). Through a one-step hydrothermal process, a uniform, epitaxial, and spontaneously poled barium titanate (BTO) layer was created on single crystalline TiO2 NWs. Compared to pristine TiO2 NWs, the 5 nm BTO-coated TiO2 NWs achieved 67% photocurrent density enhancement. By numerically calculating the potential distribution across the TiO2/BTO/electrolyte heterojunction and systematically investigating the light absorption, charge injection and separation properties of TiO2 and TiO2/BTO NWs, the PEC performance gain was proved to be a result of the increased charge separation efficiency induced by the ferroelectric polarization of the BTO shell. The ferroelectric polarization could be switched by external electric field poling and yielded PEC performance gain or loss based on the direction of the polarization. This study evidence that the piezotronic effect (ferroelectric or piezoelectric potential-induced band structure engineering) holds great promises in improving the performance of PEC photoelectrodes in addition to chemistry and structure optimization.

  13. Ferroelectric Polarization-Enhanced Photoelectrochemical Water Splitting in TiO2-BaTiO3 Core-Shell Nanowire Photoanodes.

    PubMed

    Yang, Weiguang; Yu, Yanhao; Starr, Matthew B; Yin, Xin; Li, Zhaodong; Kvit, Alexander; Wang, Shifa; Zhao, Ping; Wang, Xudong

    2015-11-11

    The performances of heterojunction-based electronic devices are extremely sensitive to the interfacial electronic band structure. Here we report a largely enhanced performance of photoelectrochemical (PEC) photoanodes by ferroelectric polarization-endowed band engineering on the basis of TiO2/BaTiO3 core/shell nanowires (NWs). Through a one-step hydrothermal process, a uniform, epitaxial, and spontaneously poled barium titanate (BTO) layer was created on single crystalline TiO2 NWs. Compared to pristine TiO2 NWs, the 5 nm BTO-coated TiO2 NWs achieved 67% photocurrent density enhancement. By numerically calculating the potential distribution across the TiO2/BTO/electrolyte heterojunction and systematically investigating the light absorption, charge injection and separation properties of TiO2 and TiO2/BTO NWs, the PEC performance gain was proved to be a result of the increased charge separation efficiency induced by the ferroelectric polarization of the BTO shell. The ferroelectric polarization could be switched by external electric field poling and yielded PEC performance gain or loss based on the direction of the polarization. This study evidence that the piezotronic effect (ferroelectric or piezoelectric potential-induced band structure engineering) holds great promises in improving the performance of PEC photoelectrodes in addition to chemistry and structure optimization. PMID:26492362

  14. Physical properties of single crystalline BaSn{sub 5}

    SciTech Connect

    Lin, Xiao; Budko, Sergey; Canfield, Paul

    2012-01-30

    We present a comprehensive study of the binary intermetallic superconductor, BaSn{sub 5}. High-quality single crystalline BaSn{sub 5} was grown out of a Sn flux. Detailed thermodynamic and transport measurements were performed to study BaSn{sub 5}'s normal and superconducting state properties. This material appears to be a strongly coupled, multiband superconductor. H{sub c2}(T) is almost isotropic. De Haas–van Alphen oscillations were observed and two effective masses were estimated from the FFT spectra. Hydrostatic pressure causes a decrease in the superconducting transition temperature at the rate of ≈−0.053 ± 0.001 K/kbar.

  15. Single-crystalline octahedral Au-Ag nanoframes.

    PubMed

    Hong, Xun; Wang, Dingsheng; Cai, Shuangfei; Rong, Hongpan; Li, Yadong

    2012-11-01

    We report the formation of single-crystalline octahedral Au-Ag nanoframes by a modified galvanic replacement reaction. Upon sequential addition of AgNO(3), CuCl, and HAuCl(4) to octadecylamine solution, truncated polyhedral silver nanoparticles formed first and then changed into octahedral Au-Ag nanoframes, without requiring a conventional Ag removal step with additional oxidation etchant. The nanoframes have 12 sides, and all of the eight {111} faces are empty. The side grows along the [110] direction, and the diameter is less than 10 nm. The selective gold deposition on the high-energy (110) surface, the diffusion, and the selective redeposition of Au and Ag atoms are the key reasons for the formation of octahedral nanoframes.

  16. Single crystalline Si substrate growth by lateral diffusion epitaxy

    NASA Astrophysics Data System (ADS)

    Li, Bo; Yu, Hao Ling; Shen, Huaxiang; Kitai, Adrian

    2013-03-01

    A novel crystal growth method named lateral diffusion epitaxy (LDE) as well as the necessary growth apparatus are described in detail. Single crystalline Si strips are grown on (1 1 1) Si substrates by LDE. The thickness of the LDE Si strips is around 100 μm, and the aspect ratio of width to thickness is around 2 which is an improvement compared with Si strips grown by conventional liquid phase epitaxy (LPE). The LDE Si strip can be peeled off from the substrate for further device processing since the 100 μm thickness provides reasonable mechanical strength. Due to the low cost of LDE technology it is potentially a good candidate for PV application if the LDE can achieve continuous growth and therefore grow Si strips in sizes for practical application.

  17. Periodic magnetic domains in single-crystalline cobalt filament arrays

    NASA Astrophysics Data System (ADS)

    Chen, Fei; Wang, Fan; Jia, Fei; Li, Jingning; Liu, Kai; Huang, Sunxiang; Luan, Zhongzhi; Wu, Di; Chen, Yanbin; Zhu, Jianmin; Peng, Ru-Wen; Wang, Mu

    2016-02-01

    Magnetic structures with controlled domain wall pattern may be applied as potential building blocks for three-dimensional magnetic memory and logic devices. Using a unique electrochemical self-assembly method, we achieve regular single-crystalline cobalt filament arrays with specific geometric profile and crystallographic orientation, and the magnetic domain configuration can be conveniently tailored. We report the transition of periodic antiparallel magnetic domains to compressed vortex magnetic domains depending on the ratio of height to width of the wires. A "phase diagram" is obtained to describe the dependence of the type of magnetic domain and the geometrical profiles of the wires. Magnetoresistance of the filaments demonstrates that the contribution of a series of 180∘ domain walls is over 0.15 % of the zero-field resistance ρ (H =0 ) . These self-assembled magnetic nanofilaments, with controlled periodic domain patterns, offer an interesting platform to explore domain-wall-based memory and logic devices.

  18. Fatigue crack propagation behavior of a single crystalline superalloy

    NASA Technical Reports Server (NTRS)

    Lerch, B. A.; Antolovich, Stephen D.

    1990-01-01

    Crack propagation mechanisms occurring at various temperatures in a single crystalline Ni-base alloy, Rene N4, were investigated. The rates of crack growth at 21, 704, 927, 1038, and 1093 C were measured in specimens with 001-line and 110-line directions parallel to the load axis and the machined notch, respectively, using a pulsed dc potential drop apparatus, and the fracture surfaces at each temperature were examined using SEM. Crack growth rates (CGRs) for specimens tested at or below 927 C were similar, while at two higher temperatures, the CGRs were about an order of magnitude higher than at the lower temperatures. Results of SEM observations showed that surface morphologies depended on temperature.

  19. Preparation and photoelectric property of TiO2 nanoparticles with controllable phase junctions

    NASA Astrophysics Data System (ADS)

    Wang, Hongmei; Tan, Xin; Yu, Tao

    2014-12-01

    To explore the effect of phase composition on the photoelectric property of anatase-rutile mixed crystal nanoparticles, a series of TiO2 nanoparticles with phase junctions controlling were synthetized by hydrolysis of TiCl4 in hydrochloric acid, an ionic liquid-assisted method was used during this process. Crystalline size and the ratio of anatase to rutile of as-prepared samples were calculated by the XRD. The surface area was measured by nitrogen sorption measurements using the BET method. The micro-structure of phase junctions was characterized by TEM. Optical transmittance properties of TiO2 with controllable phase junctions were examined via ultraviolet-visible diffuse reflection spectroscopy (UV-vis DRS). The particles were manufactured into films using the doctor-blade technique on FTO glasses. To test photocurrent density, and spatial separation capacity of electron-holes pairs, photo-electro method was employed. The photocatalytic activities of the resulting samples were examined in the degradation of methyl orange (MO) under artificial solar light irradiation. Mechanisms of separation and transfer of photogenerated charge and the effect of phase composition on photoelectric property of anatase-rutile nanoparticles were discussed.

  20. Reactive wetting properties of TiO2 nanoparticles predicted by ab initio molecular dynamics simulations

    NASA Astrophysics Data System (ADS)

    Brandt, Erik G.; Agosta, Lorenzo; Lyubartsev, Alexander P.

    2016-07-01

    coordination numbers); radial distribution functions for all O-Ti pairs over the entire data domain; comparison of coordination number distributions for dry and wet nanoparticles; dynamics of water reactivity; high-resolution electron density for the rutile NP. A movie of the simulation trajectory for the rutile (TiO2)24.30H2O system. See DOI: 10.1039/C6NR02791A

  1. A mini-review on rare earth metal-doped TiO2 for photocatalytic remediation of wastewater.

    PubMed

    Saqib, Najm Us; Adnan, Rohana; Shah, Irfan

    2016-08-01

    Titanium dioxide (TiO2) has been considered a useful material for the treatment of wastewater due to its non-toxic character, chemical stability and excellent electrical and optical properties which contribute in its wide range of applications, particularly in environmental remediation technology. However, the wide band gap of TiO2 photocatalyst (anatase phase, 3.20 eV) limits its photocatalytic activity to the ultraviolet region of light. Besides that, the electron-hole pair recombination has been found to reduce the efficiency of the photocatalyst. To overcome these problems, tailoring of TiO2 surface with rare earth metals to improve its surface, optical and photocatalytic properties has been investigated by many researchers. The surface modifications with rare earth metals proved to enhance the efficiency of TiO2 photocatalyts by way of reducing the band gap by shifting the working wavelength to the visible region and inhibiting the anatase-to-rutile phase transformations. This review paper summarises the attempts on modification of TiO2 using rare earth metals describing their effect on the photocatalytic activities of the modified TiO2 photocatalyst. PMID:27335012

  2. Effect of model dissolved organic matter coating on sorption of phenanthrene by TiO2 nanoparticles.

    PubMed

    Wang, Xilong; Ma, Enxing; Shen, Xiaofang; Guo, Xiaoying; Zhang, Meng; Zhang, Haiyun; Liu, Ye; Cai, Fei; Tao, Shu; Xing, Baoshan

    2014-11-01

    Dissolved organic matter (DOM) may alter the sorption of hydrophobic organic contaminants (HOC) to metal oxide nanoparticles (NPs), but the role of DOM and NP types is poorly understood. Here, phenanthrene sorption was quantified on four types of nano-TiO2 (three rutile, one anatase), and a bulk, raw TiO2 powder. Prior to the sorption experiments, these nanoparticles were coated using four different organic materials: Lignin (LIG), tannic acid (TAN), Congo red (CON), and capsorubin (CAP). Lignin, tannic acid, congo red and capsorubin coating substantially enhanced phenanthrene sorption to various TiO2 particles. After coating with a specific DOM, Kd values by the DOM-coated TiO2 particles on percent organic carbon content and surface area (SA) basis (Koc/SA) generally followed the order: TiO2 NPs with hydrophobic surfaces > bulk TiO2 particles > other TiO2 NPs. Different Koc/SA values of various DOM-TiO2 complexes resulted from distinct conformation of the coated DOM and aggregation.

  3. In situ growing directional spindle TiO2 nanocrystals on cellulose fibers for enhanced Pb(2+) adsorption from water.

    PubMed

    Li, Yanxiang; Cao, Lixia; Li, Lei; Yang, Chuanfang

    2015-05-30

    TiO2/cellulose nanocomposite was synthesized by in situ generation of titanium dioxide (TiO2) nanocrystals on cellulose fibers (CF) via facile hydrolysis of TiOSO4. Cellulose was intended as a scaffold to immobilize TiO2 nanoparticles (NPs), but turned out surprisingly to be also a chemical template that directed the crystal growth. As a result, spindle rutile TiO2 crystals were nicely formed on the surface of cellulose. These crystals were further controlled to disperse uniformly without agglomeration for better use of their surface area to adsorb heavy metals. The TiO2/CF composite showed enhanced adsorption capacity, good regenerability and selectivity for lead (Pb(2+)) removal. In addition, the composite fibers were readily fabricated into a nonwoven filter bed through which dynamic filtration experiment was conducted. A 12-fold increase in filtered bed volume was achieved for TiO2/CF bed compared with pure CF bed before breakthrough took place. This work provides a green pathway for fabricating low cost, high efficiency and engineering application possible nanosorbents for water decontamination. PMID:25723888

  4. Photocatalytic antibacterial effect of TiO(2) film formed on Ti and TiAg exposed to Lactobacillus acidophilus.

    PubMed

    Choi, Jung-Yoon; Kim, Kyung-Ho; Choy, Kwang-Chul; Oh, Keun-Taek; Kim, Kyoung-Nam

    2007-02-01

    When irradiated under near-ultraviolet (UV) light, TiO(2) exhibits strong bactericidal activity. The TiO(2) photocatalyst would be effective on orthodontic appliances after its antibacterial effect on the carcinogenic microorganism Lactobacillus acidophilus is evaluated. To compare the antibacterial effect of two crystalline forms of TiO(2), rutile and anatase, thermal oxidation and anodic oxidation were employed to form each structure, respectively. The antibacterial effect of TiO(2) film on TiAg was also compared with that on Ti. Bacterial solutions were pipetted onto the TiO(2)-coated specimen and illuminated with UVA (2 x 15 W, black light, 356 nm) up to 100 min and the reaction solutions were incubated to count the colony-forming units. The antibacterial activity of the coated specimens was similar to that of the uncoated group. The antibacterial activity of the coated specimens of TiAg was not different from that of Ti. TiO(2) coatings formed on both Ti and TiAg specimens did not exhibit cytotoxicity on the L-929 cells of mice. PMID:16850466

  5. A mini-review on rare earth metal-doped TiO2 for photocatalytic remediation of wastewater.

    PubMed

    Saqib, Najm Us; Adnan, Rohana; Shah, Irfan

    2016-08-01

    Titanium dioxide (TiO2) has been considered a useful material for the treatment of wastewater due to its non-toxic character, chemical stability and excellent electrical and optical properties which contribute in its wide range of applications, particularly in environmental remediation technology. However, the wide band gap of TiO2 photocatalyst (anatase phase, 3.20 eV) limits its photocatalytic activity to the ultraviolet region of light. Besides that, the electron-hole pair recombination has been found to reduce the efficiency of the photocatalyst. To overcome these problems, tailoring of TiO2 surface with rare earth metals to improve its surface, optical and photocatalytic properties has been investigated by many researchers. The surface modifications with rare earth metals proved to enhance the efficiency of TiO2 photocatalyts by way of reducing the band gap by shifting the working wavelength to the visible region and inhibiting the anatase-to-rutile phase transformations. This review paper summarises the attempts on modification of TiO2 using rare earth metals describing their effect on the photocatalytic activities of the modified TiO2 photocatalyst.

  6. Nanoporous SiO2/TiO2 coating with enhanced interfacial compatibility for orthopedic applications

    NASA Astrophysics Data System (ADS)

    Zhao, Xiaobing; Cao, Hengchun; You, Jing; Cheng, Xingbao; Xie, Youtao; Cao, Huiliang; Liu, Xuanyong

    2015-11-01

    Topographic modification in nanoscale is one of the most often used strategies to enhance the interfacial biocompatibility of implant materials. The aim of this work is to produce SiO2/TiO2 coatings with nanoporous structures and favorable biological properties by atmospheric plasma spraying technology and subsequently hydrothermal etching method in hydrogen fluoride solution. The effects of hydrothermal time and temperature on the microstructures and osteoblast behavior of the SiO2/TiO2 coatings were investigated. Results demonstrated that the as-sprayed SiO2/TiO2 coating was mainly composed of rutile and quartz phases. After etching, nanoporous topographies were formed on the surface of the coatings and the hydrothermal parameters had important influences on the size and shape of the pores. The interconnected network pores on the coating surface could only produce at the appropriate hydrothermal conditions (the hydrothermal time and temperature were 60 min and 100 °C, respectively). Compared to TiO2 and SiO2/TiO2 coatings, nanoporous SiO2/TiO2 coatings could enhance osteoblast adhesion and promote cell proliferation. The results suggested the potential application of the porous coatings for enhancing the biological performance of the currently used dental and orthopedic implant materials.

  7. In situ growing directional spindle TiO2 nanocrystals on cellulose fibers for enhanced Pb(2+) adsorption from water.

    PubMed

    Li, Yanxiang; Cao, Lixia; Li, Lei; Yang, Chuanfang

    2015-05-30

    TiO2/cellulose nanocomposite was synthesized by in situ generation of titanium dioxide (TiO2) nanocrystals on cellulose fibers (CF) via facile hydrolysis of TiOSO4. Cellulose was intended as a scaffold to immobilize TiO2 nanoparticles (NPs), but turned out surprisingly to be also a chemical template that directed the crystal growth. As a result, spindle rutile TiO2 crystals were nicely formed on the surface of cellulose. These crystals were further controlled to disperse uniformly without agglomeration for better use of their surface area to adsorb heavy metals. The TiO2/CF composite showed enhanced adsorption capacity, good regenerability and selectivity for lead (Pb(2+)) removal. In addition, the composite fibers were readily fabricated into a nonwoven filter bed through which dynamic filtration experiment was conducted. A 12-fold increase in filtered bed volume was achieved for TiO2/CF bed compared with pure CF bed before breakthrough took place. This work provides a green pathway for fabricating low cost, high efficiency and engineering application possible nanosorbents for water decontamination.

  8. The effects of atmosphere and calcined temperature on photocatalytic activity of TiO2 nanofibers prepared by electrospinning

    PubMed Central

    2013-01-01

    TiO2-based nanofibers were synthesized using a sol–gel method and electrospinning technique. The as-spun composite fibers were heat-treated at different temperatures (500°C, 550°C, 600°C, and 650°C) and atmospheres (ammonia and nitrogen) for 4 h. The fibers had diameters of 50 to 200 nm and mainly featured anatase and rutile phases. The anatase phase decreased and the rutile phase increased with increasing temperature. Different nitrogen conditions exerted minimal effects on the TiO2 crystalline phase. Different nitriding atmospheres during preservation heating yielded various effects on fibers. The effect of nitrogen in ammonia atmosphere is better than that in nitrogen atmosphere. The fibers heat-treated at 600°C and subjected to preservation heating in NH3 showed high photocatalytic activity. PMID:24373382

  9. A Study of Phase Stability and Properties of TiO2 Polymorphs with Diffusion Monte Carlo

    NASA Astrophysics Data System (ADS)

    Luo, Ye; Benali, Anouar; Shulenburger, Luke; Krogel, Jaron; Heinonen, Olle; Kent, Paul

    In the past decades, many studies have focused on the fundamental properties of TiO2 due to its important role in effectively converting solar energy such as in photovoltaic batteries and photocatalic water splitting. TiO2 presents many stable and metastable phases of which, Rutile Anatase and Brookite are the most studied. Using density functional theory (DFT), the energy ordering of these phases depends strongly on the scheme describing the electronic correlation, for instance GGA+U and Hybrid functionals, often tied to an empirical parameter for reproducibility with no guarantee of predictability. We present the first analysis of the polymorphic energy ordering and properties of three naturally existing phases Rutile, Anatase and Brookite, by performing the highly accurate ab initio calculation with fixed node diffusion Monte Carlo (DMC) implemented in QMCPACK

  10. The effects of atmosphere and calcined temperature on photocatalytic activity of TiO2 nanofibers prepared by electrospinning

    NASA Astrophysics Data System (ADS)

    Hu, MeiLing; Fang, MingHao; Tang, Chao; Yang, Tao; Huang, ZhaoHui; Liu, YanGai; Wu, XiaoWen; Min, Xin

    2013-12-01

    TiO2-based nanofibers were synthesized using a sol-gel method and electrospinning technique. The as-spun composite fibers were heat-treated at different temperatures (500°C, 550°C, 600°C, and 650°C) and atmospheres (ammonia and nitrogen) for 4 h. The fibers had diameters of 50 to 200 nm and mainly featured anatase and rutile phases. The anatase phase decreased and the rutile phase increased with increasing temperature. Different nitrogen conditions exerted minimal effects on the TiO2 crystalline phase. Different nitriding atmospheres during preservation heating yielded various effects on fibers. The effect of nitrogen in ammonia atmosphere is better than that in nitrogen atmosphere. The fibers heat-treated at 600°C and subjected to preservation heating in NH3 showed high photocatalytic activity.

  11. The effects of atmosphere and calcined temperature on photocatalytic activity of TiO2 nanofibers prepared by electrospinning.

    PubMed

    Hu, Meiling; Fang, Minghao; Tang, Chao; Yang, Tao; Huang, Zhaohui; Liu, Yangai; Wu, Xiaowen; Min, Xin

    2013-12-30

    TiO2-based nanofibers were synthesized using a sol-gel method and electrospinning technique. The as-spun composite fibers were heat-treated at different temperatures (500°C, 550°C, 600°C, and 650°C) and atmospheres (ammonia and nitrogen) for 4 h. The fibers had diameters of 50 to 200 nm and mainly featured anatase and rutile phases. The anatase phase decreased and the rutile phase increased with increasing temperature. Different nitrogen conditions exerted minimal effects on the TiO2 crystalline phase. Different nitriding atmospheres during preservation heating yielded various effects on fibers. The effect of nitrogen in ammonia atmosphere is better than that in nitrogen atmosphere. The fibers heat-treated at 600°C and subjected to preservation heating in NH3 showed high photocatalytic activity.

  12. Synthesis, characterization and application of TiO2 nanopowders as special paper coating pigment

    NASA Astrophysics Data System (ADS)

    El-Sherbiny, Samya; Morsy, Fatma; Samir, Marwa; Fouad, Osama A.

    2013-03-01

    TiO2 nanopigments in two pure crystallographic forms (anatase and rutile) have been synthesized successfully by two methods; hydrothermal and hydrolysis. The produced pigments from the two methods were investigated physicochemically by several analyses tools. Then they were applied in paper coating mixtures and their influence on coated paper properties was systematically investigated. XRD and FTIR investigations showed that the prepared pigments using hydrothermal method at 100 and 120 °C were a mixture of anatase and brookite and pure anatase, respectively, whereas hydrolysis method produced pure rutile phase pigment. TEM investigation showed that the crystallite size of anatase, mixture of anatase and brookite and rutile samples are 6.2, 11.7, and 9.2 nm, respectively. BET studies proved that anatase pigment has 140.74 m2/g, 0.237 cc/g and 18.33 Å, whereas rutile has 60.621 m2/g, 0.122 cc/g and 14.669 Å, surface area, pore volume and pore diameter, respectively. UV-Vis absorption and PL emission characteristics of the prepared pigments showed that the energy gaps for anatase, mixture of anatase and brookite and rutile are 3.36, 3.30 and 3.37 eV, respectively. The addition of the prepared nanopigments in conjugation with clay in coating mixture increased both brightness and opacity of the coated papers. The greatest effect was obtained upon using rutile nanopigment. Also there was a significant decrease in coated paper roughness while the air permeance started to decrease then increased at 50 % addition levels. In all coated paper, rutile pigment showed the highest enhancement effect on coated paper properties.

  13. Synthesis, characterization and application of TiO2 nanopowders as special paper coating pigment

    NASA Astrophysics Data System (ADS)

    El-Sherbiny, Samya; Morsy, Fatma; Samir, Marwa; Fouad, Osama A.

    2014-03-01

    TiO2 nanopigments in two pure crystallographic forms (anatase and rutile) have been synthesized successfully by two methods; hydrothermal and hydrolysis. The produced pigments from the two methods were investigated physicochemically by several analyses tools. Then they were applied in paper coating mixtures and their influence on coated paper properties was systematically investigated. XRD and FTIR investigations showed that the prepared pigments using hydrothermal method at 100 and 120 °C were a mixture of anatase and brookite and pure anatase, respectively, whereas hydrolysis method produced pure rutile phase pigment. TEM investigation showed that the crystallite size of anatase, mixture of anatase and brookite and rutile samples are 6.2, 11.7, and 9.2 nm, respectively. BET studies proved that anatase pigment has 140.74 m2/g, 0.237 cc/g and 18.33 Å, whereas rutile has 60.621 m2/g, 0.122 cc/g and 14.669 Å, surface area, pore volume and pore diameter, respectively. UV-Vis absorption and PL emission characteristics of the prepared pigments showed that the energy gaps for anatase, mixture of anatase and brookite and rutile are 3.36, 3.30 and 3.37 eV, respectively. The addition of the prepared nanopigments in conjugation with clay in coating mixture increased both brightness and opacity of the coated papers. The greatest effect was obtained upon using rutile nanopigment. Also there was a significant decrease in coated paper roughness while the air permeance started to decrease then increased at 50 % addition levels. In all coated paper, rutile pigment showed the highest enhancement effect on coated paper properties.

  14. Genotoxic potential of TiO2 on bottlenose dolphin leukocytes.

    PubMed

    Bernardeschi, Margherita; Guidi, Patrizia; Scarcelli, Vittoria; Frenzilli, Giada; Nigro, Marco

    2010-01-01

    Titanium dioxide is extensively used in a variety of products, including industrial materials and cosmetics. Studies mainly performed on human cell lines and in vivo exposure on experimental animals have raised concern about the toxic effects of ultrafine titanium dioxide; however, scarce information is available about its impact on aquatic life. The aim of this article was to assess the genotoxic potential of TiO(2) (anatase and rutile) on bottlenose dolphin leukocytes. Blood samples were obtained from four male and one female specimens reared at the Adriatic SeaWorld "Oltremare" (Riccione, Italy). Leukocytes were isolated by the lyses procedure and in vitro exposed to TiO(2) in RPMI. Experimental solutions were sonicated immediately before dosing the cells. Three exposure times (4, 24 and 48 h) and three doses (20, 50 and 100 microg/ml) were tested. Genotoxicity was detected by the single-cell gel electrophoresis (or comet assay) at pH > or = 13, assessing single/double-strand breaks and alkali-labile sites. Cytotoxicity was also detected by the Trypan blue exclusion method. Results showed that both the crystalline forms of TiO(2) were genotoxic for bottlenose dolphin leukocytes, with a statistically significant increase of DNA fragmentation after exposure to 50 and 100 microg/ml for 24 and 48 h. Although preliminary, these are the first data regarding the genetic susceptibility of toothed cetaceans toward an "emerging" pollutant, such as TiO(2) particles. PMID:19915826

  15. In situ synthesis of TiO2/polyethylene terephthalate hybrid nanocomposites at low temperature

    NASA Astrophysics Data System (ADS)

    Peng, Xinyan; Ding, Enyong; Xue, Feng

    2012-06-01

    TiO2 nanoflowers were in situ grown on polyethylene terephthalate (PET) non-woven fabric by hydrolysis of TiCl4 in aqueous solution in the presence of nanocrystal cellulose grafted PET fabric (NCC-g-PET) at a low temperature of 70 °C. Nanocrystal cellulose (NCC) pre-grafted on PET fabric acted as hydrophilic substrate and morphology inducing agent to promote the nucleation and crystal growth of TiO2. Detailed information on the synthetic process was presented. The resulting samples were characterized using FE-SEM, EDS, ATR-IR, Raman microscopy, XRD and TG analysis. The photocatalytic activity of the samples was evaluated by the degradation of orange methyl under solar light. Characteristic results indicate that rutile TiO2 nanoflowers have grown abundantly on PET non-woven fabric, and the established hydrogen bonding strengthens the interfacial interaction between the inorganic particles and the polymeric substrates. The methyl orange decoloration test under natural solar light demonstrates that this TiO2/PET hybrid nanocomposites exhibit excellent self-cleaning performance which is expected to have a good potential for commercialization.

  16. Synthesis and optical properties of TiO2-based magnetic nanocomposites

    NASA Astrophysics Data System (ADS)

    Scarisoreanu, M.; Morjan, I.; Fleaca, C.-T.; Morjan, I. P.; Niculescu, A.-M.; Dutu, E.; Badoi, A.; Birjega, R.; Luculescu, C.; Vasile, E.; Danciu, V.; Filoti, G.

    2015-05-01

    Magnetic titania nanoparticles covered/embedded in SiO2 shell/matrix were simultaneously manufactured by the single-step laser pyrolysis. The present study is a continuation of our previous investigations on the TiO2/Fe and TiO2/HMDSO (hexamethyldisiloxane) derived-systems. The aim of this work is to study the synthesis by IR (Infrared) laser pyrolysis of magnetic TiO2 based nanocomposites which implies many concurrent processes induced in the gas phase by the laser radiation. The dependence between characteristic properties and the synthesis parameters was determined by many analytical and complementary methods: XRD (X-ray diffraction) structural analysis, UV-vis (ultraviolet-visible) and EDAX (energy-dispersive X-ray) spectroscopy, TEM and HRTEM (transmission electron microscopy at low and high resolution) analysis and magnetic measurements. The results of analysis indicate the presence of disordered silica, Fe, α-Fe2O3 and mixtures of anatase and rutile phases with mean crystallite dimensions (in the 14-34 nm range) with typical character of diluted magnetic oxide systems and a lower bandgap energy (Eg = 1.85 eV) as compared with TiO2 P25 Degussa sample.

  17. Fe-Doped TiO2 Thin Films for CO Gas Sensing

    NASA Astrophysics Data System (ADS)

    Kumar, Mukesh; Kumar, Dinesh; Gupta, Anil Kumar

    2015-01-01

    Fe-doped TiO2 thin films were prepared by the sol-gel technique on silicon substrate. The thin films were evaluated for detection of carbon monoxide (CO) gas at room temperature. The TiO2 films were characterized by x-ray diffraction (XRD) analysis, field-emission scanning electron microscopy, and ultraviolet-visible (UV) spectroscopy. The characterization revealed that, as the doping concentration was increased, the grain size decreased. XRD patterns revealed the phase transition from rutile to anatase with addition of different percentages (weight/volume) of Fe. The bandgap determined from UV spectroscopy was found to decrease with increasing Fe doping concentration. Fe doping was observed to have a significant effect on the resistivity of the doped TiO2 thin films. The gas sensing behavior of the films was studied by exposure to different concentrations of CO gas with measurement of the electrical resistance. It was observed that Fe-doped (7% weight/volume) TiO2 exhibited high sensitivity and good response/recovery on exposure to CO gas in the concentration range from 100 ppm to 900 ppm in Ar.

  18. Electronic structures and optical properties of TiO2: Improved density-functional-theory investigation

    NASA Astrophysics Data System (ADS)

    Gong, Sai; Liu, Bang-Gui

    2012-05-01

    TiO2 has been recently used to realize high-temperature ferromagnetic semiconductors. In fact, it has been widely used for a long time as white pigment and sunscreen because of its whiteness, high refractive index, and excellent optical properties. However, its electronic structures and the related properties have not been satisfactorily understood. Here, we use Tran and Blaha's modified Becke-Johnson (TB-mBJ) exchange potential (plus a local density approximation correlation potential) within the density functional theory to investigate electronic structures and optical properties of rutile and anatase TiO2. Our comparative calculations show that the energy gaps obtained from mBJ method agree better with the experimental results than that obtained from local density approximation (LDA) and generalized gradient approximation (GGA), in contrast with substantially overestimated values from many-body perturbation (GW) calculations. As for optical dielectric functions (both real and imaginary parts), refractive index, and extinction coefficients as functions of photon energy, our mBJ calculated results are in excellent agreement with the experimental curves. Our further analysis reveals that these excellent improvements are achieved because mBJ potential describes accurately the energy levels of Ti 3d states. These results should be helpful to understand the high temperature ferromagnetism in doped TiO2. This approach can be used as a standard to understand electronic structures and the related properties of such materials as TiO2.

  19. Generation of Organic Radicals During Photocatalytic Reactions on TiO2

    SciTech Connect

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

    2011-04-01

    Using a variety of organic carbonyl molecules (R1C(O)R2) and the rutile TiO2(110) surface as a model photocatalyst, we demonstrate both experimentally and theoretically that ejection of organic radicals from TiO2 surfaces is likely a prevalent reaction process occurring during heterogeneous photooxidationof organic molecules. Organic carbonyls react with coadsorbed oxygen species to form organic diolates which are more strongly bound to TiO2 than are the parent carbonyls. The parent carbonyls, when bound to TiO2(110) in an η1 configuration, are photo-inactive. However, the diolates are shown to photodecompose by ejection one of the two R substituents from the surface into the gas phase, leaving behind the carboxylate of the other R group. Theoretical calculations using DFT show that in most cases the choice of which R group is ejected can be predicted based on the C-R bond energies and, to a lesser extent, the stability of the ejected R group.

  20. Genotoxic potential of TiO2 on bottlenose dolphin leukocytes.

    PubMed

    Bernardeschi, Margherita; Guidi, Patrizia; Scarcelli, Vittoria; Frenzilli, Giada; Nigro, Marco

    2010-01-01

    Titanium dioxide is extensively used in a variety of products, including industrial materials and cosmetics. Studies mainly performed on human cell lines and in vivo exposure on experimental animals have raised concern about the toxic effects of ultrafine titanium dioxide; however, scarce information is available about its impact on aquatic life. The aim of this article was to assess the genotoxic potential of TiO(2) (anatase and rutile) on bottlenose dolphin leukocytes. Blood samples were obtained from four male and one female specimens reared at the Adriatic SeaWorld "Oltremare" (Riccione, Italy). Leukocytes were isolated by the lyses procedure and in vitro exposed to TiO(2) in RPMI. Experimental solutions were sonicated immediately before dosing the cells. Three exposure times (4, 24 and 48 h) and three doses (20, 50 and 100 microg/ml) were tested. Genotoxicity was detected by the single-cell gel electrophoresis (or comet assay) at pH > or = 13, assessing single/double-strand breaks and alkali-labile sites. Cytotoxicity was also detected by the Trypan blue exclusion method. Results showed that both the crystalline forms of TiO(2) were genotoxic for bottlenose dolphin leukocytes, with a statistically significant increase of DNA fragmentation after exposure to 50 and 100 microg/ml for 24 and 48 h. Although preliminary, these are the first data regarding the genetic susceptibility of toothed cetaceans toward an "emerging" pollutant, such as TiO(2) particles.

  1. Structure and photoluminescence of the TiO2 films grown by atomic layer deposition using tetrakis-dimethylamino titanium and ozone.

    PubMed

    Jin, Chunyan; Liu, Ben; Lei, Zhongxiang; Sun, Jiaming

    2015-01-01

    TiO2 films were grown on silicon substrates by atomic layer deposition (ALD) using tetrakis-dimethylamino titanium and ozone. Amorphous TiO2 film was deposited at a low substrate temperature of 165°C, and anatase TiO2 film was grown at 250°C. The amorphous TiO2 film crystallizes to anatase TiO2 phase with annealing temperature ranged from 300°C to 1,100°C in N2 atmosphere, while the anatase TiO2 film transforms into rutile phase at a temperature of 1,000°C. Photoluminescence from anatase TiO2 films contains a red band at 600 nm and a green band at around 515 nm. The red band exhibits a strong correlation with defects of the under-coordinated Ti(3+) ions, and the green band shows a close relationship with the oxygen vacancies on (101) oriented anatase crystal surface. A blue shift of the photoluminescence spectra reveals that the defects of under-coordinated Ti(3+) ions transform to surface oxygen vacancies in the anatase TiO2 film annealing at temperature from 800°C to 900°C in N2 atmosphere. PMID:25852391

  2. Synthesis of TiO2 visible light catalysts with controllable crystalline phase and morphology from Ti-bearing electric arc furnace molten slag.

    PubMed

    Li, Yang; Liu, Lulu; Guo, Min; Zhang, Mei

    2016-09-01

    TiO2 visible light catalysts with different crystalline phases and morphologies were synthesized from titanium-bearing electric arc furnace molten slag (Ti-bearing EAF slag) by using a simple acidolysis process. The effects of the pH of the HCl solution, liquid to solid ratio (RL/S, HCl solution to the residue ratio, mL/g) and acidolysis time on the micro-morphology and crystalline phase of as-prepared TiO2 photocatalysts were systematically investigated. The results indicated that with decreasing pH in the HCl solution and increasing RL/S, the crystalline phase and micro-morphology of the obtained TiO2 nanostructures tended to transform from anatase type TiO2 with spherical nanoparticle structures to rutile type TiO2 with needle-like nanorod structures. The acidolysis time had little influence on the crystalline phase but great impact on the size of the obtained TiO2. The growth mechanism of TiO2 from Ti-bearing EAF slag during the acidolysis process was also discussed. In addition, the influence of RL/S on the photocatalytic properties of the synthesized nanostructured TiO2 was studied. The results showed that the photodegradation efficiency for Rhodamine B solution could reach 91.00% in 120min when the RL/S was controlled at 50:1.

  3. Structure and photoluminescence of the TiO2 films grown by atomic layer deposition using tetrakis-dimethylamino titanium and ozone.

    PubMed

    Jin, Chunyan; Liu, Ben; Lei, Zhongxiang; Sun, Jiaming

    2015-01-01

    TiO2 films were grown on silicon substrates by atomic layer deposition (ALD) using tetrakis-dimethylamino titanium and ozone. Amorphous TiO2 film was deposited at a low substrate temperature of 165°C, and anatase TiO2 film was grown at 250°C. The amorphous TiO2 film crystallizes to anatase TiO2 phase with annealing temperature ranged from 300°C to 1,100°C in N2 atmosphere, while the anatase TiO2 film transforms into rutile phase at a temperature of 1,000°C. Photoluminescence from anatase TiO2 films contains a red band at 600 nm and a green band at around 515 nm. The red band exhibits a strong correlation with defects of the under-coordinated Ti(3+) ions, and the green band shows a close relationship with the oxygen vacancies on (101) oriented anatase crystal surface. A blue shift of the photoluminescence spectra reveals that the defects of under-coordinated Ti(3+) ions transform to surface oxygen vacancies in the anatase TiO2 film annealing at temperature from 800°C to 900°C in N2 atmosphere.

  4. Structure and photoluminescence of the TiO2 films grown by atomic layer deposition using tetrakis-dimethylamino titanium and ozone

    NASA Astrophysics Data System (ADS)

    Jin, Chunyan; Liu, Ben; Lei, Zhongxiang; Sun, Jiaming

    2015-02-01

    TiO2 films were grown on silicon substrates by atomic layer deposition (ALD) using tetrakis-dimethylamino titanium and ozone. Amorphous TiO2 film was deposited at a low substrate temperature of 165°C, and anatase TiO2 film was grown at 250°C. The amorphous TiO2 film crystallizes to anatase TiO2 phase with annealing temperature ranged from 300°C to 1,100°C in N2 atmosphere, while the anatase TiO2 film transforms into rutile phase at a temperature of 1,000°C. Photoluminescence from anatase TiO2 films contains a red band at 600 nm and a green band at around 515 nm. The red band exhibits a strong correlation with defects of the under-coordinated Ti3+ ions, and the green band shows a close relationship with the oxygen vacancies on (101) oriented anatase crystal surface. A blue shift of the photoluminescence spectra reveals that the defects of under-coordinated Ti3+ ions transform to surface oxygen vacancies in the anatase TiO2 film annealing at temperature from 800°C to 900°C in N2 atmosphere.

  5. Synthesis of TiO2 visible light catalysts with controllable crystalline phase and morphology from Ti-bearing electric arc furnace molten slag.

    PubMed

    Li, Yang; Liu, Lulu; Guo, Min; Zhang, Mei

    2016-09-01

    TiO2 visible light catalysts with different crystalline phases and morphologies were synthesized from titanium-bearing electric arc furnace molten slag (Ti-bearing EAF slag) by using a simple acidolysis process. The effects of the pH of the HCl solution, liquid to solid ratio (RL/S, HCl solution to the residue ratio, mL/g) and acidolysis time on the micro-morphology and crystalline phase of as-prepared TiO2 photocatalysts were systematically investigated. The results indicated that with decreasing pH in the HCl solution and increasing RL/S, the crystalline phase and micro-morphology of the obtained TiO2 nanostructures tended to transform from anatase type TiO2 with spherical nanoparticle structures to rutile type TiO2 with needle-like nanorod structures. The acidolysis time had little influence on the crystalline phase but great impact on the size of the obtained TiO2. The growth mechanism of TiO2 from Ti-bearing EAF slag during the acidolysis process was also discussed. In addition, the influence of RL/S on the photocatalytic properties of the synthesized nanostructured TiO2 was studied. The results showed that the photodegradation efficiency for Rhodamine B solution could reach 91.00% in 120min when the RL/S was controlled at 50:1. PMID:27593268

  6. Density and structural effects in the radiation tolerance of TiO2 polymorphs

    NASA Astrophysics Data System (ADS)

    Qin, M. J.; Y Kuo, E.; Whittle, K. R.; Middleburgh, S. C.; Robinson, M.; Marks, N. A.; Lumpkin, G. R.

    2013-09-01

    The radiation response of TiO2 has been studied using molecular dynamics. The simulations are motivated by experimental observations that the three low-pressure polymorphs, rutile, brookite and anatase, exhibit vastly different tolerances to amorphization under ion-beam irradiation. To understand the role of structure we perform large numbers of simulations using the small thermal spike method. We quantify to high statistical accuracy the number of defects created as a function of temperature and structure type, and reproduce all the main trends observed experimentally. To evaluate a hypothesis that volumetric strain relative to the amorphous phase is an important driving force for defect recovery, we perform spike simulations in which the crystalline density is varied over a wide range. Remarkably, the large differences between the polymorphs disappear once the density difference is taken into account. This finding demonstrates that density is an important factor which controls radiation tolerance in TiO2.

  7. Charge storage in oxygen deficient phases of TiO2: defect Physics without defects.

    PubMed

    Padilha, A C M; Raebiger, H; Rocha, A R; Dalpian, G M

    2016-01-01

    Defects in semiconductors can exhibit multiple charge states, which can be used for charge storage applications. Here we consider such charge storage in a series of oxygen deficient phases of TiO2, known as Magnéli phases. These Magnéli phases (TinO2n-1) present well-defined crystalline structures, i.e., their deviation from stoichiometry is accommodated by changes in space group as opposed to point defects. We show that these phases exhibit intermediate bands with an electronic quadruple donor transitions akin to interstitial Ti defect levels in rutile TiO2. Thus, the Magnéli phases behave as if they contained a very large pseudo-defect density: ½ per formula unit TinO2n-1. Depending on the Fermi Energy the whole material will become charged. These crystals are natural charge storage materials with a storage capacity that rivals the best known supercapacitors. PMID:27364139

  8. Charge storage in oxygen deficient phases of TiO2: defect Physics without defects

    NASA Astrophysics Data System (ADS)

    Padilha, A. C. M.; Raebiger, H.; Rocha, A. R.; Dalpian, G. M.

    2016-07-01

    Defects in semiconductors can exhibit multiple charge states, which can be used for charge storage applications. Here we consider such charge storage in a series of oxygen deficient phases of TiO2, known as Magnéli phases. These Magnéli phases (TinO2n-1) present well-defined crystalline structures, i.e., their deviation from stoichiometry is accommodated by changes in space group as opposed to point defects. We show that these phases exhibit intermediate bands with an electronic quadruple donor transitions akin to interstitial Ti defect levels in rutile TiO2. Thus, the Magnéli phases behave as if they contained a very large pseudo-defect density: ½ per formula unit TinO2n-1. Depending on the Fermi Energy the whole material will become charged. These crystals are natural charge storage materials with a storage capacity that rivals the best known supercapacitors.

  9. Study of adsorption and degradation of dimethylphthalate on TiO2-based photocatalysts

    NASA Astrophysics Data System (ADS)

    Pulido Melián, E.; Henríquez-Cárdenes, E.; González Díaz, O.; Doña Rodríguez, J. M.

    2016-08-01

    This work studied the degradation and adsorption of dimethylphthalate (DMP) using various TiO2-based photocatalysts: TiO2 Aeroxide P25, Kronos vlp7000, Hombikat UV-100, Kemira 650 and a synthesized photocatalyst named SG750. As the photocatalysts with mixed anatase and rutile phases, P25 and SG750, showed greater activity than those of pure phase, an in-depth study was undertaken of these two catalysts in the adsorption and degradation of DMP. The degradation results were fitted with a high degree of correlation to the Langmuir-Hinshelwood model and those for adsorption to the Freundlich model. The Freundlich constants showed good correlation with FTIR observations of the DMP-P25 and DMP-SG750 interactions. These two photocatalysts were additionally modified by photodeposition with Pt and Au (0.5-1.5 wt%) to study the effect of these metals on degradation and mineralization kinetics.

  10. Charge storage in oxygen deficient phases of TiO2: defect Physics without defects

    PubMed Central

    Padilha, A. C. M.; Raebiger, H.; Rocha, A. R.; Dalpian, G. M.

    2016-01-01

    Defects in semiconductors can exhibit multiple charge states, which can be used for charge storage applications. Here we consider such charge storage in a series of oxygen deficient phases of TiO2, known as Magnéli phases. These Magnéli phases (TinO2n−1) present well-defined crystalline structures, i.e., their deviation from stoichiometry is accommodated by changes in space group as opposed to point defects. We show that these phases exhibit intermediate bands with an electronic quadruple donor transitions akin to interstitial Ti defect levels in rutile TiO2. Thus, the Magnéli phases behave as if they contained a very large pseudo-defect density: ½ per formula unit TinO2n−1. Depending on the Fermi Energy the whole material will become charged. These crystals are natural charge storage materials with a storage capacity that rivals the best known supercapacitors. PMID:27364139

  11. Novel three-dimensional dandelion-like TiO 2 structure with high photocatalytic activity

    NASA Astrophysics Data System (ADS)

    Bai, Xuelian; Xie, Bin; Pan, Nan; Wang, Xiaoping; Wang, Haiqian

    2008-03-01

    Pure rutile phase crystalline TiO 2 powder with novel 3D dandelion-like structure was synthesized by using a facile hydrothermal method with TiCl 3 as the main starting material. In such a 3D structure, the nanometer-scale construction elements aggregate together and form a micrometer-scale artificial unit. The typical 3D dandelion structure has an average diameter of 1.5-2 μm and is packed radially by nanorods with [001] preference growth direction. Each individual nanorod is hundreds of nanometers in length, and tens of nanometers in diameter. The obtained 3D dandelion-like TiO 2 powder has a high photocatalytic activity, which is equivalent to that of the commercial available P25 titania powder. Mechanisms of the formation of the dandelion-like structure were also discussed. A different oxidation process of Ti(III) to Ti(IV) during hydrothermal was suggested.

  12. Identification of the Active Species in Photochemical Hole Scavenging Reactions of Methanol on TiO2

    SciTech Connect

    Shen, Mingmin; Henderson, Michael A.

    2011-11-03

    Molecular and dissociative methanol adsorption species were prepared on rutile TiO2(110) surfaces to study photocatalytic oxidation of methanol in ultrahigh vacuum (UHV) using temperature-programmed desorption (TPD). Adsorbed methoxy groups (CH3O-) were found to be the photoactive form of adsorbed methanol converted to adsorbed formaldehyde and a surface OH group by hole-mediated C-H bond cleavage. These results suggest that adsorbed methoxy is the effective hole scavenger in photochemical reactions involving methanol.

  13. 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.

  14. 3D periodic multiscale TiO2 architecture: a platform decorated with graphene quantum dots for enhanced photoelectrochemical water splitting

    NASA Astrophysics Data System (ADS)

    Xu, Zhen; Yin, Min; Sun, Jing; Ding, Guqiao; Lu, Linfeng; Chang, Paichun; Chen, Xiaoyuan; Li, Dongdong

    2016-03-01

    Micropatterned TiO2 nanorods (TiO2NRs) via three-dimensional (3D) geometry engineering in both microscale and nanoscale decorated with graphene quantum dots (GQDs) have been demonstrated successfully. First, micropillar (MP) and microcave (MC) arrays of anatase TiO2 films are obtained through the sol-gel based thermal nanoimprinting method. Then they are employed as seed layers in hydrothermal growth to fabricate the 3D micropillar/microcave arrays of rutile TiO2NRs (NR), which show much-improved photoelectrochemical water-splitting performance than the TiO2NRs grown on flat seed layer. The zero-dimensional GQDs are sequentially deposited onto the surfaces of the microscale patterned nanorods. Owing to the fast charge separation that resulted from the favorable band alignment of the GQDs and rutile TiO2, the MP-NR-GQDs electrode achieves a photocurrent density up to 2.92 mA cm-2 under simulated one-sun illumination. The incident-photon-to-current-conversion efficiency (IPCE) value up to 72% at 370 nm was achieved on the MP-NR-GQDs electrode, which outperforms the flat-NR counterpart by 69%. The IPCE results also imply that the improved photocurrent mainly benefits from the distinctly enhanced ultraviolet response. The work provides a cost-effective and flexible pathway to develop periodic 3D micropatterned photoelectrodes and is promising for the future deployment of high performance optoelectronic devices.

  15. Oxygen vacancy induced phase formation and room temperature ferromagnetism in undoped and Co-doped TiO2 thin films

    NASA Astrophysics Data System (ADS)

    Mohanty, P.; Mishra, N. C.; Choudhary, R. J.; Banerjee, A.; Shripathi, T.; Lalla, N. P.; Annapoorni, S.; Rath, Chandana

    2012-08-01

    TiO2 and Co-doped TiO2 (CTO) thin films deposited at various oxygen partial pressures by pulsed laser deposition exhibit room temperature ferromagnetism (RTFM) independent of their phase. Films deposited at 0.1 mTorr oxygen partial pressure show a complete rutile phase confirmed from glancing angle x-ray diffraction and Raman spectroscopy. At the highest oxygen partial pressure, i.e. 300 mTorr, although the TiO2 film shows a complete anatase phase, a small peak corresponding to the rutile phase along with the anatase phase is identified in the case of CTO film. An increase in O to Ti/(Ti+Co) ratio with increase in oxygen partial pressure is observed from Rutherford backscattering spectroscopy. It is revealed from x-ray photoelectron spectroscopy (XPS) that oxygen vacancies are found to be higher in the CTO film than TiO2, while the valency of cobalt remains in the +2 state. Therefore, the CTO film deposited at 300 mTorr does not show a complete anatase phase unlike the TiO2 film deposited at the same partial pressure. We conclude that RTFM in both films is not due to impurities/contaminants, as confirmed from XPS depth profiling and cross-sectional transmission electron microscopy (TEM), but due to oxygen vacancies. The magnitude of moment, however, depends not only on the phase of TiO2 but also on the crystallinity of the films.

  16. Niobian rutile in an Apollo 14 KREEP fragment.

    NASA Technical Reports Server (NTRS)

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

    1972-01-01

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

  17. Sea grass like arranged TiO2 nanorods sensitized by natural dyes for solar cell applications

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

    Rutile-phase seagrass-like-arranged TiO2 nanorods have been synthesized by low-temperature template-free hydrothermal method. These TiO2 nanorods have been sensitized by flowers of Sesbania grandiflora, leaves of Camellia sinensis and roots of Rubia tinctorum. The sensitized TiO2 nanorods-based films have been used as photoanode in natural dye-sensitized solar cells. The films were photoelectrochemically active, and the fabricated solar cells had short-circuit photocurrent density (JSC) lying in the range of 3.7-4.7mAcm-2. The efficiency of the fabricated natural dye-sensitized solar cells was found to lie in the range of 0.6-1.036 %, respectively

  18. Photochromism-based detection of volatile organic compounds by W-doped TiO2 nanofibers.

    PubMed

    Jin, Ming; Zhang, Xintong; Pu, Hongting; Nishimoto, Shunsuke; Murakami, Taketoshi; Fujishima, Akira

    2011-10-01

    W-doped TiO(2) nanofibers with various compositions (W/Ti: 2-8%) were fabricated by the electrospinning method from respective precursor solutions containing tungsten(V) pentaethoxide, titanium tetraisopropoxide (TTIP), and polyvinylpyrrolidone (PVP), followed with calcination at 550 °C. Morphological and structural characteristics of these nanofibers were studied with SEM, XRD and XPS. W-doping inhibited the crystal growth and anatase-to-rutile transformation of TiO(2) nanofibers. W-doped TiO(2) nanofiber mats showed good photocatalytic oxidation abilities for acetone. Obvious color change from white to blue of mats during the photocatalysis process can be detected by naked eyes, which provides a good way in detection of pollutants in indoor air, especially for the volatile organic compounds (VOCs). PMID:21741658

  19. Rietveld analysis of the effect of annealing atmosphere on phase evolution of nanocrystalline TiO2 powders.

    PubMed

    Salari, M; Rezaee, M; Chidembo, A T; Konstantinov, K; Liu, H K

    2012-06-01

    The structural evolution of nanocrystalline TiO2 was studied by X-ray diffraction (XRD) and the Rietveld refinement method (RRM). TiO2 powders were prepared by the sol-gel technique. Post annealing of as-synthesized powders in the temperature range from 500 degrees C to 800 degrees C under air and argon atmospheres led to the formation of TiO2 nanoparticles with mean crystallite size in the range of 37-165 nm, based on the Rietveld refinement results. It was found that the phase structure, composition, and crystallite size of the resulting particles were dependent on not only the annealing temperature, but also the annealing atmosphere. Rietveld refinement of the XRD data showed that annealing the powders under argon atmosphere promoted the polymorphic phase transformation from anatase to rutile. Field emission scanning electron microscopy (FESEM) was employed to investigate the morphology and size of the annealed powders.

  20. Apatite formation on alkaline-treated dense TiO2 coatings deposited using the solution precursor plasma spray process.

    PubMed

    Chen, Dianying; Jordan, Eric H; Gell, Maurice; Wei, Mei

    2008-05-01

    A dense titania (TiO2) coating was deposited from an ethanol-based solution containing titanium isopropoxide using the solution precursor plasma spray (SPPS) process. XRD and Raman spectrum analyses confirmed that the coating is exclusively composed of rutile TiO2. SEM micrographs show the as-sprayed coating is dense with a uniform thickness and there are no coarse splat boundaries. The as-sprayed coating was chemically treated in 5M NaOH solution at 80 degrees C for 48 h. The bioactivity of as-sprayed and alkaline-treated coatings was investigated by immersing the coatings in simulated body fluid (SBF) for 14-28 days, respectively. After 28 days immersion, there is a complete layer of carbonate-containing apatite formed on the alkaline-treated TiO2 coating surface, but none formed on the as-sprayed coating.

  1. CdS-sensitized TiO2 in phenazopyridine photo-degradation: catalyst efficiency, stability and feasibility assessment.

    PubMed

    Zyoud, Ahed H; Zaatar, Nidal; Saadeddin, Iyad; Ali, Cheknane; Park, DaeHoon; Campet, Guy; Hilal, Hikmat S

    2010-01-15

    Mineralization of phenazopyridine, 1, in water, under solar-simulator radiation was efficiently achieved using nanoparticle CdS-sensitized rutile TiO(2), TiO(2)/CdS, 2, as photo-catalysts. Despite that, 2 showed two main drawbacks. Firstly, the system was difficult to recover by simple filtration, and demanded centrifugation. Secondly, the sensitizer CdS showed relatively high tendency to leach out hazardous Cd(2+) ions under photo-degradation reaction conditions. In an attempt to solve out such difficulties, 2 was supported onto sand surface. The sand/TiO(2)/CdS system, 3, was easier to recover but showed slightly lower catalytic activity compared to 2. On the other hand, the support failed to prevent leaching of Cd(2+). This indicates limited future applicability of CdS-sensitized TiO(2) photo-catalyst systems, in solar-based water purification strategies, unless leaching out tendency is completely prevented.

  2. Transmission Electron Microscopy and Scanning Transmission X-Ray Microscopy Studies on the Bioaccumulation and Tissue Level Absorption of TiO2 Nanoparticles in Daphnia magna.

    PubMed

    Kwon, Dongwook; Nho, Hyun Woo; Yoon, Tae Hyun

    2015-06-01

    In this study, bioaccumulation and tissue-level absorption of TiO2 nanoparticles (NPs) in freshwater invertebrates were investigated using transmission electron microscopy (TEM) and scanning transmission X-ray microscopy (STXM). The TiO2 NPs were used to test impacts of core sizes (i.e., 5 ± 2 nm and 23 ± 7 nm for TiO2(SYN) and TiO2(P25), respectively) and agglomerations (i.e., well dispersed vs. highly agglomerated) on the uptake of TiO2 NPs in Daphnia magna (D. magna). Highly agglomerated TiO2 NPs, regardless of their core sizes, were heavily taken up into the digestive tract of D. magna and no detectable penetration of both TiO2 NPs into the gut epithelial cells of D. magna was observed in TEM and STXM images. However, significant damages involving morphological changes in the microvilli and gut epithelial cells (e.g., irregular shaped microvilli, epithelial cell protrusion, and dilatation of cytoplasmic inclusion) were observed only with the commercial TiO2 NPs (TiO2(P25)) with larger core size and mixed crystalline phase, while the laboratory synthesized TiO2 NPs (TiO2(Syn)) with smaller core size and single crystalline phase showed slight morphological changes in the gut microvilli and epithelial cells. In the case of D. magna exposed to the well dispersed synthetic TiO2 NP ((Cit)TiO2(Syn)), only a negligible amount of TiO2 NPs were found within the digestive tract of the D. magna without any significant damages in the gut microvilli and epithelial cells and any detectable penetrations of TiO2 NPs into epithelial cells of D. magna gut. These TEM and STXM observations confirmed us that uptake of NP into D. magna are strongly dependent on their agglomeration (i.e., hydrodynamic sizes), rather than their core sizes, while direct penetration of NPs into tissues of digestive tract seems unlikely without significant morphological changes (e.g., collapse of the epithelial tissue) caused by high toxicity of NPs or released metal ions.

  3. Preparation and characterization of Cu-doped TiO2 materials for electrochemical, photoelectrochemical, and photocatalytic applications

    NASA Astrophysics Data System (ADS)

    Ganesh, Ibram; Kumar, Polkampally P.; Annapoorna, Ibram; Sumliner, Jordan M.; Ramakrishna, Mantripragada; Hebalkar, Neha Y.; Padmanabham, Gade; Sundararajan, Govindan

    2014-02-01

    The Cu-doped TiO2 (Cu = 0-50 wt.%) powders and thin films were prepared by following a homogeneous co-precipitation method and sol-gel dip-coating technique, respectively, and were treated through 400-800 °C, and then thoroughly investigated by following various characterization techniques. The characterization results suggest that the pure TiO2 powder formed at 550 °C is in rutile phase, whereas the 0.1-10 wt.% Cu-doped TiO2 powders formed at 550 °C are mainly in anatase phase. These latter powders possess low band-gap energies (3.247-3.265 eV) and flat-band potentials amenable to water oxidation reaction. The 0.5-wt.% Cu-doped TiO2 thin film formed at 550 °C exhibited n-type semiconducting behavior and considerable photocurrent among various investigated powders. The CO2 reduction with a Faradaic efficiency of 82% and ˜ 96% CO selectivity in a two-compartment electrochemical cell was noted at -2500 mV (vs. Ag/Ag+) on pre-reduced (at -2000 mV vs. Ag/AgCl) 50 wt.% Cu-doped TiO2 thin film electrode in conjunction with an ionic liquid. The UV-light-induced TiO2 was found to be responsible for photocatalytic methylene blue (MB) degradation, and TiO2 is not sensitized by MB. The in situ formed compounds of TiO2 and CuO/Cu2O were found to absorb visible light, but showed little visible-light-induced photocatalytic activity.

  4. Dielectric relaxation and conduction mechanisms in sprayed TiO2 thin films as a function of the annealing temperature

    NASA Astrophysics Data System (ADS)

    Juma, Albert; Acik, Ilona Oja; Mere, Arvo; Krunks, Malle

    2016-04-01

    The electrical properties of TiO2 thin films deposited by chemical spray pyrolysis onto Si substrates were investigated in the metal-oxide-semiconductor (MOS) configuration using current-voltage characteristics and impedance spectroscopy. The electrical properties were analyzed in relation to the changes in microstructure induced during annealing in air up to a temperature of 950 °C. Anatase to rutile transformation started after annealing at 800 °C, and at 950 °C, only the rutile phase was present. The dielectric relaxation strongly depended upon the microstructure of TiO2 with the dielectric constant for the anatase phase between 45 and 50 and that for the rutile phase 123. Leakage current was reduced by three orders of magnitude after annealing at 700 °C due to the densification of the TiO2 film. A double-logarithmic plot of the current-voltage characteristics showed a linear relationship below 0.12 V consistent with Ohmic conduction, while space-charge-limited conduction mechanism as described by Child's law dominated for bias voltages above 0.12 V.

  5. Influence of TiO2 nanoparticles on cellular antioxidant defense and its involvement in genotoxicity in HepG2 cells

    NASA Astrophysics Data System (ADS)

    Petković, Jana; Žegura, Bojana; Filipič, Metka

    2011-07-01

    We investigated the effects of two types of TiO2 nanoparticles (<25 nm anatase, TiO2-An; <100 nm rutile, TiO2-Ru) on cellular antioxidant defense in HepG2 cells. We previously showed that in HepG2 cells, TiO2 nanoparticles are not toxic, although they induce oxidative DNA damage, production of intracellular reactive oxygen species, and up-regulation of mRNA expression of DNA-damage-responsive genes (p53, p21, gadd45α and mdm2). In the present study, we measured changes in mRNA expression of several antioxidant enzymes: catalase, superoxide dismutase, glutathione peroxidase, nitric oxide synthase, glutathione reductase and glutamate-cysteine ligase. As reduced glutathione has a central role in cellular antioxidant defense, we determined the effects of TiO2 nanoparticles on changes in the intracellular glutathione content. To confirm a role for glutathione in protection against TiO2-nanoparticle-induced DNA damage, we compared the extent of TiO2-nanoparticle-induced DNA damage in HepG2 cells that were glutathione depleted with buthionine-(S,R)-sulfoximine pretreatment and in nonglutathione-depleted cells. Our data show that both types of TiO2 nanoparticles up-regulate mRNA expression of oxidative-stress-related genes, with TiO2-Ru being a stronger inducer than TiO2-An. Both types of TiO2 nanoparticles also induce dose-dependent increases in intracellular glutathione levels, and in glutathione-depleted cells, TiO2-nanoparticle-induced DNA damage was significantly greater than in nonglutathione-depleted cells. Interestingly, the glutathione content and the extent of DNA damage were significantly higher in TiO2-An- than TiO2-Ru-exposed cells. Thus, we show that TiO2 nanoparticles cause activation of cellular antioxidant processes, and that intracellular glutathione has a critical role in defense against this TiO2-nanoparticle-induced DNA damage.

  6. 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

  7. Femtosecond laser deposition of TiO2 nanoparticle-assembled films with embedded CdS nanoparticles

    NASA Astrophysics Data System (ADS)

    Ni, Xiao-chang; Sang, Li-xia; Zhang, Hong-jie; Kiliyanamkandy, Anoop; Amoruso, Salvatore; Wang, Xuan; Fittipaldi, Rosalba; Li, Tong; Hu, Ming-lie; Xu, Li-juan

    2014-01-01

    Based on the normal pulsed laser ablation method, femtosecond pulsed laser deposition (fs-PLD) is adopted in vacuum for the production of TiO2 nanoparticle-assembled films. We study the morphology and electronic characteristics of TiO2 nanoparticle-assembled films deposited at different oxygen background gas pressures from high vacuum (˜10-4 Pa) to 100 Pa and different deposition time. Our results show that TiO2 nanoparticle-assembled films obtained in high vacuum present both a mixture with rutile phase and anatase phase and a pure rutile phase. At the same time, there are more mesoporous structures in the film after annealing, which is beneficial for the enhancement of photocatalytic activity. In water splitting experiment, part of the TiO2 nanoparticle-assembled films embedded with a small mass fraction of CdS nanoparticles (˜5%) present an interesting photocurrent enhancement with a maximum value of ˜0.2 mA/cm2 under a solar simulator.

  8. Formation of TiO2 Thin Films using NH3 as Catalyst by Metalorganic Chemical Vapor Deposition

    NASA Astrophysics Data System (ADS)

    Jung, Sung-Hoon; Kang, Sang-Won

    2001-05-01

    We have studied metalorganic chemical vapor deposition of TiO2 thin films using titanium tetra-isopropoxide [TTIP, Ti(O--C3H7)4] and NH3 as a catalyst at deposition temperatures ranging from 250 to 365°C. At deposition temperatures above 330°C, pyrolytic self-decomposition of TTIP is dominant regardless of the use of NH3, and the activation energy for TiO2 film formation is 152 kJ/mol. At deposition temperatures below 330°C, the films can be formed with the help of the catalytic activity of NH3, and the activation energy is reduced to 55 kJ/mol. TiO2 films deposited through the pyrolytic self-decomposition of TTIP have an anatase structure before and after performing post-deposition annealing in oxygen ambient for 30 min at 750°C. On the other hand, the as-deposited films formed through the catalytic reaction of TTIP with NH3 incorporate nitrogen impurities and have microcrystallites of the rutile structure within the amorphous matrix. However, the post-deposition annealing, the nitrogen impurities are completely removed from the films, and the films are converted into polycrystalline TiO2 films with the rutile structure, which have a high dielectric constant of 82 and a low leakage current.

  9. Synthesis and characterization of undoped and cobalt-doped TiO2 nanoparticles via sol-gel technique

    NASA Astrophysics Data System (ADS)

    Mugundan, S.; Rajamannan, B.; Viruthagiri, G.; Shanmugam, N.; Gobi, R.; Praveen, P.

    2015-04-01

    TiO2 nanoparticles doped with different concentrations of cobalt (4, 8, 12 and 16 %) were synthesized by sol-gel method at room temperature with appropriate reactants. In general, TiO2 can exist in anatase, rutile, and brookite phases. In this present study, we used titanium tetra iso propoxide and 2-propanol as a common starting materials and the obtained products were calcined at 500 °C and 800 °C to get anatase and rutile phases, respectively. The crystalline sizes of the doped and undoped TiO2 nanoparticles were observed with X-ray diffraction (XRD) analysis. The functional groups of the samples were identified by Fourier transform infrared spectroscopy (FTIR). From UV-VIS diffuse reflectance spectra (DRS), the band gap energy and excitation wavelength of doped and undoped TiO2 nanoparticles were identified. The defect oriented emissions were seen from photoluminescence (PL) study. The spherical uniform size distribution of particles and elements present in the samples was determined using two different techniques viz., scanning electron microscopy (SEM) with energy-dispersive spectrometer (EDX) and transmission electron microscope (TEM) with selected area electron diffraction (SAED) pattern. The second harmonic generation (SHG) efficiency was also found and the obtained result was compared with potassium di hydrogen phosphate (KDP).

  10. Single-crystalline aluminum film for ultraviolet plasmonic nanolasers

    PubMed Central

    Chou, Bo-Tsun; Chou, Yu-Hsun; Wu, Yen-Mo; Chung, Yi-Cheng; Hsueh, Wei-Jen; Lin, Shih-Wei; Lu, Tien-Chang; Lin, Tzy-Rong; Lin, Sheng-Di

    2016-01-01

    Significant advances have been made in the development of plasmonic devices in the past decade. Plasmonic nanolasers, which display interesting properties, have come to play an important role in biomedicine, chemical sensors, information technology, and optical integrated circuits. However, nanoscale plasmonic devices, particularly those operating in the ultraviolet regime, are extremely sensitive to the metal and interface quality. Thus, these factors have a significant bearing on the development of ultraviolet plasmonic devices. Here, by addressing these material-related issues, we demonstrate a low-threshold, high-characteristic-temperature metal-oxide-semiconductor ZnO nanolaser that operates at room temperature. The template for the ZnO nanowires consists of a flat single-crystalline Al film grown by molecular beam epitaxy and an ultrasmooth Al2O3 spacer layer synthesized by atomic layer deposition. By effectively reducing the surface plasmon scattering and metal intrinsic absorption losses, the high-quality metal film and the sharp interfaces formed between the layers boost the device performance. This work should pave the way for the use of ultraviolet plasmonic nanolasers and related devices in a wider range of applications. PMID:26814581

  11. Atomically flat single-crystalline gold nanostructures for plasmonic nanocircuitry.

    PubMed

    Huang, Jer-Shing; Callegari, Victor; Geisler, Peter; Brüning, Christoph; Kern, Johannes; Prangsma, Jord C; Wu, Xiaofei; Feichtner, Thorsten; Ziegler, Johannes; Weinmann, Pia; Kamp, Martin; Forchel, Alfred; Biagioni, Paolo; Sennhauser, Urs; Hecht, Bert

    2010-01-01

    Deep subwavelength integration of high-definition plasmonic nanostructures is of key importance in the development of future optical nanocircuitry for high-speed communication, quantum computation and lab-on-a-chip applications. To date, the experimental realization of proposed extended plasmonic networks consisting of multiple functional elements remains challenging, mainly because of the multi-crystallinity of commonly used thermally evaporated gold layers. This can produce structural imperfections in individual circuit elements that drastically reduce the yield of functional integrated nanocircuits. In this paper we demonstrate the use of large (>100 μm(2)) but thin (<80 nm) chemically grown single-crystalline gold flakes that, after immobilization, serve as an ideal basis for focused ion beam milling and other top-down nanofabrication techniques on any desired substrate. Using this methodology we obtain high-definition ultrasmooth gold nanostructures with superior optical properties and reproducible nano-sized features over micrometre-length scales. Our approach provides a possible solution to overcome the current fabrication bottleneck and realize high-definition plasmonic nanocircuitry. PMID:21267000

  12. Single-crystalline aluminum film for ultraviolet plasmonic nanolasers.

    PubMed

    Chou, Bo-Tsun; Chou, Yu-Hsun; Wu, Yen-Mo; Chung, Yi-Cheng; Hsueh, Wei-Jen; Lin, Shih-Wei; Lu, Tien-Chang; Lin, Tzy-Rong; Lin, Sheng-Di

    2016-01-01

    Significant advances have been made in the development of plasmonic devices in the past decade. Plasmonic nanolasers, which display interesting properties, have come to play an important role in biomedicine, chemical sensors, information technology, and optical integrated circuits. However, nanoscale plasmonic devices, particularly those operating in the ultraviolet regime, are extremely sensitive to the metal and interface quality. Thus, these factors have a significant bearing on the development of ultraviolet plasmonic devices. Here, by addressing these material-related issues, we demonstrate a low-threshold, high-characteristic-temperature metal-oxide-semiconductor ZnO nanolaser that operates at room temperature. The template for the ZnO nanowires consists of a flat single-crystalline Al film grown by molecular beam epitaxy and an ultrasmooth Al2O3 spacer layer synthesized by atomic layer deposition. By effectively reducing the surface plasmon scattering and metal intrinsic absorption losses, the high-quality metal film and the sharp interfaces formed between the layers boost the device performance. This work should pave the way for the use of ultraviolet plasmonic nanolasers and related devices in a wider range of applications. PMID:26814581

  13. Epitaxial Growth of Zinc Oxide on Single Crystalline Gold Plates

    NASA Astrophysics Data System (ADS)

    Greenberg, Kathryn; Joo, John; Baram, Mor; Clarke, David; Hu, Evelyn

    2012-02-01

    Although metal-oxide interfaces are the critical components of many electronic and optical devices, it is rare to find epitaxial metal-oxide structures. We demonstrate for the first time, a method for the low temperature, epitaxial growth of zinc oxide (ZnO) on single crystalline gold plates. The gold plates, up to 100μm in width, are grown from a gold-surfactant complex. Even with the large lattice mismatch between (111) gold and (0001) ZnO, we are able to form epitaxial zinc oxide at 90^oC on top of the single crystal gold plates. This epitaxial growth is confirmed using transmission electron microscopy, electron diffraction, and electron backscatterer diffraction. Micro-photoluminescence is also performed to investigate the optical properties of the epitaxial zinc oxide. We remove the grown ZnO membranes from the gold plates using a stamping and etching process. These membranes can potentially be used to fabricate high quality microdisks and photonic crystals. The metal-oxide interfaces that we have fabricated may have the ability to be used in a number of technologically important applications, including as better electrical contacts and for improved light extraction from planar LED structures.

  14. Synthesis and magnetic properties of single-crystalline magnetite nanowires

    NASA Astrophysics Data System (ADS)

    Han, Qin; Liu, Zhenghui; Xu, Yingying; Zhang, Han

    2007-09-01

    By carefully controlling the reaction conditions, nanowires of Fe 3O 4 are directly acquired from nanowires of α-Fe 2O 3 in a reduced atmosphere at 410-430 °C. X-ray diffraction, Raman spectrum, and transmission electron microscopic analyses demonstrate that the product is single-crystalline Fe 3O 4. The nanowires have diameters of 40-90 nm and lengths of 10-20 μm, which are close to those of the pristine α-Fe 2O 3 nanowires. By studying different growth conditions, we find that hydrogen can push the conversion of the crystal structures, while temperature determines the chemical composition of the final products. The magnetic properties of as-prepared Fe 3O 4 nanowires are measured using a quantum design magnetic property measurement system. The nanowires show a ferrimagnetic behavior at room temperature and their magnetic properties are strongly influenced by surface and interface effects. The Verwey transition temperature ( TV=116 K) is found to be a little lower than that of bulk materials, which can be attributed to the small deviation from stoichiometry caused by the oxygen vacancies near the surfaces. Below 12 K, the nanowires show a spin-glass-like behavior owing to the disordered frozen magnetic state at the surfaces.

  15. Large-Scale Synthesis of Transition-Metal-Doped TiO2 Nanowires with Controllable Overpotential

    SciTech Connect

    Liu, Bin; Chen, HaoMing; Liu, Chong; Andrews, Sean; Han, Chris; Yang, Peidong

    2013-03-13

    Practical implementation of one-dimensional semiconductors into devices capable of exploiting their novel properties is often hindered by low product yields, poor material quality, high production cost, or overall lack of synthetic control. Here, we show that a molten-salt flux scheme can be used to synthesize large quantities of high-quality, single-crystalline TiO2 nanowires with controllable dimensions. Furthermore, in situ dopant incorporation of various transition metals allows for the tuning of optical, electrical, and catalytic properties. With this combination of control, robustness, and scalability, the molten-salt flux scheme can provide high-quality TiO2 nanowires to satisfy a broad range of application needs from photovoltaics to photocatalysis.

  16. Increased visible-light photocatalytic activity of TiO2 via band gap manipulation

    NASA Astrophysics Data System (ADS)

    Pennington, Ashley Marie

    Hydrogen gas is a clean burning fuel that has potential applications in stationary and mobile power generation and energy storage, but is commercially produced from non-renewable fossil natural gas. Using renewable biomass as the hydrocarbon feed instead could provide sustainable and carbon-neutral hydrogen. We focus on photocatalytic oxidation and reforming of methanol over modified titanium dioxide (TiO2) nanoparticles to produce hydrogen gas. Methanol is used as a model for biomass sugars. By using a photocatalyst, we aim to circumvent the high energy cost of carrying out endothermic reactions at commercial scale. TiO2 is a semiconductor metal oxide of particular interest in photocatalysis due to its photoactivity under ultraviolet illumination and its stability under catalytic reaction conditions. However, TiO2 primarily absorbs ultraviolet light, with little absorption of visible light. While an effective band gap for absorbance of photons from visible light is 1.7 eV, TiO2 polymorphs rutile and anatase, have band gaps of 3.03 eV and 3.20 eV respectively, which indicate ultraviolet light. As most of incident solar radiation is visible light, we hypothesize that decreasing the band gap of TiO2 will increase the efficiency of TiO2 as a visible-light active photocatalyst. We propose to modify the band gap of TiO2 by manipulating the catalyst structure and composition via metal nanoparticle deposition and heteroatom doping in order to more efficiently utilize solar radiation. Of the metal-modified Degussa P25 TiO2 samples (P25), the copper and nickel modified samples, 1%Cu/P25 and 1%Ni/P25 yielded the lowest band gap of 3.05 eV each. A difference of 0.22 eV from the unmodified P25. Under visible light illumination 1%Ni/P25 and 1%Pt/P25 had the highest conversion of methanol of 9.9% and 9.6%, respectively.

  17. 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.

  18. Ultra-long Pt nanolawns supported on TiO2-coated carbon fibers as 3D hybrid catalyst for methanol oxidation

    PubMed Central

    2012-01-01

    In this study, TiO2 thin film photocatalyst on carbon fibers was used to synthesize ultra-long single crystalline Pt nanowires via a simple photoreduction route (thermally activated photoreduction). It also acted as a co-catalytic material with Pt. Taking advantage of the high-aspect ratio of the Pt nanostructure as well as the excellent catalytic activity of TiO2, this hybrid structure has the great potential as the active anode in direct methanol fuel cells. The electrochemical results indicate that TiO2 is capable of transforming CO-like poisoning species on the Pt surface during methanol oxidation and contributes to a high CO tolerance of this Pt nanowire/TiO2 hybrid structure. PMID:22546416

  19. Molecular-Level Insights into Photocatalysis from Scanning Probe Microscopy Studies on TiO2(110)

    SciTech Connect

    Henderson, Michael A.; Lyubinetsky, Igor

    2013-06-12

    The field of heterogeneous photocatalysis has grown considerably in the decades since Fujishima and Honda's ground-breaking publications of photoelectrochemistry on TiO2. Numerous review articles continue to point to both progress made in the use of heterogeneous materials (such as TiO2) to perform photoconversion processes, and the many opportunities and challenges in heterogeneous photocatalysis research such as solar energy conversion and environmental remediation. The past decade has also seen an increase in the use of molecular-level approaches applied to model single crystal surfaces in an effort to obtain new insights into photocatalytic phenomena. In particular, scanning probe techniques (SPM) have enabled researchers to take a ‘nanoscale’ approach to photocatalysis that includes interrogation of the reactivities of specific sites and adsorbates on a model photocatalyst surface. The rutile TiO2(110) surface has become the prototypical oxide single crystal surface for fundamental studies of many interfacial phenomena. In particular, TiO2(110) has become an excellent model surface for probing photochemical and photocatalytic reactions at the molecular level. A variety of experimental approaches have emerged as being ideally suited for studying photochemical reactions on TiO2(110), including desorption-oriented approaches and electronic spectroscopies, but perhaps the most promising techniques for evaluating site-specific properties are those of SPM. In this review, we highlight the growing use of SPM techniques in providing molecular-level insights into surface photochemistry on the model photocatalyst surface of rutile TiO2(110). Our objective is to both illustrate the unique knowledge that scanning probe techniques have already provided the field of photocatalysis, and also to motivate a new generation of effort into the use of such approaches to obtain new insights into the molecular level details of photochemical events occurring at interfaces

  20. The large-scale synthesis of one-dimensional TiO2 nanostructures using palladium as catalyst at low temperature.

    PubMed

    Xia, Mingxia; Zhang, Qinglin; Li, Hongxing; Dai, Guozhang; Yu, Hongchun; Wang, Taihong; Zou, Bingsuo; Wang, Yanguo

    2009-02-01

    The synthesis of TiO(2) nanostructures including nanowires and nanobelts has been demonstrated experimentally by anodization of Ti foil in an electrolyte, and by treatment in a PdCl(2) ethanol solution together with UV light irradiation and annealing at a temperature below 800 degrees C. The TiO(2) nanotube arrays resulting from the anodization were used as source precursor and transformed into nanowires and nanobelts respectively with high efficiency during the subsequent processes. The resulting TiO(2) nanowires and nanobelts, characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and Raman and surface photovoltage (SPV) spectroscopy, are single rutile crystals of high quality. In addition to the synthesis of the nanostructure at low temperature, this method also shows great advantages for the selectable morphology of the final TiO(2) nanostructures via adjustment of the UV light irradiation time and annealing temperature.

  1. Effect of vanadium admixing on the surface structure of TiO2(110) under non-oxidizing conditions

    NASA Astrophysics Data System (ADS)

    Song, Xin; Primorac, Elena; Kuhlenbeck, Helmut; Freund, Hans-Joachim

    2016-11-01

    Single crystalline Ti + V mixed oxide layers have been prepared by doping vanadium into TiO2(110) thin films on TiO2(110) single crystal substrates with a Ti + Ta mixed oxide interlayer between the film and the substrate. The interlayer prevents the diffusion of vanadium into the substrate and also the diffusion of Ti3 + between substrate and overlayer. Mixing vanadium into the TiO2 lattice increases the reducibility of the host oxide as concluded from an appreciable degree of reduction produced by comparatively mild annealing. A high density of bridging oxygen vacancies was identified at the surface of films with a low vanadium content (2%) while a (1 × 2) reconstruction as also known for massively reduced TiO2(110) was observed for layers with 8% of vanadium. Studies of methanol adsorption indicate that the vanadium atoms are mostly located below the surface since there is no indication of a vanadium-methanol interaction. We provide evidence that the reducibility of the vanadium ions in the thin film is higher than that of the titanium ions and we suggest that this is the origin of the increased reducibility of the mixed oxide.

  2. 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

  3. Structural, photoluminescent and photocatalytic properties of TiO2:Eu3+ coatings formed by plasma electrolytic oxidation

    NASA Astrophysics Data System (ADS)

    Stojadinović, Stevan; Radić, Nenad; Grbić, Boško; Maletić, Slavica; Stefanov, Plamen; Pačevski, Aleksandar; Vasilić, Rastko

    2016-05-01

    In this paper, we used plasma electrolytic oxidation (PEO) of titanium in water solution containing 10 g/L Na3PO4·12H2O + 2 g/L Eu2O3 powder for preparation of TiO2:Eu3+ coatings. The surfaces of obtained coatings exhibit a typical PEO porous structure. The energy dispersive X-ray spectroscopy analysis showed that the coatings are mainly composed of Ti, O, P, and Eu; it is observed that Eu content in the coatings increases with PEO time. The X-ray diffraction analysis indicated that the coatings are crystallized and composed of anatase and rutile TiO2 phases, with anatase being the dominant one. X-ray photoelectron spectroscopy revealed that Ti 2p spin-orbit components of TiO2:Eu3+ coatings are shifted towards higher binding energy, with respect to pure TiO2 coatings, suggesting that Eu3+ ions are incorporated into TiO2 lattice. Diffuse reflectance spectroscopy showed that TiO2:Eu3+ coatings exhibit evident red shift with respect to the pure TiO2 coatings. Photoluminescence (PL) emission spectra of TiO2:Eu3+ coatings are characterized by sharp emission bands in orange-red region ascribed to f-f transitions of Eu3+ ions from excited level 5D0 to lower levels 7FJ (J = 0, 1, 2, 3, and 4). The excitation PL spectra of TiO2:Eu3+ coatings can be divided into two regions: the broad band region from 250 nm to 350 nm associated with charge transfer state of Eu3+ and the series of sharp peaks in the range from 350 nm to 550 nm corresponding to direct excitation of the Eu3+ ions. It is observed that the intensity of peaks in excitation and emission PL spectra increases with the concentration of Eu3+, but the peak positions remain practically unchanged. The ratio of PL emission for electric and magnetic dipole transitions indicates highly asymmetric environment around Eu3+ ions. The photocatalytic activity (PA) of TiO2:Eu3+ coatings is evaluated by measuring the photodegradation of methyl orange under simulated sunlight conditions. It is shown that PEO time, i.e., the amount

  4. Relationship of O2 Photodesorption in Photooxidation of Acetone on TiO2

    SciTech Connect

    Henderson, Michael A.

    2008-07-31

    Organic photooxidation on TiO2 invariably involves the coexistence of organic species with oxygen on the surface at the same time. In the case of acetone and oxygen, both species exhibit their own interesting photochemistry on TiO2, but interdependences between the two are not understood. In this study, a rutile TiO2(110) surface possessing 7% surface oxygen vacancy sites is used as a model surface to probe the relationship between O2 photodesorption and acetone photodecomposition. Temperature programmed desorption (TPD) and photon stimulated desorption (PSD) measurements indicate that coadsorbed oxygen is essential to acetone photodecomposition on this surface, however the form of oxygen (molecular and dissociative) is not known. The first steps in acetone photodecomposition on TiO2(110) involve thermal activation with oxygen to form an acetone diolate ((CH3)2COO) species followed by photochemical decomposition to adsorbed acetate (CH3COO) and an ejected CH3 radical that is detected in PSD. Depending on the surface conditions, O2 PSD is also observed during the latter process. However, the time scales for the two PSD events (CH3 and O2) are quite different, withthe former occurring at ~10 times faster than the latter. By varying the preheating conditions or performing pre-irradiation on an O2 exposed surface, it becomes clear that the two PSD events are uncorrelated. That is, the O2 species responsible for O2 PSD is not a significant participant in the photochemistry of acetone on TiO2(110) and likely originates from a minority form of O2 on the surface. The CH3 and O2 PSD events do not appear to be in competition with each other suggesting either that ample charge carriers exist under the experimental conditions employed or that different charge carriers or excitation mechanisms are involved.

  5. Porous TiO2 Assembled from Monodispersed Nanoparticles

    NASA Astrophysics Data System (ADS)

    Liu, Xu; Duan, Weijie; Chen, Yan; Jiao, Shihui; Zhao, Yue; Kang, Yutang; Li, Lu; Fang, Zhenxing; Xu, Wei; Pang, Guangsheng

    2016-03-01

    Porous TiO2 were assembled by evaporating or refluxing TiO2 colloid, which was obtained by dispersing the TiO2 nanoparticles with a crystallite size (d XRD) of 3.2 nm into water or ethanol without any additives. Porous transparent bulk TiO2 was obtained by evaporating the TiO2-C2H5OH colloid at room temperature for 2 weeks, while porous TiO2 nanospheres were assembled by refluxing the TiO2-H2O colloid at 80 °C for 36 h. Both of the porous TiO2 architectures were pore-size-adjustable depending on the further treating temperature. Porous TiO2 nanospheres exhibited enhanced photocatalysis activity compared to the nanoparticles.

  6. Combined single-crystalline and polycrystalline CVD diamond substrates for diamond electronics

    SciTech Connect

    Vikharev, A. L. Gorbachev, A. M.; Dukhnovsky, M. P.; Muchnikov, A. B.; Ratnikova, A. K.; Fedorov, Yu. Yu.

    2012-02-15

    The fabrication of diamond substrates in which single-crystalline and polycrystalline CVD diamond form a single wafer, and the epitaxial growth of diamond films on such combined substrates containing polycrystalline and (100) single-crystalline CVD diamond regions are studied.

  7. Electron-Hole Recombination Time at TiO2 Single-Crystal Surfaces: Influence of Surface Band Bending.

    PubMed

    Ozawa, Kenichi; Emori, Masato; Yamamoto, Susumu; Yukawa, Ryu; Yamamoto, Shingo; Hobara, Rei; Fujikawa, Kazushi; Sakama, Hiroshi; Matsuda, Iwao

    2014-06-01

    Photocatalytic activity is determined by the transport property of photoexcited carriers from the interior to the surface of photocatalysts. Because the carrier dynamics is influenced by a space charge layer (SCL) in the subsurface region, an understanding of the effect of the potential barrier of the SCL on the carrier behavior is essential. Here we have investigated the relaxation time of the photoexcited carriers on single-crystal anatase and rutile TiO2 surfaces by time-resolved photoelectron spectroscopy and found that carrier recombination, taking a nanosecond time scale at room temperature, is strongly influenced by the barrier height of the SCL. Under the flat-band condition, which is realized in nanometer-sized photocatalysts, the carriers have a longer lifetime on the anatase surface than the rutile one, naturally explaining the higher photocatalytic activity for anatase than rutile.

  8. Influence of pH on the formulation of TiO2 powder prepared by co-precipitation of TiCl3 and photocatalytic activity

    NASA Astrophysics Data System (ADS)

    Yudoyono, Gatut; Zharvan, Vicran; Ichzan, Nur; Daniyati, Rizqa; Indarto, Bachtera; Pramono, Yono Hadi; Zainuri, Mochamad; Darminto

    2016-02-01

    Titanium dioxide (titania) nanoparticle were synthesized by coprecipitation process of titanium trichloride (TiCl3) in aqueous medium, with NH4OH as pH regulator. The pH solution was varied during the synthesis process between pH 3-8.4, and all samples were calcined temperature at 400°C for 3 hours. Characteristics and properties of the TiO2 powder were investigated using X-ray diffraction (XRD), Scanning Electron Microscopy (SEM). XRD results show that the single-phase rutile formed when the pH is less than 5, anatase single phase formed began pH 8, and the pH of the solution between 5-8 formed mixed phase rutile-anatase-brookite, rutile-brookite or anatase-brookite. Methylene Blue (MB) photodegradation test were performed in order to evaluate photocatalytic activity. Nanoparticles TiO2 rutile, anatase phase, and mixed phase rutile-brookite, anatase-brookite used to test the photocatalytic activity by measuring the absorbance spectrum photodegradation using UV-Vis spectrometer. The test results showed that the mixture phase of rutile-brookite provide the greatest photodegradation than other phases.

  9. Preparation of micro/nanostructure TiO2 spheres by controlling pollen as hard template and soft template.

    PubMed

    Yang, Xiaohui; Xu, Bin; Zhang, Xuehong; Song, Xiuqin; Chen, Rufen

    2014-09-01

    In this paper, micro/nanostructure TiO2 spheres were synthesized by a sunflower pollen induced and self-assembly mineralization process, in which a titania precursor and pollen reacted in one-pot at normal pressure. In this paper, the bio-template advantage, as hard and soft template is fully demonstrated. The superiority of our synthesis is that we not only can control pollen as hard template, but also can control it as soft template only by changing reactions temperature. Under 80 degrees C of water bath, TiO2 microspheres which replicated the morphology of pollen were prepared by controlling pollen as hard template. Under 100 degrees C, hierarchical TiO2 spheres with complicated morphology, different from pollen template, were synthesized by using pollen as soft template. At the same time, judicious choice of the amount of pollen affords the synthesis of hierarchical structures spheres with adjustable morphology and crystal structure. The morphology can be tuned from microspheres constructed from TiO2 nanorods to nanospheres constructed from TiO2 nanoparticles, and the crystal structure can be tuned from rutile to anatase. More over this anatase phase can be keep better even at high temperature of 1000 degrees C. The as-prepared micro/nano structure photocatalysts not only have high photocatalytic activities, but also have good separability and reuse performance.

  10. Template-free formation of vertically oriented TiO2 nanorods with uniform distribution for organics-sensing application.

    PubMed

    Mu, Qinghui; Li, Yaogang; Zhang, Qinghong; Wang, Hongzhi

    2011-04-15

    High-density arrays of vertically oriented TiO(2) nanorods with uniform distribution on Ti foil have been formed through template-free oxidation of Ti in hydrogen peroxide solutions. Subsequent thermal treatment was applied for growing mixed crystal structures to pursue higher performance. Morphology characterization using field emission scanning electron microscopy (FESEM) shows a nanorod diameter in the range of 20-50 nm with a length of 1.5 μm. X-ray diffraction (XRD) measurement demonstrates the crystallization of the TiO(2) nanorods prior to thermal treatment and the formation of anatase and rutile mixed phase after thermal treatment. The mixed crystal TiO(2) nanorods show a much higher performance than pure anatase in photoelectrochemical experiments. Steady-state photocurrent resulted from photocatalytic oxidation of organic compounds by TiO(2) nanorods is employed as response signal in determination of the organics to yield a linear range of 0-1.1mM for glucose. For other organics, an excellent linear relationship between the net steady-state photocurrent and the concentration of electrons transferred in exhaustive oxidation for these organics is obtained, which empowers the mixed crystal TiO(2) nanorods to serve as versatile material in organics-sensing application.

  11. Linear and nonlinear optical studies of bare and copper doped TiO2 nanoparticles via sol gel technique

    NASA Astrophysics Data System (ADS)

    Rajamannan, B.; Mugundan, S.; Viruthagiri, G.; Praveen, P.; Shanmugam, N.

    2014-01-01

    In general, the nanoparticles of TiO2 may exist in the phases of anatase, rutile and brookite. In the present work, we used titanium terta iso propoxide and 2-propanol as a common starting material to prepare the precursors of bare and copper doped nanosized TiO2. Then the synthesized products were calcinated at 500 °C and after calcination the pure TiO2 nanoparticles in anatase phase were harvested. The crystallite sizes of bare and copper doped TiO2 nanoparticles were calculated from X-ray diffraction analysis. The existence of functional groups of the samples was identified by Fourier transform infrared spectroscopy. The optical properties of bare and doped samples were carried out using UV-DRS and photoluminescence measurements. The surface morphology and the element constitution of the copper doped TiO2 nanoparticles were studied by scanning electron microscope fitted with energy dispersive X-ray spectrometer arrangement. The nonlinear optical properties of the products were confirmed by Kurtz second harmonic generation (SHG) test and the output power generated by the nanoparticle was compared with that of potassium di hydrogen phosphate (KDP).

  12. Thermodynamic Effects on Phase Stabilities and Structural Properties of TiO2 from the First-principles

    NASA Astrophysics Data System (ADS)

    Aoki, Yuta; Saito, Susumu

    2013-03-01

    Titanium dioxide (TiO2) is one of the most representative photocatalytic materials and much attention is focused on understanding and improvement of its photocatalytic activity. At the same time, TiO2 is known to be a highly polymorphic material and as many as eleven crystal phases have been identified so far. It is expected that TiO2 show various photocatalytic properties depending on crystal phases. However, relative stabilities of these identified phases are still controversial. In order to clarify the thermodynamic phase stabilities of TiO2, we obtain the free energies of its several representative phases, rutile, anatase, brookite, and TiO2-II within the framework of the density-functional theory using the pseudopotential method. We calculate both the static energy and the contribution of phonons to the free energy through the quasiharmonic approximation for each phase. It is found that treatment of semicore electrons in constructing the pseudopotential of the Ti atom significantly affects the relative phase stabilities. From the phase diagram obtained, we find that the anatase phase is the most stable at lower temperature and pressure. We also discuss the thermodynamic effects on structural properties such as thermal expansion. We acknowledge the financial supports from the Global Center-of-Excellence Program by MEXT, Japan through the Nanoscience and Quantum Physics Project of Tokyo Institute of Technology, and the Elements Science and Technology Project by MEXT.

  13. Optical and structural characterization of TiO2 films doped with silver nanoparticles obtained by sol-gel method

    NASA Astrophysics Data System (ADS)

    Ivanova, T.; Harizanova, A.; Koutzarova, T.; Vertruyen, B.

    2013-12-01

    Nanostructured titanium oxide films with incorporated Ag nanoparticles were deposited by sol-gel spin coating method. The films were annealed at 300 °C, 400 °C, 500 °C and 600 °C in oxygen and nitrogen ambient. X-ray diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR) and UV-VIS spectroscopy had been applied for studying the influence of the thermal treatments and the gas ambient on the structural and optical properties of TiO2 and TiO2:Ag films. The XRD analysis revealed the presence of metallic Ag phase without traces of silver oxides and these results were confirmed by FTIR spectra. It has been revealed that the annealing temperatures and the ambient, where the annealing is carried out is crucial for TiO2 crystallization, when there is Ag incorporation and especially for appearance of anatase and rutile phase. The nitrogen and oxygen ambient influences quite different the crystallization of TiO2:Ag films. Transmission and absorption spectra have been analyzed. Optical band gap values were evaluated for pure titania and Ag incorporated TiO2 films.

  14. Photocatalytic degradation of dyestuff wastewater with Zn(2+)-TiO2-SiO2 nanocomposite.

    PubMed

    Sui, Guozhe; Liu, Tao; Li, Jinlong; Jia, Lihua; Lv, Jun

    2013-06-01

    A novel photocatalyst of Zn(2+)-TiO2-SiO2 nanocomposite has been prepared by a sol-gel method, which is used for the degradation of Rhodamine B (RhB) and Congo red (CR) as the probe dyestuff that are notorious organic compounds present in dyes wastewater. The prepared samples are characterized by low temperature N2 adsorption (BET), X-ray diffraction (XRD), scanning electron microscopy (SEM), UV-vis diffuse reflectance spectroscopy (DRS) and Fourier transformed infrared spectroscopy (FT-IR). It is found that the nanocomposite of Zn(2+)-TiO2-SiO2 exhibits much higher photocatalytic activity under both UV light and visible light irradiation as compared with Degussa P25, Zn(2+)-TiO2 and SiO2-TiO2. The photodegradation efficiencies of RhB (5 mg/L) and CR (10 mg/L) can reach above 90% and 83% for 1.5 h visible light irradiation, respectively. Synergetic effect between Zn(2+)-SiO2-doping not only inhibit the crystal growth and anatase-to-rutile transformation of TiO2 nanocatalyst, but also extend the light response to the visible region, which provides a good way and material in the degradation field of dyes wastewater.

  15. Self-organized TiO2 nanotube arrays in the photocatalytic degradation of methylene blue under UV light irradiation

    NASA Astrophysics Data System (ADS)

    Chung, Eun Hyuk; Baek, Seong Rim; Yu, Seong Mi; Kim, Jong Pil; Hong, Tae Eun; Kim, Hyun Gyu; Bae, Jong-Seong; Jeong, Euh Duck; Khan, F. Nawaz; Jung, Ok-sang

    2015-04-01

    Nanostructured titanium dioxide (NTiO2) is known to possess efficient photocatalytic activity and to have diverse applications in many fields due to its chemical stability, high surface area/volume ratio, high transmittance, and high refractive index in the visible and the near-ultraviolet regions. These facts prompted us to develop TiO2 nanotube (TiO2 NT) arrays through electrochemical anodic oxidation involving different electrolytes comprised of phosphoric acid — hydrofluoric acid aqueous systems by varying the voltage and the time. The annealing temperature of the nanotubes, TiO2 NTs, were varied to modify the surface morphology and were characterized by using X-ray diffraction and scanning electron microscopy. Scanning electron microscopy and X-ray diffraction results showed that the samples had uniform morphologies and good crystalline structures of the anatase phase at lower annealing temperatures and of the rutile phase at higher annealing temperatures. A secondary-ion mass-spectrometry analysis was used to investigate the surface atoms and to conduct a depth profile analysis of the TiO2 NTs. The efficiency of the photocatalytic activity of the TiO2 NT arrays in degrading methylene blue (MB) was investigated under UV-Vis light irradiation. The maximum photocatalytic activity was achieved for the samples with lower annealing temperatures due to their being in the anatase phase and having a higher surface area and a smaller crystal size, which play important roles in the degradation of organic pollutants.

  16. Linear and nonlinear optical studies of bare and copper doped TiO2 nanoparticles via sol gel technique.

    PubMed

    Rajamannan, B; Mugundan, S; Viruthagiri, G; Praveen, P; Shanmugam, N

    2014-01-24

    In general, the nanoparticles of TiO2 may exist in the phases of anatase, rutile and brookite. In the present work, we used titanium terta iso propoxide and 2-propanol as a common starting material to prepare the precursors of bare and copper doped nanosized TiO2. Then the synthesized products were calcinated at 500°C and after calcination the pure TiO2 nanoparticles in anatase phase were harvested. The crystallite sizes of bare and copper doped TiO2 nanoparticles were calculated from X-ray diffraction analysis. The existence of functional groups of the samples was identified by Fourier transform infrared spectroscopy. The optical properties of bare and doped samples were carried out using UV-DRS and photoluminescence measurements. The surface morphology and the element constitution of the copper doped TiO2 nanoparticles were studied by scanning electron microscope fitted with energy dispersive X-ray spectrometer arrangement. The nonlinear optical properties of the products were confirmed by Kurtz second harmonic generation (SHG) test and the output power generated by the nanoparticle was compared with that of potassium di hydrogen phosphate (KDP).

  17. Photocatalytic degradation of herbicide bentazone in aqueous suspension of TiO2: mineralization, identification of intermediates and reaction pathways.

    PubMed

    Mir, Niyaz A; Haque, M M; Khan, A; Muneer, M; Vijayalakshmi, S

    2014-01-01

    Semiconductor-mediated hydrogen peroxide-assisted photocatalytic degradation of a selected herbicide, Bentazone (1) has been investigated in aqueous suspensions of TiO2 under a variety of conditions. The degradation was studied by monitoring the depletion in total organic carbon content as a function of irradiation time. The degradation kinetics was investigated under different conditions such as type of TiO2 (Anatase/Anatase-Rutile mixture), reaction pH, catalyst dosage and hydrogen peroxide (H202) concentration. The degradation rates were found to be strongly influenced by all the above parameters. Titanium dioxide Degussa P25 was found to be more efficient as compared with other two commercially available TiO2 powders like Hombikat UV100 and PC500 from Millennium Inorganic Chemicals. Gas Chromatography-Mass Spectrometry (GC-MS) analysis of the irradiated mixture of Bentazone (1) indicates the formation of several intermediate products which have been characterized on the basis of molecular ion/mass fragmentation pattern and also on comparison with the National Institute of Standards and Technology (NIST) library. Plausible mechanism for the formation of different products during photocatalytic treatment of Bentazone in the presence of TiO2 has been proposed. The use of H202 substantially increased the efficiency of TiO2 photocatalytic degradation.

  18. Development of high efficient visible light-driven N, S-codoped TiO2 nanowires photocatalysts

    NASA Astrophysics Data System (ADS)

    Zhang, Yanlin; Liu, Peihong; Wu, Honghai

    2015-02-01

    One-dimensional (1D) nanowire material (especially nonmetal doped 1D nanowires) synthesized by a facile way is of great significance and greatly desired as it has higher charge carrier mobility and lower carrier recombination rate. N, S-codoped TiO2 nanowires were synthesized using titanium sulfate as a precursor and isopropanol as a protective capping agent by a hydrothermal route. The obtained doped nanowires were characterized by XRD, SEM, HRTEM, SAED, XPS, BET and UV-vis absorption spectrum. The incorporation of N and S into TiO2 NWs can lead to the expansion of its lattice and remarkably lower its electron-transfer resistance. Photocatalytic activity measurement showed that the N, S-codoped TiO2 nanowires with high quantum efficiency revealed the best photocatalytic performance for atrazine degradation under visible light irradiation compared to N, S-codoped TiO2 nanoparticles and S-doped TiO2 nanowires, which was attributed to (i) the synergistic effect of N and S doping in narrowing the band gap, separating electron-hole pairs and increasing the photoinduced electrons, and (ii) extending the anatase-to-rutile transformation temperature above 600 °C.

  19. Low-temperature preparation of F-doped TiO 2 film and its photocatalytic activity under solar light

    NASA Astrophysics Data System (ADS)

    Xu, Jingjing; Ao, Yanhui; Fu, Degang; Yuan, Chunwei

    2008-03-01

    A novel and simple method for preparing F-doped anatase TiO 2 (defined as FTO) film with high photocatalytic activity was developed using titanium- n-butoxide and NH 4F as TiO 2 and fluorine precursors under mild condition, i.e. low temperature (lower than 373 K) and ambient pressure. The prepared samples were characterized by XRD, SEM, X-ray photoelectron spectroscopy (XPS), diffuse reflectance spectrum (DRS), photoluminescence spectrum (PL) and TG-DSC analysis. The photocatalytic activity was evaluated by decomposing X-3B under artificial solar light. The results showed that the crystallinity of TiO 2 was improved by F-doping. F - ions can prevent the grain growth, and the transformation of anatase to rutile phase was also inhibited. The doped fluorine atoms existed in two chemical forms, and the ones incorporated into TiO 2 lattice might take a positive role in photocatalysis. Compared with surface fluorination samples, FTO film exhibited better photocatalytic activity. The high photocatalytic activity of FTO may due to extrinsic absorption through the creation of oxygen vacancies rather than the excitation of the intrinsic absorption band of bulk TiO 2. Furthermore, the FTO can be recycled with little photocatalytic activity depression. Without any further treatment besides rinsing, after 6 recycle utilization, the photocatalytic activity of FTO film was still higher than 79%.

  20. Confirmation of hydroxyl radicals (•OH) generated in the presence of TiO2 supported on AC under microwave irradiation.

    PubMed

    Zhang, Zhaohong; Yu, Fengyang; Huang, Lirong; Jiatieli, Jianaerguli; Li, Yuanyuan; Song, Lijun; Yu, Ning; Dionysiou, Dionysios D

    2014-08-15

    In order to study the degradation mechanism of technology of microwave (MW) combined with TiO2 supported on activated carbon (TiO2/AC), the reactive oxygen species (ROS) was explored through oxidation of 1,5-diphenyl carbazide (DPCI) to 1,5-diphenyl carbazone (DPCO). Furthermore, 2,6-di-tert-butyl-4-methylphenol (BHT), Mannitol (MT) and Vitamin C (VC) were used as radical scavengers to confirm the generation of the hydroxyl radicals ((•)OH). In addition, the influence of some parameters such as TiO2 mass ratio content, irradiation time, material dose, DPCI concentration and MW power on the determination of (•)OH were examined. The results showed that the (•)OH could be generated under MW combined with loaded TiO2/AC. Also, anatase TiO2/AC can generate more (•)OH radicals than rutile TiO2/AC under MW irradiation. This work would provide new mechanistic insights on the enhanced degradation effect of organic pollutants in water using the supported TiO2/AC coupled with MW technology.

  1. Influence of transition metal doping on the structural, optical, and magnetic properties of TiO2 films deposited on Si substrates by a sol–gel process

    PubMed Central

    2013-01-01

    Transition metal (TM)-doped TiO2 films (TM = Co, Ni, and Fe) were deposited on Si(100) substrates by a sol–gel method. With the same dopant content, Co dopants catalyze the anatase-to-rutile transformation (ART) more obviously than Ni and Fe doping. This is attributed to the different strain energy induced by the different dopants. The optical properties of TM-doped TiO2 films were studied with spectroscopic ellipsometry data. With increasing dopant content, the optical band gap (EOBG) shifts to lower energy. With the same dopant content, the EOBG of Co-doped TiO2 film is the smallest and that of Fe-doped TiO2 film is the largest. The results are related to electric disorder due to the ART. Ferromagnetic behaviors were clearly observed for TM-doped TiO2 films except the undoped TiO2 film which is weakly magnetic. Additionally, it is found that the magnetizations of the TM-doped TiO2 films decrease with increasing dopant content. PMID:24350904

  2. Effect of TiO2 nanoparticles on adipose derived stromal cell differentiation, morphology, ECM deposition and its susceptibility to bacterial infections

    NASA Astrophysics Data System (ADS)

    Mironava, Tatsiana; Xu, Yan; Rafailovich, Miriam

    The growing annual production of Titanium dioxide (TiO2) nanoparticles is proportional to an increase in the chances of occupational and consumer exposure. Considering, that these nanoparticles are currently being used in multiple personal care products many concerns have arisen about their health impact. Human skin is in constant contact with the external environment and is one of the most important routes of exposure to TiO2. In this study we have investigated the effect of two forms of TiO2, rutile and anatase, on human adipose derived stromal cells (ADSCs). Here, we focus on the effects of TiO2 exposure on intracellular lipid accumulation and expression of adipogenic markers; on whether different forms of TiO2 have similar effects on cell function; and whether nanoparticle localization inside cells correlates with loss of cell function. In addition presence of bacteria on the skin is taken into account in its complex interaction with ADSCs and TiO2 nanoparticles. Altogether, the present study indicates that nanosized TiO2 particles adversely effects the differentiation of ADSCs, have profound effects on cell function and increase the rate of bacterial infection.

  3. In field conditions, commercial pigment grade TiO2 was not harmful to terrestrial isopods but reduced leaf litter fragmentation.

    PubMed

    Jemec, Anita; Kos, Monika; Drobne, Damjana; Koponen, Ismo Kalevi; Vukić, Jovan; Ferreira, Nuno G C; Loureiro, Susana; McShane, Heather V A

    2016-11-15

    We investigated the effects of a commercial pigment grade rutile TiO2 on the terrestrial isopod Porcellio scaber in three locations that differed in terms of abiotic and biotic conditions: the laboratory, open air, and the closed barn. Mortality and isopod energy reserves (digestive gland total proteins, lipids and carbohydrates) were not affected following 14days exposure to up to 1000mg TiO2 per kg dry leaves (mg/kg) under any experimental scenario. However, in the field tests, isopods consumption of TiO2-coated leaves was reduced compared to that of uncoated leaves and the decrease was not dose-dependent. The highest reduction was in the closed barn (45-56%) rather than in the open-air (38-40%). In laboratory-based food choice tests, isopods neither preferred nor avoided leaves coated with TiO2, suggesting that rather than sensing the TiO2 on the leaves directly, the isopods under open-air and barn exposure responded to altered attractiveness and/or palatability of the TiO2 amended leaves. We propose that this could be due to altered microbial population on the leaves, a hypothesis that requires further investigation. Although short-term exposure to atmospheric deposition of up to 1000mg/kg commercial TiO2 is unlikely to pose an immediate threat to isopod mortality and energy balance, reduced leaf feeding may have implications for the decomposition of plant material. PMID:27481455

  4. In field conditions, commercial pigment grade TiO2 was not harmful to terrestrial isopods but reduced leaf litter fragmentation.

    PubMed

    Jemec, Anita; Kos, Monika; Drobne, Damjana; Koponen, Ismo Kalevi; Vukić, Jovan; Ferreira, Nuno G C; Loureiro, Susana; McShane, Heather V A

    2016-11-15

    We investigated the effects of a commercial pigment grade rutile TiO2 on the terrestrial isopod Porcellio scaber in three locations that differed in terms of abiotic and biotic conditions: the laboratory, open air, and the closed barn. Mortality and isopod energy reserves (digestive gland total proteins, lipids and carbohydrates) were not affected following 14days exposure to up to 1000mg TiO2 per kg dry leaves (mg/kg) under any experimental scenario. However, in the field tests, isopods consumption of TiO2-coated leaves was reduced compared to that of uncoated leaves and the decrease was not dose-dependent. The highest reduction was in the closed barn (45-56%) rather than in the open-air (38-40%). In laboratory-based food choice tests, isopods neither preferred nor avoided leaves coated with TiO2, suggesting that rather than sensing the TiO2 on the leaves directly, the isopods under open-air and barn exposure responded to altered attractiveness and/or palatability of the TiO2 amended leaves. We propose that this could be due to altered microbial population on the leaves, a hypothesis that requires further investigation. Although short-term exposure to atmospheric deposition of up to 1000mg/kg commercial TiO2 is unlikely to pose an immediate threat to isopod mortality and energy balance, reduced leaf feeding may have implications for the decomposition of plant material.

  5. D-sorbitol-induced phase control of TiO2 nanoparticles and its application for dye-sensitized solar cells.

    PubMed

    Shaikh, Shoyebmohamad F; Mane, Rajaram S; Min, Byoung Koun; Hwang, Yun Jeong; Joo, Oh-shim

    2016-02-09

    Using a simple hydrothermal synthesis, the crystal structure of TiO2 nanoparticles was controlled from rutile to anatase using a sugar alcohol, D-sorbitol. Adding small amounts of D-sorbitol to an aqueous TiCl4 solution resulted in changes in the crystal phase, particle size, and surface area by affecting the hydrolysis rate of TiCl4. These changes led to improvements of the solar-to-electrical power conversion efficiency (η) of dye-sensitized solar cells (DSSC) fabricated using these nanoparticles. A postulated reaction mechanism concerning the role of D-sorbitol in the formation of rutile and anatase was proposed. Fourier-transform infrared spectroscopy, (13)C NMR spectroscopy, and dynamic light scattering analyses were used to better understand the interaction between the Ti precursor and D-sorbitol. The crystal phase and size of the synthesized TiO2 nanocrystallites as well as photovoltaic performance of the DSSC were examined using X-ray diffraction, Raman spectroscopy, field-emission scanning electron microscopy, high-resolution transmission electron microscopy, and photocurrent density-applied voltage spectroscopy measurement techniques. The DSSC fabricated using the anatase TiO2 nanoparticles synthesized in the presence of D-sorbitol, exhibited an enhanced η (6%, 1.5-fold improvement) compared with the device fabricated using the rutile TiO2 synthesized without D-sorbitol.

  6. D-sorbitol-induced phase control of TiO2 nanoparticles and its application for dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Shaikh, Shoyebmohamad F.; Mane, Rajaram S.; Min, Byoung Koun; Hwang, Yun Jeong; Joo, Oh-Shim

    2016-02-01

    Using a simple hydrothermal synthesis, the crystal structure of TiO2 nanoparticles was controlled from rutile to anatase using a sugar alcohol, D-sorbitol. Adding small amounts of D-sorbitol to an aqueous TiCl4 solution resulted in changes in the crystal phase, particle size, and surface area by affecting the hydrolysis rate of TiCl4. These changes led to improvements of the solar-to-electrical power conversion efficiency (η) of dye-sensitized solar cells (DSSC) fabricated using these nanoparticles. A postulated reaction mechanism concerning the role of D-sorbitol in the formation of rutile and anatase was proposed. Fourier-transform infrared spectroscopy, 13C NMR spectroscopy, and dynamic light scattering analyses were used to better understand the interaction between the Ti precursor and D-sorbitol. The crystal phase and size of the synthesized TiO2 nanocrystallites as well as photovoltaic performance of the DSSC were examined using X-ray diffraction, Raman spectroscopy, field-emission scanning electron microscopy, high-resolution transmission electron microscopy, and photocurrent density-applied voltage spectroscopy measurement techniques. The DSSC fabricated using the anatase TiO2 nanoparticles synthesized in the presence of D-sorbitol, exhibited an enhanced η (6%, 1.5-fold improvement) compared with the device fabricated using the rutile TiO2 synthesized without D-sorbitol.

  7. D-sorbitol-induced phase control of TiO2 nanoparticles and its application for dye-sensitized solar cells

    PubMed Central

    Shaikh, Shoyebmohamad F.; Mane, Rajaram S.; Min, Byoung Koun; Hwang, Yun Jeong; Joo, Oh-shim

    2016-01-01

    Using a simple hydrothermal synthesis, the crystal structure of TiO2 nanoparticles was controlled from rutile to anatase using a sugar alcohol, D-sorbitol. Adding small amounts of D-sorbitol to an aqueous TiCl4 solution resulted in changes in the crystal phase, particle size, and surface area by affecting the hydrolysis rate of TiCl4. These changes led to improvements of the solar-to-electrical power conversion efficiency (η) of dye-sensitized solar cells (DSSC) fabricated using these nanoparticles. A postulated reaction mechanism concerning the role of D-sorbitol in the formation of rutile and anatase was proposed. Fourier-transform infrared spectroscopy, 13C NMR spectroscopy, and dynamic light scattering analyses were used to better understand the interaction between the Ti precursor and D-sorbitol. The crystal phase and size of the synthesized TiO2 nanocrystallites as well as photovoltaic performance of the DSSC were examined using X-ray diffraction, Raman spectroscopy, field-emission scanning electron microscopy, high-resolution transmission electron microscopy, and photocurrent density-applied voltage spectroscopy measurement techniques. The DSSC fabricated using the anatase TiO2 nanoparticles synthesized in the presence of D-sorbitol, exhibited an enhanced η (6%, 1.5-fold improvement) compared with the device fabricated using the rutile TiO2 synthesized without D-sorbitol. PMID:26857963

  8. Photoreduction of CO2 on TiO 2/SrTiO 3 Heterojunction Network Film.

    PubMed

    Bi, Yongsheng; Zong, Lanlan; Li, Chen; Li, Qiuye; Yang, Jianjun

    2015-12-01

    Nanotube titanic acid (NTA) network film has a porous structure and large BET surface area, which lead them to possessing high utilization of the incident light and strong adsorption ability. We used NTA as the precursor to fabricate a TiO2/ SrTiO3 heterojunction film by the hydrothermal method. In the process of the reaction, part of NTA reacted with SrCl2 to form SrTiO3 nanocubes, and the remainder dehydrated to transform to the rutile TiO2. The ratio of TiO2 and SrTiO3 varied with the hydrothermal reaction time. SEM and TEM images indicated that SrTiO3 nanocubes dispersed uniformly on TiO2 film, and the particle size and crystallinity of SrTiO3 nanocubes increased with the reaction time prolonging. The TiO2/SrTiO3 heterojunction obtained by 1 h showed the best activity for CO2 photoreduction, where the mole ratio of TiO2 and SrTiO3 was 4:1. And the photo-conversion efficiency of CO2 to CH4 improved remarkably after the foreign electron traps of Pt and Pd nanoparticles were loaded. The highest photocatalytic production rate of CH4 reached 20.83 ppm/h cm(2). In addition, the selectivity of photoreduction product of CO2 was also increased apparently when Pd acted as the cocatalyst on TiO2/SrTiO3 heterojunction film.

  9. Photoreduction of CO2 on TiO2/SrTiO3 Heterojunction Network Film

    NASA Astrophysics Data System (ADS)

    Bi, Yongsheng; Zong, Lanlan; Li, Chen; Li, Qiuye; Yang, Jianjun

    2015-08-01

    Nanotube titanic acid (NTA) network film has a porous structure and large BET surface area, which lead them to possessing high utilization of the incident light and strong adsorption ability. We used NTA as the precursor to fabricate a TiO2/ SrTiO3 heterojunction film by the hydrothermal method. In the process of the reaction, part of NTA reacted with SrCl2 to form SrTiO3 nanocubes, and the remainder dehydrated to transform to the rutile TiO2. The ratio of TiO2 and SrTiO3 varied with the hydrothermal reaction time. SEM and TEM images indicated that SrTiO3 nanocubes dispersed uniformly on TiO2 film, and the particle size and crystallinity of SrTiO3 nanocubes increased with the reaction time prolonging. The TiO2/SrTiO3 heterojunction obtained by 1 h showed the best activity for CO2 photoreduction, where the mole ratio of TiO2 and SrTiO3 was 4:1. And the photo-conversion efficiency of CO2 to CH4 improved remarkably after the foreign electron traps of Pt and Pd nanoparticles were loaded. The highest photocatalytic production rate of CH4 reached 20.83 ppm/h cm2. In addition, the selectivity of photoreduction product of CO2 was also increased apparently when Pd acted as the cocatalyst on TiO2/SrTiO3 heterojunction film.

  10. Metallization of Epitaxial VO2 Films by Ionic Liquid Gating through Initially Insulating TiO2 Layers.

    PubMed

    Passarello, Donata; Altendorf, Simone G; Jeong, Jaewoo; Samant, Mahesh G; Parkin, Stuart S P

    2016-09-14

    Ionic liquid gating has been shown to metallize initially insulating layers formed from several different oxide materials. Of these vanadium dioxide (VO2) is of especial interest because it itself is metallic at temperatures above its metal-insulator transition. Recent studies have shown that the mechanism of ionic liquid gated induced metallization is entirely distinct from that of the thermally driven metal-insulator transition and is derived from oxygen migration through volume channels along the (001) direction of the rutile structure of VO2. Here we show that it is possible to metallize the entire volume of 10 nm thick layers of VO2 buried under layers of rutile titanium dioxide (TiO2) up to 10 nm thick. Key to this process is the alignment of volume channels in the respective oxide layers, which have the same rutile structure with clamped in-plane lattice constants. The metallization of the VO2 layers is accompanied by large structural expansions of up to ∼6.5% in the out-of-plane direction, but the structure of the TiO2 layer is hardly affected by gating. The TiO2 layers become weakly conducting during the gating process, but in contrast to the VO2 layers, the conductivity disappears on exposure to air. Indeed, even after air exposure, X-ray photoelectron spectroscopy studies show that the VO2 films have a reduced oxygen content after metallization. Ionic liquid gating of the VO2 films through initially insulating TiO2 layers is not consistent with conventional models that have assumed the gate induced carriers are of electrostatic origin. PMID:27479461

  11. GROWTH, SURFACE CHARACTERIZATION, AND REACTIVITY OF TIO2 ANATASE FILMS-EPSCOR

    SciTech Connect

    Diebold, Ulrike

    2004-12-15

    TiO2 is as promising photocatalyst for environmental degradation of organic compounds and solar energy conversion. Commercial titania is a mixture of rutile and anatase phases, and, for as of yet unknown reasons, anatase is the photocatalytically more active form. In contrast to rutile, atomic-scale information on well-characterized anatase surfaces and their chemical properties was virtually absent at the beginning of this project. We have performed surface science investigations of anatase with the goal to understand, and ultimately control, the surface chemistry underlying its diverse applications. We have of (1) characterized all main crystallographic surface orientations of anatase, namely the (101), (100), (001), and (103) surfaces (2) have investigated the influence of surface imperfections such as defects and steps; (3) have investigated the influence of dopants on epitaxial (001) anatase films; and (3) have investigated the chemical and adsorption and reaction processes of simple molecules (water and methanol) on anatase surfaces. The experiments were performed in collaboration with Pacific Northwest National Laboratory (PNNL) using a variety of complementary surface science techniques. They have lead to a thorough characterization of this model system and have provided a more complete understanding of TiO2, which could possibly lead to improved efficiency in of photocatalytic applications.

  12. 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

  13. Preparation of TiO2/SnO2 thin films by sol-gel method and periodic B3LYP simulations.

    PubMed

    Floriano, Emerson A; Scalvi, Luis V A; Saeki, Margarida J; Sambrano, Julio R

    2014-08-01

    Titanium dioxide (TiO2) thin films are grown by the sol-gel dip-coating technique, in conjunction with SnO2 in the form of a heterostructure. It was found that the crystalline structure of the most internal layer (TiO2) depends on the thermal annealing temperature and the substrate type. Films deposited on glass substrate submitted to thermal annealing until 550 °C present anatase structure, whereas films deposited on quartz substrate transform to rutile structure at much higher temperatures, close to 1000 °C, unlike powder samples where the phase transition takes place at about 780 °C. When structured as rutile, the oxide semiconductors TiO2/SnO2 have very close lattice parameters, making the heterostructure assembling easier. The SnO2 and TiO2 have their electronic properties evaluated by first-principles calculations by means of DFT/B3LYP. Taking into account the calculated band structure diagram of these materials, the TiO2/SnO2 heterostructure is qualitatively investigated and proposed to increase the detection efficiency as gas sensors. This efficiency can be further improved by doping the SnO2 layer with Sb atoms. This assembly may be also useful in photoelectrocatalysis processes. PMID:24824227

  14. Preparation of TiO2/SnO2 thin films by sol-gel method and periodic B3LYP simulations.

    PubMed

    Floriano, Emerson A; Scalvi, Luis V A; Saeki, Margarida J; Sambrano, Julio R

    2014-08-01

    Titanium dioxide (TiO2) thin films are grown by the sol-gel dip-coating technique, in conjunction with SnO2 in the form of a heterostructure. It was found that the crystalline structure of the most internal layer (TiO2) depends on the thermal annealing temperature and the substrate type. Films deposited on glass substrate submitted to thermal annealing until 550 °C present anatase structure, whereas films deposited on quartz substrate transform to rutile structure at much higher temperatures, close to 1000 °C, unlike powder samples where the phase transition takes place at about 780 °C. When structured as rutile, the oxide semiconductors TiO2/SnO2 have very close lattice parameters, making the heterostructure assembling easier. The SnO2 and TiO2 have their electronic properties evaluated by first-principles calculations by means of DFT/B3LYP. Taking into account the calculated band structure diagram of these materials, the TiO2/SnO2 heterostructure is qualitatively investigated and proposed to increase the detection efficiency as gas sensors. This efficiency can be further improved by doping the SnO2 layer with Sb atoms. This assembly may be also useful in photoelectrocatalysis processes.

  15. High-performance photodetectors and enhanced photocatalysts of two-dimensional TiO2 nanosheets under UV light excitation

    NASA Astrophysics Data System (ADS)

    Yang, Jiao; Jiang, Yi-Lin; Li, Lin-Jie; Muhire, Elisée; Gao, Mei-Zhen

    2016-04-01

    Due to the large surface area-to-volume ratio and rapid electron transfer, two-dimensional (2D) TiO2 nanosheets with ultrathin thicknesses are synthesized by using a bottom-up strategy and these self-assembled nanosheet (NS)-based photocatalysts and photodetectors were explored for the first time. The influence of calcination temperature on microstructures and photocatalytic activity of TiO2 nanosheets were discovered and presented. The as-obtained TiO2 nanosheets were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Brunauer-Emmett-Teller (BET) analysis, Fourier transform infrared (FTIR) spectroscopy, UV-vis spectrophotometry, and X-ray photoelectron spectroscopy (XPS). The following heat treatment process induced phase evolution from rutile to anatase. The TiO2 nanosheets calcined at 500 °C exhibited the best activity for photo-degradation of organic dyes under UV light irradiation. The obtained photodetector exhibits excellent performance with a high photocurrent to dark current ratio and fast response and recovery times. Additionally, we demonstrated that the device may have potential applications in the future low-power optoelectronics system.Due to the large surface area-to-volume ratio and rapid electron transfer, two-dimensional (2D) TiO2 nanosheets with ultrathin thicknesses are synthesized by using a bottom-up strategy and these self-assembled nanosheet (NS)-based photocatalysts and photodetectors were explored for the first time. The influence of calcination temperature on microstructures and photocatalytic activity of TiO2 nanosheets were discovered and presented. The as-obtained TiO2 nanosheets were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Brunauer-Emmett-Teller (BET) analysis, Fourier transform infrared (FTIR) spectroscopy, UV-vis spectrophotometry, and X-ray photoelectron spectroscopy (XPS). The following

  16. X-ray diffraction and Raman scattering study of thermal-induced phase transformation in vertically aligned TiO 2 nanocrystals grown on sapphire(1 0 0) via metal organic vapor deposition

    NASA Astrophysics Data System (ADS)

    Chen, C. A.; Chen, K. Y.; Huang, Y. S.; Tsai, D. S.; Tiong, K. K.; Chien, F. Z.

    2008-07-01

    We report a detailed study of thermal-induced phase transformation in TiO 2 nanocrystals (NCs) via X-ray diffraction (XRD) and Raman scattering (RS) spectroscopy. Vertically aligned anatase TiO 2(1 1 0) NCs were grown on the sapphire (SA)(1 0 0) substrate at 550 °C by metal organic chemical vapor deposition, using titanium-tetraisopropoxide (TTIP, Ti[OCH(CH 3) 2] 4), as the source reagent. The effects of thermal annealing of TiO 2 NCs in oxygen atmosphere between 600 and 1000 °C were investigated. XRD and RS spectra showed the onset of the phase transformation process from the as-grown anatase TiO 2(1 1 0) NCs into rutile TiO 2(0 0 1) at the annealing temperature of 800 °C. At annealing temperature higher than 900 °C, pure rutile phase of TiO 2(0 0 1) NCs were formed and the crystalline quality of TiO 2 NCs could be further improved upon higher annealing temperature.

  17. Hydrogen photo-production from ethanol on TiO2: a surface science and catalysis study

    NASA Astrophysics Data System (ADS)

    Nadeem, A. M.; Muir, J. M. R.; Waterhouse, G. W. N.; Idriss, H.

    2011-10-01

    In this work we present an overview of the photo-reaction of ethanol over the surface of TiO2 (110) single crystal under photo-excitation and compare it to that over Au/TiO2 nano-particle. Over rutile TiO2(110) surface ethanol is present mainly in ethoxide (CH3CH2O(a)) form at 300K as evidenced by the presence of XPS C1s peak at 286.5 eV due to the -CH2-O(a) function; (a) for adsorbed. DFT computation of the same system indicated that the surface coverage is 50% or less in line with previous experimental results [1]. Exposing a pre-dosed surface to UV light in presence of oxygen resulted in the formation of acetaldehyde (CH3CHO(g); (g) for gas phase) with the extent of reaction depending on the square root of the O2 pressure in the 10-10 - 10-6torr range. Over the Au/TiO2 powder system we have focused the attention on the production of hydrogen as the oxidation of ethanol of ethanol to acetaldehyde has been previously studied [2]. The reaction is found to be sensitive to the polymorph nature of TiO2 with anatase showing two orders of magnitudes higher activity than rutile. We have also addressed the TiO2 particle size effect on the reaction and found that the TiO2 particles, in the 150 to 10 nm range, to have the same reactivity.

  18. First-principles study of lattice dynamics of TiO2 in brookite and cotunnite structures

    NASA Astrophysics Data System (ADS)

    Shojaee, E.; Abbasnejad, M.; Saeedian, M.; Mohammadizadeh, M. R.

    2011-05-01

    The zone-center phonons and dielectric properties of orthorhombic brookite and cotunnite structures TiO2 were studied in the framework of density functional perturbative theory. The dielectric properties of brookite and anatase structures are similar. The calculated static dielectric permittivity of brookite is found to be slightly higher than that of anatase, but far lower than that of the rutile structure. This is in contrast with the recent experimental report on brookite flowers. Our study suggests that the static dielectric constant of cotunnite structure is smaller than those of rutile and brookite structures. We obtained the full phonon band structure and elastic properties of these structures. The bulk modulus and Debye temperature of brookite are intermediate between those of the anatase and rutile structures. The obtained value of 301 GPa for the bulk modulus of cotunnite is in good agreement with the stiffness of the material reported experimentally. Because of the similarity in z-direction packing of the TiO6 tetrahedron between brookite and rutile structures, the elastic constants associated with the z-polarized movement of atoms in brookite are similar to those of the rutile structure. The elastic constants of brookite associated with the movement of the atoms in x-y plane, are similar to the corresponding constants in anatase and rutile structures. This demonstrates the similarity between the packing character of the brookite structure with both anatase and rutile structures. So, the lattice dynamics of brookite is intermediate between those of anatase and rutile polymorphs. The calculated phonon density of states of cotunnite shows that it is stable at ambient pressure.

  19. Flame-made Nb-doped TiO2 ethanol and acetone sensors.

    PubMed

    Phanichphant, Sukon; Liewhiran, Chaikarn; Wetchakun, Khatcharin; Wisitsoraat, Anurat; Tuantranont, Adisorn

    2011-01-01

    Undoped TiO(2) and TiO(2) nanoparticles doped with 1-5 at.% Nb were successfully produced in a single step by flame spray pyrolysis (FSP). The phase and crystallite size were analyzed by XRD. The BET surface area (SSA(BET)) of the nanoparticles was measured by nitrogen adsorption. The trend of SSA(BET) on the doping samples increased and the BET equivalent particle diameter (d(BET)) (rutile) increased with the higher Nb-doping concentrations while d(BET) (anatase) remained the same. The morphology and accurate size of the primary particles were further investigated by high-resolution transmission electron microscopy (HRTEM). The crystallite sizes of undoped and Nb-doped TiO(2) spherical were in the range of 10-20 nm. The sensing films were prepared by spin coating technique. The mixing sample was spin-coated onto the Al(2)O(3) substrates interdigitated with Au electrodes. The gas sensing of acetone (25-400 ppm) was studied at operating temperatures ranging from 300-400 °C in dry air, while the gas sensing of ethanol (50-1,000 ppm) was studied at operating temperatures ranging from 250-400 °C in dry air. PMID:22346586

  20. Modeling the effects of water content on TiO2 nanoparticles transport in porous media

    NASA Astrophysics Data System (ADS)

    Toloni, Ivan; Lehmann, François; Ackerer, Philippe

    2016-08-01

    The transport of manufactured titanium dioxide (TiO2, rutile) nanoparticles (NP) in porous media was investigated by metric scale column experiments under different water saturation and ionic strength (IS) conditions. The NP breakthrough curves showed that TiO2 NP retention on the interface between air and water (AWI) and the interface between the solid and the fluid (SWI) is insignificant for an IS equal to or smaller than 3 mM KCl. For larger IS, the retention is depending on the water content and the fluid velocity. The experiments, conducted with an IS of 5 mM KCl, showed a significantly higher retention of NP than that observed under saturated conditions and very similar experimental conditions. Water flow was simulated using the standard Richards equation. The hydrodynamic model parameters for unsaturated flow were estimated through independent drainage experiments. A new mathematical model was developed to describe TiO2 NP transport and retention on SWI and AWI. The model accounts for the variation of water content and water velocity as a function of depth and takes into account the presence of the AWI and its role as a NP collector. Comparisons with experimental data showed that the suggested modeled processes can be used to quantify the NPs retentions at the AWI and SWI. The suggested model can be used for both saturated and unsaturated conditions and for a rather large range of velocities.

  1. Mesoporous TiO2 Nanowire Film for Dye-Sensitized Solar Cell.

    PubMed

    Xiao, Li; Xu, Jia; Liu, Xiu; Zhang, Yongzhe; Zhang, Bing; Yao, Jianxi; Dai, Songyuan; Tan, Zhanao; Pan, Xu

    2016-06-01

    In this work, TiO2 nanowire arrays were grown on fluorine-doped tin oxide (FTO) glass substrate, and then were converted into mesoporous nanowires (MNWs). The TiO2 MNWs are about 5 μm in length and 30-200 nm in diameter, with mesopores size of 5-30 nm randomly distributed on the NW surface. X-ray diffraction pattern reports show that the NWs are single crystallized rutile TiO2 and oriented grown along [001]. Through further characterization of FT-IR and TG-DSC, we proposed a reasonable explanation for pore existence. After dye-sensitized solar cells (DSSCs) assembly, the photoelectric conversion efficiency (PCE) of MNWs based DSSC achieved 3.2%. It means tenfold enhancement of photoelectric property compare with the as-grown NWs. Furthermore, dye absorb capacity of MNWs can reach up to 4.11 x 10(-8) mol/cm2. However, such MNWs can not only provide quick and efficient electron transmission channel, but also owns big specific surface area to absorb abundant dyes, thus conducive to fabricate solar cell with a high PCE.

  2. TMAA surface-molecule photon interactions on Au-supported TiO2 nanocrystals

    NASA Astrophysics Data System (ADS)

    Osgood, Richard; Potapenko, Denis; Li, Zhisheng

    2015-03-01

    Nanostructured titanium dioxide is a versatile photocatalytic material. While its photocatalytic properties have been extensively studied in liquid/gas-phase environments, studies of the physics of photoinduced dynamics and reactions on bare well characterized titania nanoparticles using surface science tools have been lacking. Here we explore these photoinduced properties of TMAA-dosed TiO2 nanocrystals prepared in situ on Au(111) substrate with Scanning Tunneling Microscopy (STM) and Temperature Programmed Desorption (TPD). Photodesorption of trimethyl acetic acid was chosen as a model for light-driven reaction dynamics since it is easily imaged with STM and since this system has been the subject of many earlier studies. For comparison, we explored dynamics of TMAA on TiO2 rutile(110) by exposing it to monochromatized UV light and by injecting charges from the STM tip. We then demonstrated that 1-3 nm high and 10-25 nm wide nanocrystals of TiO2 grown on Au(111) surface also exhibit photoreaction activity for TMAA when illumined with UV light. TPD results, which provided surface-averaged information, agree well with STM data and demonstrate TMAA desorption on a single-molecule basis.

  3. Ethyl Radical Ejection During Photodecomposition of Butanone on TiO2(110)

    SciTech Connect

    Henderson, Michael A.

    2008-10-15

    The photodecomposition of acetone and butanone were examined on the (110) surface of rutile TiO2 using temperature programmed desorption (TPD) and photon stimulated desorption (PSD). In both cases, photodecomposition was proceeded by a required thermal reaction between the adsorbed ketone and coadsorbed oxygen resulting in a diolate species. The diolate photodecomposed by ejection of an organic radical from the surface leaving behind a carboxylate species. In the acetone case, only methyl radical PSD was detected and acetate was left on the surface. In the butanone case there was a possibility of either methyl or ethyl radical ejection, with propionate or acetate left behind, respectively. However, only ethyl radical PSD was detected and the species left on the surface (acetate) was the same as in the acetone case. The preference for ethyl radical ejection is linked to the greater thermal stability of the ethyl radical over that of the methyl radical. Unlike in the acetone case, where the ejected methyl radicals did not participate in thermal chemistry on the TiO2(110) surface after photoactivation of the acetone diolate, ethyl radicals photodesorbing at 100 K from butanone diolate showed a preference for dehydrogenation to ethene through the influence of coadsorbed oxygen. These results reemphasize the mechanistic importance of organic radical production during photooxidation reactions on TiO2 surface.

  4. Ethyl Radical Ejection During Photodecomposition of Butanone on TiO2(110)

    SciTech Connect

    Henderson, Michael A.

    2008-10-15

    The photodecomposition of acetone and butanone were examined on the (110) surface of rutile TiO2 using temperature programmed desorption (TPD) and photon stimulated desorption (PSD). In both cases, photodecomposition was proceeded by a required thermal reaction between the adsorbed ketone and coadsorbed oxygen resulting in a diolate species. The diolate photodecomposed by ejection of an organic radical from the surface leaving behind a carboxylate species. In the acetone case, only methyl radical PSD was detected and acetate was left on the surface. In the butanone case there was a possibility of either methyl or ethyl radical ejection, with propionate or acetate left behind, respectively. However, only ethyl radical PSD was detected and the species left on the surface (acetate) was the same as in the acetone case. The preference for ethyl radical ejection is linked to the greater thermal stability of the ethyl radical over that of the methyl radical. Unlike in the acetone case, where the ejected methyl radicals did not participate in thermal chemistry on the TiO2(110) surface after photoactivation of the acetone diolate, ethyl radicals photodesorbing at 100 K from butanone diolate showed a preference for dehydrogenation to ethene through the influence of coadsorbed oxygen. These results reemphasize the mechanistic importance of organic radical production during photooxidation reactions on TiO2 surface. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

  5. Photocatalytic activity of multielement doped TiO 2 in the degradation of congo red

    NASA Astrophysics Data System (ADS)

    Ramakrishnan, R.; Kalaivani, S.; Amala Infant Joice, J.; Sivakumar, T.

    2012-01-01

    TiO2 although considered a promising photocatalyst for the degradation of aqueous pollutants, it suffers from poor absorption in the visible region and hence requires ultraviolet (UV) light for activation. To make TiO2 a visible active photocatalyst, multielement (C, N, B, and F) doping has been done. The synthesised CNBF/TiO2 catalysts were calcined at different temperatures and characterized by XRD, BET surface area, UV DRS, XPS, HRSEM-EDAX, and TEM techniques. These catalysts found to show less band gap values when compared to bare TiO2. These catalysts were tested for their catalytic activity towards the degradation of a textile dye - congo red (CR) under different reaction conditions. It was found that the photocatalytic activity was dependent on both doping of multielement and the calcination temperature of CNBF/TiO2. The co-doped catalysts which were calcined at 400 °C and 600 °C (100% intensity in anatase phase) were found to be the best catalysts (100% decolourisation of CR in 21/2 h and 2 h respectively). TOC analysis carried out for the samples at the reaction time of 5 h showed very high percentage (83%) degradation of CR over CNBF/TiO2 catalysts calcined at 600 °C when compared to the other catalysts calcined at different temperatures. CNBF/TiO2 (1000 °C) showed very less photocatalytic activity due to the formation of rutile phase.

  6. A DFT-D study of structural and energetic properties of TiO2 modifications

    NASA Astrophysics Data System (ADS)

    Moellmann, Jonas; Ehrlich, Stephan; Tonner, Ralf; Grimme, Stefan

    2012-10-01

    The structures and relative energies of the three naturally occurring modifications of titanium dioxide (rutile, brookite and anatase) were investigated. For an accurate description, atom-pairwise dispersion-corrected density functional theory (DFT-D) was applied. The DFT-D3 scheme was extended non-empirically to improve the description of Ti atoms in bulk systems. New dispersion coefficients were derived from TDDFT calculations for electrostatically embedded TiO2 clusters. The dispersion coefficient {C}_{6}^{{TiTi}} is reduced by a factor of 18 compared to the free atom. The three TiO2 modifications were optimized in periodic plane-wave calculations with dispersion-corrected GGA (PBE, revPBE) and hybrid density functionals (PBE0, revPBE0). The calculated lattice parameters are in good agreement with experimental data, in particular the dispersion-corrected PBE0 and revPBE0 hybrid functionals. Although the observed relative stabilities could not be reproduced in all cases, dispersion corrections improve the results. For an accurate description of bulk metal oxides, London dispersion is a prominent force that should not be neglected when energies and structures are computed with DFT. Additionally, the influence of dispersion interactions on the relaxation of the TiO2(110) surface is investigated.

  7. TiO2 Fibers: Tunable Polymorphic Phase Transformation and Electrochemical Properties.

    PubMed

    Garcia, Edna; Li, Qiang; Sun, Xing; Lozano, Karen; Mao, Yuanbing

    2015-05-01

    A series of one-dimensional (1 D) nanoparticle-assembled TiO2 fibers with tunable polymorphs were prepared via a novel and large scale ForceSpinning process of titanium tetraisopropoxide (TTIP)/polyvinylpyrrolidone (PVP) precursor fibers followed with a thermal treatment at various calcination temperatures. The thermal and structural transformations were characterized by thermogravimetric analysis/differential scanning calorimetry, scanning electron microscopy, and X-ray diffraction. The influence of polymorphic phase of the TiO2 fibers on the electrochemical performance in neutral aqueous 1 M Na2SO4 electrolyte was investigated. The polymorphic amorphous/anatase/rutile TiO2 fibers prepared at 450 degrees C achieved a highest capacitance of 21.2 F g(-1) (6.61 mF cm(-2)) at a current density of 200 mA g(-1), for which the improved electronic conductivity and activated pseudocapacitance mechanism may be responsible. This work helps bridge the gap between nanoscience and manufacturing. It also makes polymorphism control of functional materials a potential strategy for further improving supercapacitive output of metal oxides. PMID:26505001

  8. Synthesis of self-organized TiO2 nanotube arrays: Microstructural, stereoscopic, and topographic studies

    NASA Astrophysics Data System (ADS)

    Quiroz, Heiddy P.; Dussan, A.

    2016-08-01

    In this work, titanium dioxide nanotubes were prepared by using titanium foils via electrochemical anodization in ethylene glycol solutions containing different amounts of water and fluoride in the ranges of 1%-3% and 0.15%-0.5%, respectively, to determine their effects on morphology, optical, and crystalline structure properties. Annealing processes were performed on all samples in the range between 273 and 723 K. Morphology and structure properties of the samples were studied by scanning electron microscopy, X-ray diffraction (XRD), and transmission electron microscopy. Titanium dioxide (TiO2) nanotubes, through anodization method, are strongly influenced by conditions, like fluoride concentration and applied voltages. Tube lengths between 2 and 7 μm were obtained, exhibiting different diameters and wall thicknesses. When alternating voltage was applied, the outer surface of the nanotubes exhibited evenly spaced ring-shaped regions, while smooth tubes were observed when constant voltage was applied. Reflection peaks, corresponding to Brookite, Anatase, and Rutile, of TiO2 phases, were observed from the XRD pattern. These phases were corroborated via μXRD measurements, and the Ti3O5 phase was also observed in detail. Absorption coefficient (α), optical band gap (Eg), and extinction coefficient (ɛ) of TiO2 nanotubes were calculated by transmittance spectra in the UV-Vis range. Strong absorption was noted in the UV region from reflectance and absorbance measurements. A correlation between synthesis parameters and physical properties is presented.

  9. Unconventional ratiometric-enhanced optical sensing of oxygen by mixed-phase TiO2

    NASA Astrophysics Data System (ADS)

    Lettieri, S.; Pallotti, D. K.; Gesuele, F.; Maddalena, P.

    2016-07-01

    We show that mixed-phase titanium dioxide (TiO2) can be effectively employed as an unconventional, inorganic, dual-emitting, and ratiometric optical sensor of O2. Simultaneous availability of rutile and anatase TiO2 photoluminescence (PL) and their peculiar "anti-correlated" PL responses to O2 allow using their ratio as a measurement parameter associated with the O2 concentration, leading to an experimental responsivity being by construction larger than the one obtainable for single-phase PL detection. A proof of this concept is given, showing a two-fold enhancement of the optical responsivity provided by the ratiometric approach. Besides the peculiar ratiometric-enhanced responsivity, other characteristics of mixed phase TiO2 can be envisaged as favorable for O2 optical probing, namely (a) low production costs, (b) absence of heterogeneous components, and (c) self-supporting properties. These characteristics encourage experimenting with its use for applications requiring high indicator quantities at a competitive price, possibly also tackling the need to develop supporting matrixes that carry the luminescent probes and avoiding issues related to the use of different components for ratiometric sensing.

  10. C-doped mesoporous anatase TiO2 comprising 10nm crystallites.

    PubMed

    Xie, Chong; Yang, Shenghui; Li, Beibei; Wang, Hongkong; Shi, Jian-Wen; Li, Guodong; Niu, Chunming

    2016-08-15

    We report a C-doped mesoporous anatase TiO2 with high surface area synthesized using multi-walled carbon nanotube (MWCNT) mat as a "rigid" template and carbon doping source. The characterization by SEM, HRTEM, X-ray diffraction and nitrogen adsorption revealed that TiO2 samples have a porous structure which are figuratively a inverse copy of MWCNT network and pore walls are formed by interconnected TiO2 nanoparticles with average diameter of ∼10nm. We found that annealing temperatures from 400 to 1000°C before MWCNT template removal had very limited effect on particle size (∼10nm), surface area (112-129m(2)/g) and total pore volume (0.74-0.85m(2)/g) of the samples through a significantly delayed phase transition from anatase to rutile started at 800°C, resulting in only ∼9.1% conversion at 1000°C. The pore size distribution is in mesopore range from 6 to 60nm peaked at ∼24nm. XPS analysis showed a relatively strong C1s peak at 288.4eV, indicating C doping at Ti sites, which is responsible for red shift of adsorption edge of UV-vis spectra and photocatalytic activity in visible-light region. PMID:27179173

  11. Photocatalytic and superhydrophilicity properties of N-doped TiO 2 nanothin films

    NASA Astrophysics Data System (ADS)

    Chekini, M.; Mohammadizadeh, M. R.; Vaez Allaei, S. M.

    2011-06-01

    Pure TiO 2 and nitrogen doped titanium dioxide (N-TiO 2) thin films were prepared by sol-gel method through spin coating on soda lime glass substrates. TiCl 4 and urea were used as Ti and N sources in the sol. XRD results showed nitrogen doping has retarded anatase to rutile phase transformation. The doping also leads to a decrease in roughness of the samples from 4 nm (TiO 2) to 1 nm (N-TiO 2). However, surface analysis by statistical methods reveals that both surfaces have self-affine structure. Optical band gap of thin films was shifted from 3.65 eV (TiO 2) to 3.47 eV (N-TiO 2). Hydrophilic conversion and photocatalytic degradation properties of thin films were investigated and exhibited that N-TiO 2 thin film has more preferable hydrophilicity and photocatalytic properties under UV illumination.

  12. Generation of Organic Radicals During Photocatalysis on TiO2

    NASA Astrophysics Data System (ADS)

    Henderson, Michael

    2008-03-01

    It is well-known that water-related radicals (such as OH. species) are produced by charge transfer events at UV-irradiated TiO2 surfaces. In contrast, organic radicals are generally viewed as being formed by reactions with OH. groups and not by direct charge transfer events. Using rutile TiO2(110) as a model photocatalyst, we show that organic radicals are generated in single-step charge transfer events during photodecomposition of adsorbed carboxylates and ketones. Some organic radicals (e.g., methyl) are ejected from the surface and, in high surface area catalysts, experience reactions away from the surface of origin. Other radicals (e.g., ethyl and t-butyl) have limited ability to escape the surface of origin without capture and subsequent thermal reactions. Understanding the chemistry associated with organic radical formation on TiO2 opens the door for more detailed examinations of charge transfer dynamics and energy redistribution during photon-initiated reactions important to heterogeneous photocatalysis.

  13. Mesoporous TiO2 Nanowire Film for Dye-Sensitized Solar Cell.

    PubMed

    Xiao, Li; Xu, Jia; Liu, Xiu; Zhang, Yongzhe; Zhang, Bing; Yao, Jianxi; Dai, Songyuan; Tan, Zhanao; Pan, Xu

    2016-06-01

    In this work, TiO2 nanowire arrays were grown on fluorine-doped tin oxide (FTO) glass substrate, and then were converted into mesoporous nanowires (MNWs). The TiO2 MNWs are about 5 μm in length and 30-200 nm in diameter, with mesopores size of 5-30 nm randomly distributed on the NW surface. X-ray diffraction pattern reports show that the NWs are single crystallized rutile TiO2 and oriented grown along [001]. Through further characterization of FT-IR and TG-DSC, we proposed a reasonable explanation for pore existence. After dye-sensitized solar cells (DSSCs) assembly, the photoelectric conversion efficiency (PCE) of MNWs based DSSC achieved 3.2%. It means tenfold enhancement of photoelectric property compare with the as-grown NWs. Furthermore, dye absorb capacity of MNWs can reach up to 4.11 x 10(-8) mol/cm2. However, such MNWs can not only provide quick and efficient electron transmission channel, but also owns big specific surface area to absorb abundant dyes, thus conducive to fabricate solar cell with a high PCE. PMID:27427603

  14. C-doped mesoporous anatase TiO2 comprising 10nm crystallites.

    PubMed

    Xie, Chong; Yang, Shenghui; Li, Beibei; Wang, Hongkong; Shi, Jian-Wen; Li, Guodong; Niu, Chunming

    2016-08-15

    We report a C-doped mesoporous anatase TiO2 with high surface area synthesized using multi-walled carbon nanotube (MWCNT) mat as a "rigid" template and carbon doping source. The characterization by SEM, HRTEM, X-ray diffraction and nitrogen adsorption revealed that TiO2 samples have a porous structure which are figuratively a inverse copy of MWCNT network and pore walls are formed by interconnected TiO2 nanoparticles with average diameter of ∼10nm. We found that annealing temperatures from 400 to 1000°C before MWCNT template removal had very limited effect on particle size (∼10nm), surface area (112-129m(2)/g) and total pore volume (0.74-0.85m(2)/g) of the samples through a significantly delayed phase transition from anatase to rutile started at 800°C, resulting in only ∼9.1% conversion at 1000°C. The pore size distribution is in mesopore range from 6 to 60nm peaked at ∼24nm. XPS analysis showed a relatively strong C1s peak at 288.4eV, indicating C doping at Ti sites, which is responsible for red shift of adsorption edge of UV-vis spectra and photocatalytic activity in visible-light region.

  15. A self-powered UV photodetector based on TiO2 nanorod arrays

    PubMed Central

    2013-01-01

    Large-area vertical rutile TiO2 nanorod arrays (TNAs) were grown on F/SnO2 conductive glass using a hydrothermal method at low temperature. A self-powered ultraviolet (UV) photodetector based on TiO2 nanorod/water solid–liquid heterojunction is designed and fabricated. These nanorods offer an enlarged TiO2/water contact area and a direct pathway for electron transport simultaneously. By connecting this UV photodetector to an ammeter, the intensity of UV light can be quantified using the output short-circuit photocurrent without a power source. A photosensitivity of 0.025 A/W and a quick response time were observed. At the same time, a high photosensitivity in a wide range of wavelength was also demonstrated. This TNA/water UV detector can be a particularly suitable candidate for practical applications for its high photosensitivity, fast response, excellent spectral selectivity, uncomplicated low-cost fabrication process, and environment-friendly feature. PMID:23618012

  16. Gallium Arsenide Layers Grown by Molecular Beam Epitaxy on Single Crystalline Germanium Islands on Insulator

    NASA Astrophysics Data System (ADS)

    Takai, Mikio; Tanigawa, Takaho; Minamisono, Tadanori; Gamo, Kenji; Namba, Susumu

    1984-05-01

    Gallium arsenide (GaAs) layers have successfully been grown by molecular beam epitaxy on single crystalline germanium (Ge) islands, recrystallized by zone melting with SiO2 capping layers, on thermally-oxidized Si-wafers. The GaAs layers, grown on the single crystalline Ge islands, show smooth surfaces without any grain-boundaries, while those, grown on the Ge islands with grain-boundaries and on the SiO2, have grain-boundaries. The GaAs layers on the single crystalline Ge islands emit photoluminescence, the intensity of which is almost comparable to that of GaAs layers on bulk Ge crystals.

  17. 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

  18. Structural and optical properties of anatase TiO2 heteroepitaxial films prepared by MOCVD

    NASA Astrophysics Data System (ADS)

    Zhao, Wei; Feng, Xianjin; Xiao, Hongdi; Luan, Caina; Ma, Jin

    2016-11-01

    High-quality single-crystal anatase TiO2(a-TiO2) thin films have been obtained on SrTiO3 (STO) substrates using the metalorganic chemical vapor deposition (MOCVD) method. The optimal preparation process was explored. The lattice structure and epitaxial relationship were investigated by X-ray diffraction (XRD, both θ-2θ and Φ scans) and transmission electron microscopy (TEM). The results indicated that the film prepared at 550 °C with the Ti precursor molar flow rate of 4×10-7 mol/min had the best single crystalline quality, for which a clear epitaxial relationship of a-TiO2 (001)||STO (100) with a-TiO2 [100]||STO [001bar] could be inferred. The elemental composition and proportion were studied by the X-ray photoelectron spectroscopy (XPS) method, which proved the deposited film approximated stoichiometric TiO2. The samples showed high transparency of 70-80% in the visible range.

  19. Plasma-assisted molecular beam epitaxy of SnO 2 on TiO 2

    NASA Astrophysics Data System (ADS)

    Tsai, M. Y.; White, M. E.; Speck, J. S.

    2008-08-01

    Epitaxial growth of SnO 2 on TiO 2 (1 1 0) substrates by plasma-assisted molecular beam epitaxy was studied under various growth conditions to explore the potential for high-quality single crystalline growth. Phase-pure (1 1 0)-oriented SnO 2 films with an optimum on-axis X-ray rocking curve scan full-width at half-maximum equal to 0.612° were grown. The film epitaxy proceeded in the Volmer-Weber growth mode. We identified different growth regimes by measuring growth rate variations correlated with increasing tin fluxes at a fixed oxygen pressure. Beginning in the oxygen-rich growth regime, growth rates increased linearly as the tin flux increased. Atomically flat surfaces were observed in the oxygen-rich regime. Continued tin flux increases resulted in a maximum growth rate of 470 nm/h. Further tin flux increases prevented SnO 2 formation on the growth surface and acted as a nucleation barrier of SnO 2 on the TiO 2 substrates identifying a metal-rich growth regime.

  20. Toxicity of TiO(2) nanoparticles to cladocerans, algae, rotifers and plants - effects of size and crystalline structure.

    PubMed

    Clément, Laura; Hurel, Charlotte; Marmier, Nicolas

    2013-01-01

    With the rapid development of nanotechnology, there is an increasing risk of human and environmental exposure to nanotechnology-based materials. However, the data on the potential environmental effects of nanoparticles are scarce. The aim of this study is to assess the effect of particle size and crystal structure (anatase and rutile) of titanium dioxide on their toxicity. Thus, acute and chronic toxicity tests included a modified acute test (72 h) using daphnies and algae, rotifers and plants as model organisms. Gradient of toxicity varied with the tested biological organisms. Our results revealed that TiO(2) nanoparticles in anatase crystal structure are toxic in the entire set of tests conducted. However, at highconcentration, through their antimicrobial properties, they significantly promoted growth of roots. Because of its lipophilicity, the rutile crystalline structure of TiO(2) NPs form larger aggregates in aqueous medium; then they have less effect on biological organisms, and thus a lower toxicity than the anatase crystalline form of TiO(2). We also demonstrated that exposure duration, aggregation and concentrations are contributing factors in nanoparticles-mediated toxicity.

  1. Photocatalytic degradation of aqueous propoxur solution using TiO2 and Hbeta zeolite-supported TiO2.

    PubMed

    Mahalakshmi, M; Vishnu Priya, S; Arabindoo, Banumathi; Palanichamy, M; Murugesan, V

    2009-01-15

    Photocatalytic activity of TiO2 and zeolites supported TiO2 were investigated using propoxur as a model pollutant. Hbeta, HY and H-ZSM-5 zeolites were examined as supports for TiO2. Hbeta was chosen as the TiO2 support based on the adsorption capacity of propoxur on these zeolites (Hbeta>HY=H-ZSM-5). TiO2/Hbeta photocatalysts with different wt.% were prepared and characterized by XRD, FT-IR and BET surface area. The progress of photocatalytic degradation of aqueous propoxur solution using TiO2 (Degussa P-25) and TiO2 supported on Hbeta zeolite was monitored using TOC analyzer, HPLC and UV-vis spectrophotometer. The degradation of propoxur was systematically studied by varying the experimental parameters in order to achieve maximum degradation efficiency. The initial rate of degradation with TiO2/Hbeta was higher than with bare TiO2. TOC results revealed that TiO2 requires 600min for complete mineralization of propoxur whereas TiO2/Hbeta requires only 480min. TiO2/Hbeta showed enhanced photodegradation due to its high adsorption capacity on which the pollutant molecules are pooled closely and hence degraded effectively.

  2. Towards TiO2 nanotubes modified by WO3 species: influence of ex situ crystallization of precursor on the photocatalytic activities of WO3/TiO2 composites

    NASA Astrophysics Data System (ADS)

    Sun, Hui; Dong, Bohua; Su, Ge; Gao, Rongjie; Liu, Wei; Song, Liang; Cao, Lixin

    2015-09-01

    TiO2 nanotubes (TNT) crystallized at different temperatures were loaded with WO3 hydrate through the reaction between (NH4)6W7O24·6H2O and an aqueous solution of HCl. The photocatalytic activities of nanocomposites firstly increase and then decrease as a function of the crystallized temperature of the TNT precursor. The structural, morphologic and optical properties of WO3/TiO2 nanocomposites were also investigated in this study. The samples, initially anatase titania (573 K-773 K), presented phase transition to rutile titania at 873 K. With the crystallized temperature increasing, an evolution of samples morphology changing from nanotube-like structure to nanorod-like structure was observed. Meanwhile, the absorption edge of samples exhibited a red shift, and correspondingly their band gap decreased. Consistent with x-ray diffraction diffractograms, the existence of rutile titania as an impurity in the precursor TNT, crystallized at higher than 873 K, depressed photocatalytic activity evidently. As a result, the degradation rate of methyl orange (MO) increased with the samples crystallinity firstly, and then reduced due to the appearance of rutile titania. In our experimental conditions, the optimal photocatalytic activity was achieved for the sample crystalized at 773 K. Its degradation rate could reach 98.76% after 90 min UV light irradiation.

  3. Characterization of the structure, thermal stability and wettability of the TiO2 nanotubes growth on the Ti-7.5Mo alloy surface

    NASA Astrophysics Data System (ADS)

    Chaves, J. M.; Escada, A. L. A.; Rodrigues, A. D.; Alves Claro, A. P. R.

    2016-05-01

    In this study, the Ti-7.5Mo experimental alloy for biomedical applications was processed showing orthorhombic (α″) martensite phase and low elastic modulus (54 GPa). The surface treatment permitted the growth of ordered TiO2 nanotubes via anodization process. The heat treatment during in situ Raman measurement revealed that the TiO2 nanotubes were transformed of the amorphous state for crystalline (anatase phase) around 400 °C. Annealing of the nanotubes was evaluated by XRD, SEM and Raman spectroscopy. Results showed a high stability of the nanostructure, since only for temperatures above of 500 °C, at which the phase rutile appears, the nanostructure tends to vanish. It was observed in Raman analysis an increasing of the average size of the crystallite of the anatase phase with annealing temperature ranging from 6.5 nm up to 13 nm, besides of the precipitation of the layer rutile in the interface nanotubes-substrate. It is believed that the contact between anatase crystallites or layer rutile of the interface lead to growth of the rutile phase, causing coalescence and subsequent collapse of the tubular nanostructure. The wettability, as well as, surface energy was dependent of the crystalline structure and morphology, becoming more hydrophilic in the anatase phase when as compared with amorphous and rutile phase. The typical features of the surface together excellent bulk properties (low elastic modulus) of the Ti-7.5Mo alloy can provide a guideline for future biomedical applications.

  4. TiO2-TiO2 composite resistive humidity sensor: ethanol crosssensitivity

    NASA Astrophysics Data System (ADS)

    Ghalamboran, Milad; Saedi, Yasin

    2016-03-01

    The fabrication method and characterization results of a TiO2-TiO2 composite bead used for humidity sensing along with its negative cross-sensitivity to ethanol vapor are reported. The bead shaped resistive sample sensors are fabricated by the drop-casting of a TiO2 slurry on two Pt wire segments. The dried bead is pre-fired at 750°C and subsequently impregnated with a Ti-based sol. The sample is ready for characterization after a thermal annealing at 600°C in air. Structurally, the bead is a composite of the micron-sized TiO2 crystallites embedded in a matrix of nanometric TiO2 particle aggregates. The performance of the beads as resistive humidity sensors is recorded at room temperature in standard humidity level chambers. Results evince the wide dynamic range of the sensors fabricated in the low relative humidity range. While the sensor conductance is not sensitive to ethanol vapor in dry air, in humid air, sensor's responses are negatively affected by the contaminant.

  5. Effect of annealing temperature on wettability of TiO2 nanotube array films

    PubMed Central

    2014-01-01

    Highly ordered TiO2 nanotube array (TN) films were prepared by anodization of titanium foil in a mixed electrolyte solution of glycerin and NH4F and then annealed at 200°C, 400°C, 600°C, and 800°C, respectively. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), water contact angle (WCA), and photoluminescence (PL). It was found that low temperature (below 600°C) has no significant influence on surface morphology, but the diameter of the nanotube increases from 40 to 50 nm with increasing temperature. At 800°C, the nanotube arrays are completely destroyed and only dense rutile film is observed. Samples unannealed and annealed at 200°C are amorphous. At 400°C, anatase phase appears. At 600°C, rutile phase appears. At 800°C, anatase phase changes into rutile phase completely. The wettability of the TN films shows that the WCAs for all samples freshly annealed at different temperatures are about 0°. After the annealed samples have been stored in air for 1 month, the WCAs increase to 130°, 133°, 135°, 141°, and 77°, respectively. Upon ultraviolet (UV) irradiation, they exhibit a significant transition from hydrophobicity to hydrophilicity. Especially, samples unannealed and annealed at 400°C show high photoinduced hydrophilicity. PMID:25426006

  6. Preparation of perpendicular oriented TiO2 films via hydrothermal method: phase selection and growth control

    NASA Astrophysics Data System (ADS)

    Gao, Yun; Guo, Meilan; Xia, Xiaohong; Shao, Guosheng

    2013-03-01

    Either rutile or anatase vertical orientated TiO2 array films were synthesized successfully on FTO (F: SnO2) substrate via hydrothermal method through controlling the concentration of Cl- and SO42- . The density of nanorods can be adjusted by varying the volume ratio of ethanol/water, and the degree of orientation and crystallinity of TiO2 nanofilms were enhanced with increasing dosage of ethanol. Meanwhile, completely dense anatase films with [004] oriented growth appear within a very narrow concentration window when adding sulfuric acid into precursor. Besides, other alcohols such as methanol, n-propanol and n-butyl were also used as solvent to examine the role of alcohol type during hydrothermal process for both two phase films. The growth rate and degree of perpendicular orientation declined as the alkyl length of solvents increases. Hydrogen sensing characteristics of dense films of both rutile and anatase phases showed that there was a remarkable improvement of sensitivity response over reported data. It was found that rutile films have higher sensitivity while anatase films have faster response. This work is supported by Ministry of Education of China (211108) and Science and Technology of Wuhan (2010CDA024, 201110821251).

  7. Frictional Properties of Single Crystalline and Quasicrystalline Surfaces

    NASA Astrophysics Data System (ADS)

    Gellman, Andrew

    2000-03-01

    The use of ultra-high vacuum surface science methods has been aplied to the problem of studying friction between single srystalline and quasicrystalline metal surfaces. A experimental apparatus has been developed that combines the ability to perform surface preparation and analysis with the ability to make measurements of macroscopic friction forces between surfaces in sliding contact. This UHV chamber allows simultaneous preparation and characterization of two sample surfaces. These are usually single crystalline samples of the same metal and can be either perfectly clean or modified by adsorbed species such as atoms or molecules. Once prepared these two surfaces can be brought into contact under an applied normal load (Fn = 0.001 0.1 N) and sheared relative to one another at constant velocity (vs = 1 100 mm/s). Both normal and shear forces are measured simultaneously enabling one to determine a coefficient of friction. This unique apparatus has been used to study a number of problems in tribology. Adsorbed species on metal surfaces serve as a lubricants and prevent direct metal-metal contact. We have addressed the issue of surface coverage effects on interfacial friction. Surfaces have been prepared with adsorbed species ranging continuously in coverage from zero monolayers to many ( 100) monolayers. These experiments have been performed with pairs of both Ni(100) and Cu(111) surfaces. The interesting observation has been that adsorbed layers of atoms have little or no influence on friction coefficients between the two surfaces at coverages below one monolayer. Adsorbed molecules such as ethanol or trifluoroethanol are more interesting in this regard. They also have little influence on friction when adsorbed at coverages of < 1 monolayer, however, once the coverage exceeds 1 monolayer the coefficient of friction drops substantially. Friction reaches its limit at coverages of 5 10 monolayer. It is quite interesting to note that these metal single crystal surface

  8. Electrical Properties and Defect Chemistry of In-Doped TiO2 in Terms of the Jonker Formalism.

    PubMed

    Nowotny, Janusz; Bak, Tadeusz; Ionescu, Mihail; Alim, Mohammad A

    2015-04-30

    The present work considers the semiconducting properties of In-doped TiO2 in terms of the Jonker formalism applied for both electrical conductivity and thermoelectric power data determined simultaneously in equilibrium with the gas phase of controlled oxygen activity. It is shown that the electrical properties of In-doped TiO2 annealed in oxidizing conditions [p(O2) > 10 Pa] can be described by the Jonker formalism very well. However, annealing of In-doped TiO2 in strongly reducing conditions [p(O2) < 10(-10) Pa], imposed by the gas phase involving hydrogen, results in a deviation of the experimental data from the Jonker's theoretical model derived for the Maxwell-Boltzmann statistics. This departure is considered in terms of the effect of hydrogen on the formation of structural domains, which are expected to be entirely different from those of oxidized TiO2 in terms of its electronic properties. It is argued that In-doped TiO2 annealed in the gas phase involving hydrogen exhibits a high concentration of donor-type ionic defects, which lead to the formation of high concentration of electrons. The related semiconducting properties are inconsistent with the model of classical semiconductor where the electrons are described by the Maxwell-Boltzmann statistics. It is concluded that strong interactions within the electron gas lead, in consequence, to the behavior resembling correlated transport of electrons. The obtained results suggest that indium incorporation into the rutile structure of TiO2 results in the formation of structural properties that exhibit extraordinary charge transport.

  9. Enhanced photoelectrical performance of dye-sensitized solar cells with double-layer TiO2 on perovskite SrTiO3 substrate

    NASA Astrophysics Data System (ADS)

    Liu, Qiuhong; Sun, Qiong; Zhang, Min; Li, Yang; Zhao, Mei; Dong, Lifeng

    2016-04-01

    In this research, perovskite SrTiO3 particles are synthesized by a hydrothermal method, and TiO2 with a double-layer structure is grown on the SrTiO3 surface by a hydrolysis-condensation process. Structural characterizations reveal that TiO2 comprises of two phases: anatase film at the bottom and single-crystal rutile nanorods grown along the [110] direction on top. The TiO2-SrTiO3 composite film is investigated as photoanode material for dye-sensitized solar cells. In comparison with pure TiO2 and SrTiO3, the composite photoanode shows a much better performance in photoelectric conversion efficiency (1.35 %), which is about 2 and 100 times as efficient as pure TiO2 and SrTiO3, respectively. This indicates that the composite structure can facilitate charge carrier transfer and reduce electron-hole recombination to enhance photoelectrical properties of TiO2-based photoanode materials.

  10. Synthesis and photocatalytic activity of TiO2 nanoparticles prepared by chemical vapor condensation method with different precursor concentration and residence time.

    PubMed

    Chin, Sungmin; Park, Eunseuk; Kim, Minsu; Bae, Gwi-Nam; Jurng, Jongsoo

    2011-10-15

    Nanosized TiO(2) photocatalysts were synthesized using a chemical vapor condensation method under a range of synthesis conditions (precursor vapor concentration and residence time in a tubular electric furnace). X-ray diffraction showed that the prepared TiO(2) powders consisted mainly of anatase (>94%) with a small amount of rutile. The mean particle diameter from the Brunauer-Emmett-Teller surface area and transmission electron microscopy measurements ranged from 9.4 to 16.6 nm. The specific surface area (92.5-163.5 m(2) g(-1)) of the prepared TiO(2) powders was found to be dependent on the synthesis conditions. The content of hydroxyl groups on the surface of the prepared TiO(2) sample was higher than those on commercial TiO(2), resulting in increased photocatalytic oxidation. The photocatalytic activity of the TiO(2) samples prepared in a methylene blue solution was strongly dependent on the crystallinity and specific surface area, which were affected by the TTIP vapor concentration and residence time. PMID:21802692

  11. Influence of optical band gap and particle size on the catalytic properties of Sm/SnO2-TiO2 nanoparticles

    NASA Astrophysics Data System (ADS)

    Javaid, Shaghraf; Farrukh, Muhammad Akhyar; Muneer, Iqra; Shahid, Maryam; Khaleeq-ur-Rahman, Muhammad; Umar, Akrajas Ali

    2015-06-01

    In this work, samarium (Sm) supported on tin oxide-titanium oxide (SnO2/TiO2) nanoparticles (Sm/SnO2-TiO2) were synthesized by sol-gel, ultrasonic and hydrothermal methods; and the optical and catalytic properties of Sm/SnO2-TiO2 nanoparticles was observed. Effect of synthetic methods on nanoparticles size and percentage composition of anatase and rutile phase in TiO2 was evaluated. The Sm/SnO2-TiO2 nanoparticles were characterized by Transmission Electron Microscopy, Scanning Electron Microscopy, Energy Dispersive X-ray spectroscopy, Powder X-ray Diffraction, Thermogravimetric Analysis and Fourier Transmission Infrared Spectroscopy. However, UV-Vis and solid phase spectroscopy were used to determine the catalytic efficiency and optical band gap, respectively. It was found out that nanoparticles synthesized by sol-gel and hydrothermal method have small optical band gap as compare to nanoparticles synthesized by ultrasonic method and ultimately showed more catalytic activity toward degradation of dye due to red shift in the optical band gap (shifting of wavelength to visible region). A direct relationship between particle size and optical band gap was investigated. It was observed that Sm reduced the optical band gap and increased catalytic efficiency when supported on SnO2/TiO2.

  12. Highly branched RuO2 Nanorods on Electrospun TiO2 Nanofibers toward Electrochemical Catalysts

    NASA Astrophysics Data System (ADS)

    Cho, Yukyung; Kim, Su-Jin; Lee, Nam-Suk; Kim, Myung Hwa; Lee, Youngmi

    2014-03-01

    We report a facile growth route to synthesize hierarchically grown single crystalline metallic RuO2 nanorods on electrospun TiO2 nanofibers via a combination of a simple vapour phase transport process with an electrospinning process. This synthetic strategy could be very useful to design a variety of highly branched network architectures of the functional hetero-nanostructures for electrochemical applications. Particularly, Ruthenium oxide (RuO2) 1-dimensional nanostructures can be used as the effective catalysts or electrochemical electrode materials. Thus, we first synthesize TiO2 nanofibers from mixture of titanium isopropoxide precursor and polymer and then ruthenium hydroxide precursor on TiO2 nanofibers are transformed into RuO2 nanorods by thermal treatment at 250oC in air. The crystalline structures of products are confirmed using scanning electron microscopy (FE-SEM), X-ray diffraction (XRD) spectrum, Raman spectroscopy, and high resolution electron microscopy (HRTEM). The fundamental electrochemical performances are examined using cyclic voltammetry (CV).

  13. A floating macro/mesoporous crystalline anatase TiO2 ceramic with enhanced photocatalytic performance for recalcitrant wastewater degradation.

    PubMed

    Xing, Zipeng; Zhou, Wei; Du, Fan; Qu, Yang; Tian, Guohui; Pan, Kai; Tian, Chungui; Fu, Honggang

    2014-01-14

    A macro/mesoporous anatase TiO2 ceramic floating photocatalyst has been successfully synthesized using highly thermally stable mesoporous TiO2 powder as a precursor, followed by a camphene-based freeze-casting process and high-temperature calcinations. The ceramics are characterized in detail by X-ray diffraction, Raman spectra, scanning electron microscopy, transmission electron microscopy and N2 adsorption-desorption isotherms. The results indicate that the TiO2 ceramics present hierarchical macro/mesoporous structures, which maintain high porosity and high compressive strength at the optimal sintering temperature of 800 °C. The ordered mesoporous TiO2 network still possesses high thermal stability and inhibits the anatase-to-rutile phase transformation during calcinations. The obtained ceramics exhibit good adsorptive and photocatalytic activity for the degradation of octane and rhodamine B, and the total organic carbon removal ratio is up to 98.8% and 98.6% after photodegradation for 3 h, respectively. The roles of active species in the photocatalytic process are compared using different types of active species scavengers, and the degradation mechanism is also proposed. Furthermore, the ceramics are recyclable, and no clear changes are observed after ten cycles. In addition, the ceramics are also active in the photodegradation of phenol, thiobencarb, and atrazine. Therefore, these novel floating photocatalysts will have wide applications, including the removal of floating organic pollutants from the wastewater surfaces or the removal of soluble organic pollutants from wastewater.

  14. Effect of Molar Concentration of NH4OH on Photocatalytic Activity in Preparation of Nanosized TiO2 Powder from Spent Titanium Chip by Sol-Gel Method.

    PubMed

    Lee, Hwan-Gyu; Lee, Young-Ho; Yun, Hyeon-Jun; Jo, Jang-Ho; Kim, Seong-Kyung; Yu, Hyeon-Jin; Kim, Ki-Joong; Kang, Byeong-Mo; Jeong, Woon-Jo; Chung, Min-Chul; Jung, Sang-Chul; Lee, Do-Jin; Ahn, Ho-Geun

    2016-05-01

    The TiO2 powder was prepared from the spent titanium chips by applying the sol-gel method. The spent titanium chip was dissolved in HCl solution, and then NH4OH solution was added. The molar concentration of NH4OH solution was 2 M, 4 M, 8 M, and 10 M. Obtained TiO2 powders were calcined at 200 degrees C, 400 degrees C, and 600 degrees C. The prepared TiO2 powder was characterized using a particle size analysis, BET surface area, and XRD analysis. The crystal structure of the TiO2 powder was rutile type and anatase. The highest BET surface area of TiO2 powder was 432.8 m2/g. The photocatalytic property of the TiO2 powder was evaluated as decomposition rate of methylene blue(MB) by using a liquid phase stirred reactor. UV source was a UV-A, and concentration of MB in most experiments was 8 ppm. The concentration of MB was measured by absorbance at 664 nm using UV spectroscopy. Photocatalytic efficiency of prepared TiO2 powder depended highly on concentration of NH4OH solution. The TiO2 powder prepared with 8 M-NH4OH solution showed the highest efficiency, the decomposition efficiency at decomposition time of 2 hr and MB concentration of pH 8 was 98%. PMID:27483804

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

    PubMed

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

    2016-03-01

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

  16. Influence of triblock copolymer (pluronic F127) on enhancing the physico-chemical properties and photocatalytic response of mesoporous TiO2

    NASA Astrophysics Data System (ADS)

    Samsudin, Emy Marlina; Hamid, Sharifah Bee Abd; Juan, Joon Ching; Basirun, Wan Jefrey

    2015-11-01

    The utilization of triblock copolymer, pluronic F127 as a structure directing agent for the preparation of TiO2 played an important role in enhancing the photocatalytic degradation rate of atrazine by a factor of 1.7. The mesoporous F127-TiO2 showed significant modification of morphology, particle and crystallite size, and presence of defect energy belt within the catalyst forbidden band as proven via photoluminescence spectra and x-ray photon spectroscopy. Hence the photogenerated carriers have longer lifespan to migrate to the catalyst surface for redox activities. Furtherance, surface reactive {0 0 1} facets proven by the formation of new geometrical single crystal of square and rhombus surfaces in F127-TiO2 facilitates atrazine degradation as well. The increased surface area of F127-TiO2 promotes greater atrazine absorption, thus governs improved interaction between absorbed atrazine molecules and surface generated active radicals as a pre-requisite for good photocatalytic activity. Interestingly, using the same synthesis procedure, it was observed that the addition of pluronic F127 significantly affects anatase crystal structure as opposed to the more thermodynamically stable rutile, generating 61% and 25% of total crystallite size modification for anatase and rutile, respectively. However, there were no changes on the final composition of anatase and rutile crystal structure. In overall, enhancement of the photocatalytic degradation of atrazine is ruled out to the following factors (1) modification of geometrical structures and size, (2) narrowing of band gap due to defect energy belt, (3) longer lifespan of photoexcited charges to the catalyst surface, (4) enhanced surface textural properties and (5) increased exposure of reactive {0 0 1} facets, which were all observed in F127-TiO2.

  17. Quantitative Structure of an Acetate Dye Molecule Analogue at the TiO2–Acetic Acid Interface

    PubMed Central

    2016-01-01

    The positions of atoms in and around acetate molecules at the rutile TiO2(110) interface with 0.1 M acetic acid have been determined with a precision of ±0.05 Å. Acetate is used as a surrogate for the carboxylate groups typically employed to anchor monocarboxylate dye molecules to TiO2 in dye-sensitized solar cells (DSSC). Structural analysis reveals small domains of ordered (2 × 1) acetate molecules, with substrate atoms closer to their bulk terminated positions compared to the clean UHV surface. Acetate is found in a bidentate bridge position, binding through both oxygen atoms to two 5-fold titanium atoms such that the molecular plane is along the [001] azimuth. Density functional theory calculations provide adsorption geometries in excellent agreement with experiment. The availability of these structural data will improve the accuracy of charge transport models for DSSC. PMID:27110318

  18. Growth of TiO2 nanorods on a Ta substrate by metal-organic chemical vapor deposition.

    PubMed

    Lee, Kang Suk; Hyun, Jae-Sung; Seo, Hyun Ook; Kim, Young Dok; Boo, Jin-Hyo

    2010-05-01

    TiO2 nanorods were successfully grown on Tantalum (Ta) substrates using titanium tetra isopropoxide (TTIP) as a single precursor without any carriers or bubbling gases. For characterization of the TiO2 structures, scanning electron microscopy (SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) were employed. For substrate temperatures below 800 degrees C, a rough film structure without nanorods could be found. However, at a sample temperature of 800 degrees C, nanorod structures with a respective diameter and length of 0.1 approximately 0.2 microm and 0.7 approximately 1.5 microm, respectively, could be synthesized. The nanorods exhibited a rutile phase with a 2:1 stoichiometry of O:Ti, identified using XRD and XPS. When the growth temperature exceeded 800 degrees C, agglomeration of the nanorods was identified. PMID:20358953

  19. Electrical Characteristics of TiO(2-x)/TiO2 Resistive Switching Memory Fabricated by Atomic Layer Deposition.

    PubMed

    Heo, Kwan-Jun; Kim, Won-You; Kim, Sung-Jin

    2016-06-01

    The rewritable low-power operated nonvolatile resistive random access memory device composed of Al(top)/TiO(2-x)/TiO2/Al(bottom) are demonstrated. The active component, the TiO2 layer of the device, is fabricated by atomic layer deposition. The oxygen vacancy TiO(2-x)/TiO2 layer annealed at 600 degrees C using rapid thermal annealing and it was proven to be in the rutile phase by X-ray diffraction analysis. The device exhibits nonvolatile memory behavior consistent with resistive switching properties, demonstrates an ON/OFF ratio of approximately 1,000:1, requires range of low voltage less than 0.4 V, and is still operational more than 120 times. PMID:27427707

  20. Morphology control studies of TiO2 microstructures via surfactant-assisted hydrothermal process for dye-sensitized solar cell applications

    NASA Astrophysics Data System (ADS)

    Lekphet, Woranan; Ke, Tsai-Chyuan; Su, Chaochin; Kathirvel, Sasipriya; Sireesha, Pedaballi; Akula, Suri Babu; Li, Wen-Ren

    2016-09-01

    The controlled morphological TiO2 particles have gained great importance in a wide variety of applications due to their promising physico-chemical properties. In this study, TiO2 microstructures with various shapes to utilize as scattering layer in dye-sensitized solar cell (DSSC) applications were successfully synthesized via different hydrothermal conditions. The effects of the versatile preparation parameters including the amount of titania precursor and surfactant, the addition of ethanol/water, and the hydrothermal process temperature and time on the TiO2 morphology were investigated. The structural and morphological analysis clearly shown that the preparation conditions played crucial roles in the morphology, particle size, and crystalline phase of the TiO2 microparticles. Different kinds of shapes such as rice- (∼1.10 μm (l) and ∼0.41 μm (w)), star- (∼3.60 μm) and flower-like (3.75 μm) TiO2 morphological structures were obtained. The morphology and size of the TiO2 particles were mainly governed by the concentrations of titanium tetraisopropoxide (TTIP) precursor, amounts of tetramethylammonium hydroxide (TMAH) surfactant and hydrothermal temperatures and durations. The as-prepared rice-shaped TiO2 was composed of mixed anatase and brookite binary phases, whereas the star- and flower-shaped TiO2 microstructures were consisted of ternary anatase, rutile, and brookite crystalline TiO2 phases. The three different rice-, star-, and flower-shaped TiO2 microstructures were employed as scattering layers for photoanodes in DSSCs. Among them, the star-like TiO2 photoanode based DSSC exhibited the highest power conversion efficiency of 9.56%, which was also better than those of the devices fabricated without scattering layer (a-TiO2, 8.38%) and with commercial P25 as scattering layer (a-TiO2/P25-TiO2, 8.52%) at the same film thickness of ∼14 μm.

  1. Photocatalytic Performance of a Nd-SiO2-TiO2 Nanocomposite for Degradation of Rhodamine B Dye Wastewater.

    PubMed

    Li, Jinlong; Liu, Tao; Sui, Guozhe; Zhen, Deshuai

    2015-02-01

    The photocatalytic performance of a novel Nd-SiO2-TiO2 nanocomposite catalyst prepared by a sol-gel method was examined in the degradation of Rhodamine B (RhB), a notorious organic compound present in dye wastewaters. The prepared samples were characterized by low-temperature N2 adsorption, X-ray diffraction (XRD), transmission electron microscopy (TEM) and UV-vis diffuse reflectance spectroscopy (DRS). Fourier-transform infrared (FT-IR) spectroscopic analysis indicated the enhanced chemical bonding of O--Ti and O--Ti--O with introduction of Nd and SiO2 dopant species into TiO2. The Nd-SiO2-TiO2 nanocomposite was found to exhibit a much higher photo- catalytic activity toward the decomposition of RhB under both UV and visible light irradiation as compared to a commercial TiO2 photocatalyst. The photodegradation efficiency of RhB (5 mg/L) was greater than 93% under visible light irradiation after 90 min. Addition of SiO2 was shown to not only inhibit crystal growth and TiO2 anatase-to-rutile phase transformation, but also enhance the adsorption of organic compounds. Nd doping has been suggested for slowing down the radiative recombination of photo-generated electrons and holes in TiO2, extending the photocatalyst light response to the visible region. The synergetic effects between Nd-SiO2 and TiO2 are described; the prepared Nd-SiO2-TiO2 represents a noteworthy contribution to the study of pollutant degradation in dye wastewaters.

  2. Three-dimensional ruthenium-doped TiO2 sea urchins for enhanced visible-light-responsive H2 production.

    PubMed

    Nguyen-Phan, Thuy-Duong; Luo, Si; Vovchok, Dimitriy; Llorca, Jordi; Sallis, Shawn; Kattel, Shyam; Xu, Wenqian; Piper, Louis F J; Polyansky, Dmitry E; Senanayake, Sanjaya D; Stacchiola, Dario J; Rodriguez, José A

    2016-06-21

    Three-dimensional (3D) monodispersed sea urchin-like Ru-doped rutile TiO2 hierarchical architectures composed of radially aligned, densely-packed TiO2 nanorods have been successfully synthesized via an acid-hydrothermal method at low temperature without the assistance of any structure-directing agent and post annealing treatment. The addition of a minuscule concentration of ruthenium dopants remarkably catalyzes the formation of the 3D urchin structure and drives the enhanced photocatalytic H2 production under visible light irradiation, not possible on undoped and bulk rutile TiO2. Increasing ruthenium doping dosage not only increases the surface area up to 166 m(2) g(-1) but also induces enhanced photoresponse in the regime of visible and near infrared light. The doping introduces defect impurity levels, i.e. oxygen vacancy and under-coordinated Ti(3+), significantly below the conduction band of TiO2, and ruthenium species act as electron donors/acceptors that accelerate the photogenerated hole and electron transfer and efficiently suppress the rapid charge recombination, therefore improving the visible-light-driven activity. PMID:27240884

  3. Effects of acid on the microstructures and properties of three-dimensional TiO2 hierarchical structures by solvothermal method

    NASA Astrophysics Data System (ADS)

    Zhou, Jing; Song, Bin; Zhao, Gaoling; Han, Gaorong

    2012-04-01

    Three-dimensional (3D) TiO2 hierarchical structures with various microstructures have been successfully synthesized via a surfactant-free and single-step solvothermal route, in which hydrochloric acid (HCl), nitric acid (HNO3), and acetic acid (HAc) are employed as the acid medium, respectively. The effects of acid medium on the microstructures and properties of 3D TiO2 hierarchical structure have been studied. The results indicate that 3D dandelion-like microspheres assembled of radial rutile nanorods are obtained in the sample prepared with HCl. Both the fraction of rutile and the diameter of nanorod enhance with the increasing HCl concentration. For the products derived from either HNO3 or HAc, 3D spheres composed of anatase nanoparticles are present. The 3D dandelion-like TiO2 hierarchical structures show low reflectance and efficient light harvesting since this ordered rod geometry offers a light-transfer path for incident light as well as multiple reflective and scattering effects. Moreover, 3D TiO2 with this unique topology shows superior photocatalytic activity despite low surface area, which can be ascribed to the enhanced light harvesting, fast electron transport, and low electron/hole recombination loss.

  4. Effects of acid on the microstructures and properties of three-dimensional TiO2 hierarchical structures by solvothermal method

    PubMed Central

    2012-01-01

    Three-dimensional (3D) TiO2 hierarchical structures with various microstructures have been successfully synthesized via a surfactant-free and single-step solvothermal route, in which hydrochloric acid (HCl), nitric acid (HNO3), and acetic acid (HAc) are employed as the acid medium, respectively. The effects of acid medium on the microstructures and properties of 3D TiO2 hierarchical structure have been studied. The results indicate that 3D dandelion-like microspheres assembled of radial rutile nanorods are obtained in the sample prepared with HCl. Both the fraction of rutile and the diameter of nanorod enhance with the increasing HCl concentration. For the products derived from either HNO3 or HAc, 3D spheres composed of anatase nanoparticles are present. The 3D dandelion-like TiO2 hierarchical structures show low reflectance and efficient light harvesting since this ordered rod geometry offers a light-transfer path for incident light as well as multiple reflective and scattering effects. Moreover, 3D TiO2 with this unique topology shows superior photocatalytic activity despite low surface area, which can be ascribed to the enhanced light harvesting, fast electron transport, and low electron/hole recombination loss. PMID:22500985

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

    NASA Astrophysics Data System (ADS)

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

    1999-03-01

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

  6. Degradation of Methyl Orange and Congo Red dyes by using TiO2 nanoparticles activated by the solar and the solar-like radiation.

    PubMed

    Ljubas, Davor; Smoljanić, Goran; Juretić, Hrvoje

    2015-09-15

    In this study we used TiO2 nanoparticles as semiconductor photocatalysts for the degradation of Methyl Orange (MO) and Congo Red (CR) dyes in an aqueous solution. Since TiO2 particles become photocatalytically active by UV radiation, two sources of UV-A radiation were used - natural solar radiation which contains 3-5% UV-A and artificial, solar-like radiation, created by using a lamp. The optimal doses of TiO2 of 500 mg/L for the CR and 1500 mg/L for the MO degradation were determined in experiments with the lamp and were also used in degradation experiments with natural solar light. The efficiency of each process was determined by measuring the absorbance at two visible wavelengths, 466 nm for MO and 498 nm for CR, and the total organic carbon (TOC), i.e. decolorization and mineralization, respectively. In both cases, considerable potential for the degradation of CR and MO was observed - total decolorization of the solution was achieved within 30-60 min, while the TOC removal was in the range 60-90%. CR and MO solutions irradiated without TiO2 nanoparticles showed no observable changes in either decolorization or mineralization. Three different commercially available TiO2 nanoparticles were used: pure-phase anatase, pure-phase rutile, and mixed-phase preparation named Degussa P25. In terms of degradation kinetics, P25 TiO2 exhibited a photocatalytic activity superior to that of pure-phase anatase or rutile. The electric energy consumption per gram of removed TOC was determined. For nearly the same degradation effect, the consumption in the natural solar radiation experiment was more than 60 times lower than in the artificial solar-like radiation experiment.

  7. Fingerprints of order and disorder in the electronic and optical properties of crystalline and amorphous TiO2

    NASA Astrophysics Data System (ADS)

    Landmann, M.; Köhler, T.; Köppen, S.; Rauls, E.; Frauenheim, T.; Schmidt, W. G.

    2012-08-01

    We have investigated the structural and electronic properties as well as the linear optical response of amorphous TiO2 within density functional theory and a numerically efficient density functional based tight-binding approach as well as many-body perturbation theory. The disordered TiO2 phase is modeled by molecular dynamics. The equivalence to experimentally characterized amorphous phases is demonstrated by atomic structure factors and radial pair-distribution functions. By density functional theory calculations, using both the semilocal Perdew-Burke-Ernzerhof functional and the nonlocal Heyd-Scuseria-Ernzerhof screened hybrid functional, the electronic energy gap is found to be larger than in the crystalline TiO2 phases rutile and brookite but close to the anatase band gap. The quasiparticle energy gap of amorphous TiO2 is determined to be ≳3.7 eV, while the optical gap is estimated to ≲3.5 eV. The disorder-induced formation of localized electronic states has been analyzed by the information entropy of the charge density distributions. The frequency-dependent optical constants, calculated from the complex dielectric function, have been determined in independent particle approximation. Besides similar absorption characteristics between the most common crystalline phases and amorphous TiO2, we find distinct differences in the optical spectra in the energy region between 5 eV and 8 eV. These differences can be assigned to the loss of symmetry in the local atomic structure of the disordered material. While the composition of the crystalline phases rutile, anatase, and brookite is well described by periodic arrangements of distorted TiO6 octahedra building blocks, the amorphous phase is characterized by partial loss of this octahedral coordination and the disorder-induced formation of under- and over-coordinated Ti ions. This leads to the absence of the characteristic crystal-field splitting of unoccupied Ti3d states into eg and t2g like subbands. The optical

  8. Photodegradation of Orange II by mesoporous TiO2.

    PubMed

    Kuang, Liyuan; Zhao, Yaping; Liu, Lu

    2011-09-01

    Mesoporous TiO(2) microspheres were prepared by a hydrothermal reaction and are characterized in this paper. Decoloration and mineralization during photodegradation of Orange II by mesoporous TiO(2) at different pH values, formation of sulfate, relative luminosity to luminous bacteria and recycling experiments of the catalyst were studied. The FTIR results further suggested that the novel mesoporous TiO(2) can not only decolor and mineralize dyes completely but also can be effectively reused several times. On the basis of the research, mesoporous TiO(2) would be a promising photocatalyst for practical use. PMID:21833403

  9. Mechanical treatment of TiO2 and ZrO2 oxide mixtures.

    PubMed

    Kraleva, Elka; Spojakina, Alla; Saladino, Maria Luisa; Caponetti, Eugenio; Jiratova, Kveta

    2010-12-01

    The mixed ZrO2-TiO2 system (5-50 wt% of ZrO2) has been studied to investigate the influence of the mechanical treatment on its physicochemical properties depending on the composition, time of milling (5, 10 and 20 min, r.p.m. 82) and temperature (400, 550 and 700 degrees C). Samples were characterized by Raman spectroscopy, X-ray powder diffraction, Scanning Electron Microscopy coupled with Energy Dispersion X-ray analyzer, High Resolution-Transmission Electron Microscopy and nitrogen adsorption porosimetry. Results show that srilankite (TiZrO4) phase has been produced. No influence of the milling time and temperature on the phase composition is observed. The presence of zirconia increases the thermal stability of anatase phase up to 700 degrees C hindering the anatase rutile phase transformation.

  10. Rheological and volumetric properties of TiO2-ethylene glycol nanofluids

    PubMed Central

    2013-01-01

    Homogeneous stable suspensions obtained by dispersing dry TiO2 nanoparticles in pure ethylene glycol were prepared and studied. Two types of nanocrystalline structure were analyzed, namely anatase and rutile phases, which have been characterized by scanning electron microscopy. The rheological behavior was determined for both nanofluids at nanoparticle mass concentrations up to 25%, including flow curves and frequency-dependent storage and loss moduli, using a cone-plate rotational rheometer. The effect of temperature over these flow curve tests at the highest concentration was also analyzed from 283.15 to 323.15 K. Furthermore, the influence of temperature, pressure, nanocrystalline structure, and concentration on the volumetric properties, including densities and isobaric thermal expansivities, were also analyzed. PMID:23763850

  11. Degradation and transformation of atrazine under catalyzed ozonation process with TiO2 as catalyst.

    PubMed

    Yang, Yixin; Cao, Hongbin; Peng, Pai; Bo, Hongmiao

    2014-08-30

    Degradation of atrazine by heterogeneously catalyzed ozonation was carried out with TiO2 in the form of rutile as the catalyst. Some experimental factors such as catalyst dose, ozone dose and initial concentration of atrazine were investigated for their influence on catalyzed ozonation process. Although atrazine was effectively removed from aqueous solution by catalyzed ozonation process, the mineralization degree only reached 56% at the experimental conditions. Five transformation products were identified by GC/MS analysis. The degradation of atrazine involved de-alkylation, de-chlorination and de-amination. Diaminotriazine and 5-azauracil were the de-chlorinated and de-aminated products, respectively. The evolution of concentration of transformation products during catalyzed ozonation process was compared with uncatalyzed ozonation to show the degradation pathway. Toxicity tests based on the inhibition of the luminescence emitted by Vibrio fisheri indicated the detoxification of atrazine by catalyzed ozonation. PMID:25106044

  12. Rheological and volumetric properties of TiO2-ethylene glycol nanofluids

    NASA Astrophysics Data System (ADS)

    Cabaleiro, David; Pastoriza-Gallego, María J.; Gracia-Fernández, Carlos; Piñeiro, Manuel M.; Lugo, Luis

    2013-06-01

    Homogeneous stable suspensions obtained by dispersing dry TiO2 nanoparticles in pure ethylene glycol were prepared and studied. Two types of nanocrystalline structure were analyzed, namely anatase and rutile phases, which have been characterized by scanning electron microscopy. The rheological behavior was determined for both nanofluids at nanoparticle mass concentrations up to 25%, including flow curves and frequency-dependent storage and loss moduli, using a cone-plate rotational rheometer. The effect of temperature over these flow curve tests at the highest concentration was also analyzed from 283.15 to 323.15 K. Furthermore, the influence of temperature, pressure, nanocrystalline structure, and concentration on the volumetric properties, including densities and isobaric thermal expansivities, were also analyzed.

  13. Frequency dependence and fuel effect on optical properties of nano TiO2-based structures

    NASA Astrophysics Data System (ADS)

    Ghasemifard, Mahdi; Ghamari, Misagh; Iziy, Meysam

    2016-06-01

    TiO2-(Ti0.5Si0.5)O2 nanopowders (TS-NPs) with average particle size around 90 nm were successfully synthesized by controlled auto-combustion method by using citric acid/nitric acid (AC:NA) and urea/metal cation (U:MC). The structure of powders was studied based on their X-ray diffraction (XRD) patterns. The XRD of TS-NPs shows that rutile and anatase are the main phases of TS-NPs for AC:NA and U:MC, respectively. Particle size and histogram of nanopowders were characterized by transmission electron microscopy (TEM) and dynamic light scattering (DLS). Optical properties of TS-NPs were calculated by Fourier transform infrared spectroscopy (FTIR) and Kramers-Kroning (KK) relation. Plasma frequencies of TS-NPs obtained from energy loss functions depend on fuels as a result of changes in crystal structure, particle size distribution, and morphology.

  14. Effect of aging on the properties of TiO2 nanoparticle

    NASA Astrophysics Data System (ADS)

    Jasbi, Nafise Ebrahim; Dorranian, Davoud

    2016-09-01

    Effect of aging on the properties of titanium dioxide nanoparticles produced by laser ablation process in water is investigated experimentally. The fundamental wavelength of a Q-switched Nd:YAG laser was employed to irradiate a high-purity Ti plate in distilled water at temperatures of 20, 35, 50 and 65 °C. Produced nanoparticles were diagnosed by UV-Vis-NIR spectroscopy, X-ray diffraction method, and dynamic light scattering device immediately after production and 1 week after. Bandgap energy of samples was extracted using Tauc method. Size of nanoparticles was increased after a week and their bandgap energy was decreased. Results show that the phase of TiO2 nanoparticles was transited from brookite to rutile after 1 week.

  15. Mechanical treatment of TiO2 and ZrO2 oxide mixtures.

    PubMed

    Kraleva, Elka; Spojakina, Alla; Saladino, Maria Luisa; Caponetti, Eugenio; Jiratova, Kveta

    2010-12-01

    The mixed ZrO2-TiO2 system (5-50 wt% of ZrO2) has been studied to investigate the influence of the mechanical treatment on its physicochemical properties depending on the composition, time of milling (5, 10 and 20 min, r.p.m. 82) and temperature (400, 550 and 700 degrees C). Samples were characterized by Raman spectroscopy, X-ray powder diffraction, Scanning Electron Microscopy coupled with Energy Dispersion X-ray analyzer, High Resolution-Transmission Electron Microscopy and nitrogen adsorption porosimetry. Results show that srilankite (TiZrO4) phase has been produced. No influence of the milling time and temperature on the phase composition is observed. The presence of zirconia increases the thermal stability of anatase phase up to 700 degrees C hindering the anatase rutile phase transformation. PMID:21121348

  16. Investigation of TiO2 nanoparticles translocation through a Caco-2 monolayer

    NASA Astrophysics Data System (ADS)

    Brun, E.; Jugan, M.-L.; Herlin-Boime, N.; Jaillard, D.; Fayard, B.; Flank, A.-M.; Mabondzo, A.; Carrière, M.

    2011-07-01

    Nanoparticles (NPs) are introduced in a growing number of commercial products, including food and beverage but their effects on gastrointestinal tract are poorly investigated. Here we focused on the translocation of TiO2 NPs through Caco-2 monolayers exposed to anatase and rutile NPs up to 24 h. Internalization was followed by transmission electronic microscopy and μ-XRF elemental mapping, coupled to XAS analysis of Ti atoms environment. This innovative technique is among the best techniques to get insights on NP fate after internalization. The originality of this project relies on the panel of microscopy techniques implemented to investigate digestive barrier translocation, bringing together biologists, chemists and physicists in a pluridisciplinary research program.

  17. The effect of calcination temperature on the crystallinity of TiO 2 nanopowders

    NASA Astrophysics Data System (ADS)

    Chen, Yung-Fang; Lee, Chi-Young; Yeng, Ming-Yu; Chiu, Hsin-Tien

    2003-01-01

    TiO 2 nanopowders have been prepared using 0.1 M titanium tetraisopropoxide (TTIP) in varied pH aqueous solution containing TMC and NP-204 surfactants. Only the powder acquired from a solution of pH=2 has a regular particle size distribution. Anatase phase powders are obtained by calcination in nitrogen in the 250-500°C temperature range. When calcined at 400°C, the diameter of the nanoparticles is approximately 10 nm with a specific surface area of 106.9 m 2/g. As the calcination temperature is increased, the particle size increases. Rutile phase powders are formed at calcination temperatures above 600°C.

  18. Origin of magnetism and quasiparticles properties in Cr-doped TiO2.

    PubMed

    Da Pieve, F; Di Matteo, S; Rangel, T; Giantomassi, M; Lamoen, D; Rignanese, G-M; Gonze, X

    2013-03-29

    Combining the local spin density approximation (LSDA)+U and an analysis of superexchange interactions beyond density functional theory, we describe the magnetic ground state of Cr-doped TiO2, an intensively studied and debated dilute magnetic oxide. In parallel, we correct our LSDA+U (+ superexchange) ground state through GW corrections (GW@LSDA+U) that reproduce the position of the impurity states and the band gaps in satisfying agreement with experiments. Because of the different topological coordinations of Cr-Cr bonds in the ground states of rutile and anatase, superexchange interactions induce either ferromagnetic or antiferromagnetic couplings of Cr ions. In Cr-doped anatase, this interaction leads to a new mechanism which stabilizes a (nonrobust) ferromagnetic ground state, in keeping with experimental evidence, without the need to invoke F-center exchange. The interplay between structural defects and vacancies in contributing to the superexchange is also unveiled.

  19. Degradation and transformation of atrazine under catalyzed ozonation process with TiO2 as catalyst.

    PubMed

    Yang, Yixin; Cao, Hongbin; Peng, Pai; Bo, Hongmiao

    2014-08-30

    Degradation of atrazine by heterogeneously catalyzed ozonation was carried out with TiO2 in the form of rutile as the catalyst. Some experimental factors such as catalyst dose, ozone dose and initial concentration of atrazine were investigated for their influence on catalyzed ozonation process. Although atrazine was effectively removed from aqueous solution by catalyzed ozonation process, the mineralization degree only reached 56% at the experimental conditions. Five transformation products were identified by GC/MS analysis. The degradation of atrazine involved de-alkylation, de-chlorination and de-amination. Diaminotriazine and 5-azauracil were the de-chlorinated and de-aminated products, respectively. The evolution of concentration of transformation products during catalyzed ozonation process was compared with uncatalyzed ozonation to show the degradation pathway. Toxicity tests based on the inhibition of the luminescence emitted by Vibrio fisheri indicated the detoxification of atrazine by catalyzed ozonation.

  20. Laser-assisted production of spherical TiO2 nanoparticles in water.

    PubMed

    Boutinguiza, M; Rodríguez-González, B; del Val, J; Comesaña, R; Lusquiños, F; Pou, J

    2011-05-13

    TiO(2) nanoparticles with controllable average diameter have been obtained by laser ablation in water. A monomode ytterbium doped fiber laser (YDFL) was used to ablate a metallic titanium target placed in deionized water. The resulting colloidal solutions were subjected to laser radiation to study the resizing effect. The crystalline phases, morphology and optical properties of the obtained nanoparticles were characterized by means of transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), x-ray energy dispersive spectroscopy (EDS) and UV-vis absorption spectroscopy. The colloidal suspensions produced consisting of titanium dioxide crystalline nanoparticles show almost perfect spherical shape with diameters ranging from 3 to 40 nm. The nanoparticles are polycrystalline and exhibit anatase as well as rutile phases. PMID:21430320