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Sample records for single-crystalline rutile tio2

  1. Transport properties in single-crystalline rutile TiO2 nanorods

    NASA Astrophysics Data System (ADS)

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

    2011-11-01

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

  2. Mössbauer study of the magnetic phase composition of single-crystalline rutile (TiO2) implanted with iron ions

    NASA Astrophysics Data System (ADS)

    Dulov, E. N.; Ivoilov, N. G.; Khripunov, D. M.; Tagirov, L. R.; Khaibullin, R. I.; Valeev, V. F.; Nuzhdin, V. I.

    2009-06-01

    Depth-resolved Mössbauer measurements have been performed for four ferromagnetic samples obtained by the implantation of iron ions (enriched to ˜ 50% with 57Fe isotope) into single-crystalline rutile (TiO2) substrates with two crystallographic orientations [(100) and (001)] at different temperatures (300 and 900 K). It is established that the ferromagnetic properties of iron-implanted rutile samples at room temperature are determined by the presence of α-Fe and Fe3O4 phases. The phase composition of samples obtained by iron implantation into substrates heated to 900 K depends on the crystallographic orientation of the substrate, which is explained by a significant anisotropy of the diffusion of iron atoms in rutile.

  3. Achievement of 6.03% conversion efficiency of dye-sensitized solar cells with single-crystalline rutile TiO2 nanorod photoanode

    NASA Astrophysics Data System (ADS)

    Yang, Weiguang; Wan, Farong; Wang, Yali; Jiang, Chunhua

    2009-09-01

    The rutile TiO2 nanorods (RTNs) with the length of 40-130 nm and diameters approximately 8-15 nm, containing some 300-500 nm sized RTN aggregates and 6% of anatase TiO2 nanocrystals, were prepared by surfactant-assisted hydrothermal method. The dye-sensitized solar cell (DSC) based on the RTNs exhibited power conversion efficiency of 6.03%. As compared to P25 TiO2 based DSC, RTNs based DSC shows improved light-harvesting and Brunauer-Emmett-Teller surface area, leading to an increase in short-circuit current (Jsc) by 40.6%.

  4. 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%.

  5. Bifunctional single-crystalline rutile nanorod decorated heterostructural photoanodes for efficient dye-sensitized solar cells.

    PubMed

    Hao, Feng; Lin, Hong; Zhou, Chen; Liu, Yizhu; Li, Jianbao

    2011-09-21

    A novel heterostructural TiO(2) nanocomposite, which consists of single-crystalline rutile TiO(2) nanorod decorated Degussa P25 nanoparticles, has been fabricated through a facile acidic hydrothermal method and successfully applied as the photoanodes for efficient dye-sensitized solar cells. The morphology, crystal structure, specific surface area and pore size distribution of the obtained nanocomposite were systematically investigated by X-ray diffraction (XRD), field-emission scanning electron microscope (FESEM), high resolution transmission electron microscope (HRTEM), selected-area electron diffraction patterns (SAED) and nitrogen adsorption-desorption measurements. Under standard illumination conditions (AM 1.5, 100 mW cm(-2)), devices with these hybrid anodes exhibited considerably enhanced photocurrent density and overall conversion efficiency in comparison with that of the commercial Degussa P25 electrodes, which can be partially attributed to the light scattering effect in the long-wavelength region as evidenced from the incident photon-to-current conversion efficiency (IPCE) response and the diffuse reflectance spectroscopy. More importantly, devices employing these hybrid anodes have demonstrated extended electron lifetimes and larger electron diffusion coefficient as validated by the intensity-modulated photocurrent/photovoltage spectroscopy measurements, which can be mainly ascribed to the fast electron transport and collection superiority of the single-crystalline nanorods.

  6. 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.

  7. Ultrahigh efficient single-crystalline TiO2 nanorod photoconductors

    NASA Astrophysics Data System (ADS)

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

    2012-03-01

    Photoconductive gain and normalized gain, which determine the device and material properties on photoconduction, respectively, have been defined for single-crystalline titanium dioxide (TiO2) nanorods (NRs) with various diameter sizes. The gain values of the NR photodetectors can reach 105 easily at a low bias of 0.1 V. By excluding the contributions of experimental parameters, the optimal normalized gain of the indirect-bandgap TiO2 NRs at 5.4 × 10-5 m2V-1 is comparable with that estimated from the direct-bandgap ZnO nanowires. The average normalized gain value at 3.3 ± 2.2 × 10-5 m2V-1 obtained from eight individual TiO2 NRs with diameters ranging from 120 to 1250 nm is also over three orders of magnitude higher than the polycrystalline nanotube counterpart. The results demonstrate the superior photoconductivity efficiency in boundary-free titania one-dimensional nanostructure, which is crucial for ultraviolet photodetector, dye-sensitized solar cell, and photochemical device applications.

  8. Growth Morphologies of Nanostructured Rutile TiO2

    NASA Astrophysics Data System (ADS)

    Huang, Yuan-Sheng; Liu, Hong-Wei

    2014-04-01

    The morphological and structural characteristics of nanostructure rutile TiO2 were investigated by using x-ray diffraction, scanning electron microscopy, electron diffraction, conventional and high resolution transmission electron microscopy. As a product of the precursor template of hydrogen titanate nanofibers, rutile could exhibit forms like tree, sheaf, or bundle. Both the branch and trunk of tree-like rutile have the same growth axis of [001]. The sheaf-like rutile forms while it grows along both [001] and [] directions. The bundle-like rutile grows along only one [001] direction. Tree-like morphology of nanocrystals rutile is revealed to be controlled by (101) twin structure. Twin formation is a possible mechanism to decrease the density of defects and reduce the system energy as the crystal grows.

  9. Effect of strontium ions on the early formation of biomimetic apatite on single crystalline rutile

    NASA Astrophysics Data System (ADS)

    Lindahl, Carl; Engqvist, Håkan; Xia, Wei

    2013-02-01

    Single crystalline rutile is a good model to investigate the growth mechanism of hydroxyapatite on bioactive Ti surfaces. Previous studies have shown the difference on different crystalline rutile faces in the early stage and during the growth of HAp crystals from simulated body fluids. It is known that the biological apatite crystal is an ion-substituted apatite. Ion substitution will influence the HAp crystal growth and morphology. In the present study, the effect of strontium ions on the adsorption of Ca and phosphate ions on three different faces of single crystalline rutile substrates has been investigated. The ion adsorption is the crucial step in the nucleation of HAp crystals on specific surfaces. Single crystalline rutile surfaces ((1 1 0), (1 0 0) and (0 0 1)) were soaked in phosphate buffer solutions containing calcium and strontium ions for different time periods. The results showed that the adsorption of Sr, Ca and P is faster on the (1 1 0) surface than on the (1 0 0) and (0 0 1) surfaces. Almost same amount of Sr ion was adsorbed on the surfaces compared to the adsorption of Ca ion. Strontium ion influenced the biological apatite formation in the early stage in this study.

  10. Band alignment of rutile and anatase TiO2

    NASA Astrophysics Data System (ADS)

    Scanlon, David O.; Dunnill, Charles W.; Buckeridge, John; Shevlin, Stephen A.; Logsdail, Andrew J.; Woodley, Scott M.; Catlow, C. Richard A.; Powell, Michael. J.; Palgrave, Robert G.; Parkin, Ivan P.; Watson, Graeme W.; Keal, Thomas W.; Sherwood, Paul; Walsh, Aron; Sokol, Alexey A.

    2013-09-01

    The most widely used oxide for photocatalytic applications owing to its low cost and high activity is TiO2. The discovery of the photolysis of water on the surface of TiO2 in 1972 launched four decades of intensive research into the underlying chemical and physical processes involved. Despite much collected evidence, a thoroughly convincing explanation of why mixed-phase samples of anatase and rutile outperform the individual polymorphs has remained elusive. One long-standing controversy is the energetic alignment of the band edges of the rutile and anatase polymorphs of TiO2 (ref. ). We demonstrate, through a combination of state-of-the-art materials simulation techniques and X-ray photoemission experiments, that a type-II, staggered, band alignment of ~ 0.4 eV exists between anatase and rutile with anatase possessing the higher electron affinity, or work function. Our results help to explain the robust separation of photoexcited charge carriers between the two phases and highlight a route to improved photocatalysts.

  11. 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

  12. Morphology and interfacial energetics controls for hierarchical anatase/rutile TiO2 nanostructured array for efficient photoelectrochemical water splitting.

    PubMed

    Yang, Jih-Sheng; Liao, Wen-Pin; Wu, Jih-Jen

    2013-08-14

    In this work, a three-dimensional (3D) hierarchical TiO2 nanostructured array is constructed on the basis of the considerations of morphology and interfacial energetics for photoelectrochemical water splitting. The photoelectrode is composed of a core-shell structure where the core portion is a rutile TiO2 nanodendrite (ND) array and the shell portion is rutile and anatase TiO2 nanoparticles (NPs) sequentially located on the surface. The TiO2 ND array provides a fast electron transport pathway due to its quasi-single-crystalline structure. The 3D configuration with NPs in the shell portion provides a larger surface area for more efficient photocharge separation without significantly sacrificing the electron collection efficiency. Moreover, anatase TiO2 NPs constructed on the surface of the ND/rutile TiO2 NP nanostructured array enhance charge separation and suppress charge recombination at the interfacial region due to the higher conduction band edge of anatase TiO2 compared to that of rutile TiO2. A photocurrent density and photoconversion efficiency of 2.08 mA cm(-2) at 1.23 V vs reversible hydrogen electrode (RHE) and 1.13% at 0.51 V vs RHE are, respectively, attained using the hierarchical TiO2 nanostructured array photoelectrochemical cell under illumination of AM 1.5G (100 mW cm(-2)).

  13. Infrared dielectric anisotropy and phonon modes of rutile TiO2

    NASA Astrophysics Data System (ADS)

    Schöche, S.; Hofmann, T.; Korlacki, R.; Tiwald, T. E.; Schubert, M.

    2013-04-01

    Spectroscopic ellipsometry in the mid-infrared and far-infrared spectral range and generalized ellipsometry in the mid-infrared spectral range are used to investigate the anisotropic dielectric response of rutile TiO2. The ordinary and extraordinary dielectric function tensor components and all infrared active phonon mode parameters of single crystalline rutile TiO2 are determined with high accuracy for wavelengths from 3 μm to 83 μm. The data were acquired from samples of (001), (100), and (111) surfaces cut from bulk single crystals. A factorized model dielectric function is employed in order to determine the frequencies and damping parameters of the transverse and longitudinal phonon modes with A2u and Eu symmetries. The bands of total reflection of s- and p-polarized light in dependence of the angle of incidence for highly symmetric sample cuts and orientations are derived. Excellent agreement with phonon modes reported in literature is obtained. Introduction of two additional modes for ordinary as well as extraordinary component of the dielectric function tensor was necessary to most accurately match the experimental data. The spectral position of the additional modes is compared to the calculated phonon density of states. The low-frequency dielectric constants are calculated from the determined phonon mode parameters and the high-frequency dielectric constants by applying the Lyddanne-Sachs-Teller relation. The presented data revise existing infrared optical function data and will be suitable for interpretation of any kind of infrared spectra for bulk TiO2 single crystal substrates, thin films, and TiO2 nanostructures.

  14. CdS/CdSe cosensitized oriented single-crystalline TiO2 nanowire array for solar cell application

    NASA Astrophysics Data System (ADS)

    Li, Ming; Liu, Yong; Wang, Hai; Shen, Hui; Zhao, Wenxia; Huang, Hong; Liang, Chaolun

    2010-11-01

    Vertically oriented single-crystalline TiO2 nanowires array was grown on transparent conductive oxide glass substrate, and then CdS and CdSe quantum dots (QDs) were deposited on nanowires to form a TiO2/CdS/CdSe core-shell structure films. The optical properties of films with different layers of QDs were compared. The QD sensitized solar cells (QD-SSCs) were assembled and the effect of coating cycles of QDs on the photovoltaic performance was investigated. Under optimum parameters, QD-SSCs assembled with 5 μm thick TiO2 nanowires film exhibited a short-circuit current density of 7.92 mA cm-2, an open-circuit voltage of 0.40 V, and a power conversion efficiency of 1.14%.

  15. Dielectric and Infrared Properties of TiO2 Films Containing Anatase and Rutile

    DTIC Science & Technology

    2005-07-18

    properties of TiO2 films containing anatase and rutile 2. Experimental details Thin films of TiO2 were deposited onto Si(1 0 0) wafers...annealed) and 7.4 nm (225 nm, deposited with a bias 872 Dielectric and infrared properties of TiO2 films containing anatase and rutile then annealed...Article POSTPRINT 3. DATES COVERED (From - To) 2001 - 2004 4. TITLE AND SUBTITLE Dielectric and infrared properties of TiO2 films

  16. 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

  17. TiO2 single-crystalline nanorod electrode for quasi-solid-state dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Song, Mi Yeon; Ahn, Young Rack; Jo, Seong Mu; Kim, Dong Young; Ahn, Jae-Pyoung

    2005-09-01

    TiO2 single-crystalline nanorods are prepared from electrospun fibers which are composed of nanofibrils with an islands-in-a-sea morphology. The mechanical pressure produces each fibril into nanorods which are converted to anatase single crystals after calcination. High-resolution transmission electron microscopy shows that the (001) plane is growing along the longitudinal direction of the rod. In this work, the nanorod electrode provides the efficient photocurrent generation in a quasi-solid-state dye-sensitized solar cell using highly viscous poly(vinylidenefluoride-co-hexafluoropropylene)-based gel electrolytes. The overall conversion efficiency of the TiO2 nanorods shows 6.2% under 100mW /cm2 (AM 1.5G) illumination.

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

    NASA Astrophysics Data System (ADS)

    Yamada, Yasuhiro; Kanemitsu, Yoshihiko

    2012-09-01

    The dynamical behavior of photoexcited states of TiO2 governs the activities of TiO2-based solar cells and photocatalysts. We determined the lifetimes of photoexcited electrons and holes in rutile and anatase TiO2 single crystals by combining advantages of time-resolved photoluminescence, photoconductance, and transient absorption spectroscopy. Electrons and holes in rutile show exponential decays with the lifetime of a few tens of nanoseconds, while non-exponential decays are observed in anatase, indicating the presence of multiple carrier trapping processes. We revealed the generic features of the carrier recombination processes in rutile and anatase TiO2.

  19. Surface structures of rutile TiO2(114)

    NASA Astrophysics Data System (ADS)

    Kubo, Toshitaka; Orita, Hideo; Nozoye, Hisakazu

    2016-11-01

    The surface structures of rutile TiO2(114) have been studied using a combination of scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. Depending on the sample preparation, the surface exhibits many complicated local nanostructures, e.g., dot-like, missing row, row-like (1 × 3), and twin dotted (2 × 2) structures. After several cycles of sputtering and high-temperature annealing, all samples exhibit triangular pyramidal structure. Microfaceted structural models, which are composed of combinations of {111} and (001) microfacets, can explain all experimental results as well as the structural variety. The calculated STM images are in good agreement with the experimental results. The decreasing density of dangling bonds, the increasing coordination number, and the evolution of non-polar structures stabilize the surface energy, which results in the microfaceted reconstructions. The formation of various nanostructures and the surface stoichiometric changes are discussed.

  20. 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.

  1. TiO2-Based Nanomaterials for Gas Sensing-Influence of Anatase and Rutile Contributions.

    PubMed

    Zakrzewska, K; Radecka, M

    2017-12-01

    The paper deals with application of three nanomaterial systems: undoped TiO2, chromium-doped TiO2:Cr and TiO2-SnO2 synthesized by flame spray synthesis (FSS) technique for hydrogen sensing. The emphasis is put on the role of anatase and rutile polymorphic forms of TiO2 in enhancing sensitivity towards reducing gases. Anatase-to-rutile transformation is achieved by annealing of undoped TiO2 in air at 700 °C, specific Cr doping and modification with SnO2. Undoped TiO2 and TiO2-SnO2 exhibit n-type behaviour and while TiO2: 5 at.% Cr is a p-type semiconductor. X-ray diffraction (XRD) has been applied to determine anatase-to-rutile weight ratio as well as anatase and rutile crystal size. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) have been used to characterize the structure and morphological parameters. Optical reflectometry enabled to find and compare the band gaps E g of anatase and rutile predominated compositions. Electrical properties, i.e. the electrical conductivity and values of constant phase element (CPE), have been established on the basis of impedance spectroscopy. Dynamic responses of the electrical resistance as a function of hydrogen concentration revealed that predominance of rutile in anatase/rutile mixture is beneficial for gas sensing. Partial transformation to rutile in all three material systems under study resulted in an increased sensitivity towards hydrogen. It is proposed that this effect can be explained in a similar way as in photocatalysis, i.e. by specific band alignment and electron transfer from rutile to anatase to facilitate oxygen preadsorption on the surface of anatase grains.

  2. Preparation and photoactivity of nanostructured anatase, rutile and brookite TiO2 thin films.

    PubMed

    Addamo, Maurizio; Bellardita, Marianna; Di Paola, Agatino; Palmisano, Leonardo

    2006-12-21

    Photoactive films consisting of pure anatase, brookite or rutile TiO2 were prepared by dip coating from water dispersions obtained by using TiCl4 as the precursor under similar mild experimental conditions.

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

    PubMed

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

    2016-06-01

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

  4. Formation of nanostructured rutile TiO2 synthesized on Ti powder via thermal oxidation

    NASA Astrophysics Data System (ADS)

    Byun, Jong Min; Choi, Hye Rim; Kim, Se Hoon; Suk, Myung-Jin; Kim, Young Do

    2017-09-01

    The nanostructured rutile TiO2 that have large specific surface area was formed on Ti powder through thermal oxidation. Thermal oxidation of Ti powder by using an external oxygen source was shown to be a simple and facile method to synthesize nanostructured rutile TiO2. Raw Ti powder was etched by using 30% HCl solution to control the surface morphology of Ti and to increase the surface area for effective diffusion of oxygen source. Then, etched powders were thermally oxidized at 750 and 850 °C with ethanol as the oxygen source. Coral-like nanostructured rutile TiO2 of size 500 nm was formed at 850 °C from Ti powder etched for more than 20 min. The specific surface area of the resulting powder, which consisted of intermediate oxide (Ti2O) cores covered with nanostructured rutile TiO2, was 48 times that of the raw Ti powder.

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

    PubMed

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

    2016-05-18

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

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

    Treesearch

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

    2015-01-01

    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...

  7. 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.

  8. 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

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

    PubMed

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

    2014-10-08

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

  10. Low Temperature Synthesis of Rutile TiO2 Nanocrystals and Their Photovoltaic and Photocatalytic Properties.

    PubMed

    Roy, Subhasis; Han, Gill Sang; Shin, Hyunjung; Lee, Jin Wook; Mun, Jinsoo; Shin, Hyunho; Jung, Hyun Suk

    2015-06-01

    We report a novel method of synthesizing rutile TiO2 nanocrystals at low temperature (200 degrees C) via a butanol rinsing process followed by heat treatment in an O2 atmosphere. The rutile nanocrystals show uniform size distribution of approximately 20 nm and good crystallinity confirmed by X-ray diffraction and transmission electron microscopy. A mechanism for the low temperature synthesis of rutile nanocrystals is rationalized in terms of an explosive thermal decomposition reaction of butoxy groups on TiO2 powders with O2 gas. Characterizations of the photovoltaic and photocatalytic properties of rutile nanocrystals exhibited higher photoactivity than large-sized conventional rutile powder, which demonstrates that this novel synthesis technology could expand applications of rutile powders to various photoactive devices beyond solar cells and photocatalysts.

  11. Synthesis of Rutile TiO2 from Panzhihua Sulfate Titanium Slag by Microwave Heating

    NASA Astrophysics Data System (ADS)

    Chen, Hufei; Chen, Guo; Wu, Yunqi; Peng, Jinhui; Srinivasakannan, C.; Chen, Jin

    2017-08-01

    This study aimed to assess the utilization of microwave heating for synthesis of rutile TiO2 by employing sulfate titanium slag produced by Panzhihua Iron and Steel Research Institute. To this end, the properties of sulfate titanium slag before and after microwave treatment, i.e., its crystal structure, surface microstructure, and surface chemical functional groups, were characterized by x-ray diffraction (XRD), scanning electron microscopy (SEM), and Fourier transformation infrared (FT-IR) spectroscopy, respectively. Results of XRD analysis showed that the anosovite phase of the sulfate titanium slag transformed to the rutile TiO2 phase under microwave heating at 1100°C for duration of 120 min. Correspondingly, the SEM images revealed that the surface of the sulfate titanium slag grew as a granular substance after microwave roasting. The granular substance was observed to be rutile TiO2 with a rod-shaped structure. FT-IR spectra demonstrated the occurrence of a blue shift at 472.15 cm-1, indicating phase transformation from anosovite to rutile TiO2 because of the roasting process. From the experimental results, it is concluded that microwave heating can be an effective and efficient approach for the synthesis of synthetic rutile TiO2 from sulfate titanium slag.

  12. Ti(3+) Self-Doped Blue TiO2(B) Single-Crystalline Nanorods for Efficient Solar-Driven Photocatalytic Performance.

    PubMed

    Zhang, Yan; Xing, Zipeng; Liu, Xuefeng; Li, Zhenzi; Wu, Xiaoyan; Jiang, Jiaojiao; Li, Meng; Zhu, Qi; Zhou, Wei

    2016-10-12

    Ti(3+) self-doped blue TiO2(B) single-crystalline nanorods (b-TR) are fabricated via a simple sol-gelation method, cooperated with hydro-thermal treatment and subsequent in situ treatment method, and afterward annealed at 350 °C in Ar. The structures are characterized by X-ray diffraction (XRD), Raman, X-ray photoelectron spectroscopy (XPS), diffuse reflectance spectroscopy (UV-vis), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The prepared b-TR with narrow band gap possesses single-crystalline TiO2(B) phase, Ti(3+) self-doping, and one-dimensional (1D) rodlike nanostructure. In addition, the improved photocatalytic performance is studied by decomposition of Rhodamine B (RhB) and hydrogen evolution. The degradation rate of RhB by Ti(3+) self-doped blue TiO2(B) single-crystalline nanorods is ∼6.9- and 2.1-times higher compared with the rates of titanium dioxide nanoparticles and pristine TiO2(B) nanorods under visible light illumination, respectively. The hydrogen evolution rate of b-TR is 26.6 times higher compared with that of titanium dioxide nanoparticles under AM 1.5 irradiation. The enhanced photocatalytic performances arise from the synergetic action of the special TiO2(B) phase, Ti(3+) self-doping, and the 1D rod-shaped single-crystalline nanostructure, favoring the visible light utilization and the separation and transportation of photogenerated charge carriers.

  13. Rutile TiO2 nanowire-based perovskite solar cells.

    PubMed

    Jiang, Qinglong; Sheng, Xia; Li, Yingxuan; Feng, Xinjian; Xu, Tao

    2014-12-07

    Different lengths of rutile TiO2 nanowires (NW) with wide-open space for effective material filling were used as photoanodes for perovskite solar cells. Cells with 900 nm nanowires as photoanodes exhibit a current density of 22 mA cm(-2) and an efficiency of 11.7%, outperforming the reported TiO2 nanowire-based perovskite solar cells.

  14. Preparation and Characterization of Rutile-Type TiO2 Doped with Cu

    NASA Astrophysics Data System (ADS)

    Tryba, B.; Orlikowski, J.; Wróbel, R. J.; Przepiórski, J.; Morawski, A. W.

    2015-03-01

    Visible-light active photocatalysts were prepared by doping Cu-TiO2 through the sol-gel method. The influence of the preparation conditions such as pH of sol-gel solution and calcination temperature on the properties of TiO2-Cu was investigated. The presence of Cu caused reduction of band-gap energy, which was more visible in the rutile-type TiO2. Low pH of sol-gel solution such as pH 1.5 favorized formation of rutile during calcination and caused slower growth of the crystallites with increasing temperature of calcination in comparison with sol-gel prepared at pH 3. XPS measurements showed that Cu was placed mostly on the surface of TiO2. For sample calcined at 600 °C, the surface concentration of copper was 1.1 wt.%. The presence of both, rutile phase and Cu, increased adsorption of phenol and facilitated its photocatalytic decomposition. Moreover, reduced band-gap energy in rutile-type TiO2-Cu photocatalyst enabled phenol decomposition under visible light.

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

    DOE PAGES

    Wang, Yang; Lee, Shinbuhm; Vilmercati, P.; ...

    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

  16. 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.

  17. Effects of Li intercalation on magnetic properties of Co-doped rutile TiO2

    NASA Astrophysics Data System (ADS)

    Park, Min Sik; Min, B. I.

    2004-12-01

    We have investigated the electronic structures and magnetic properties of Li-intercalated Co-doped rutile TiO2. For non-intercalated Ti0.9375Co0.0625O2, the half-metallic and low-spin ({\\sim }0.94~\\mu_{\\mathrm {B}}/{\\mathrm {Co}} ) ground state is obtained. By Li intercalation, Ti0.9375Co0.0625O2 becomes a paramagnetic insulator at the concentration of Li/Ti = 0.067. At the higher concentration of Li/Ti = 0.133, it becomes a paramagnetic metal. Hence, as in the transition metal doped anatase TiO2 case, we expect that the magnetic and transport properties of Co-doped rutile TiO2 can be controlled by an electric field.

  18. Photoemission Electron Microscopy of TiO2 Anatase Films Embedded with Rutile Nanocrystals

    SciTech Connect

    Xiong, Gang; Shao, Rui; Droubay, Timothy C.; Joly, Alan G.; Beck, Kenneth M.; Chambers, Scott A.; Hess, Wayne P.

    2007-09-03

    Photoemission electron microscopy (PEEM) excited by x-ray and UV sources is used to investigate epitaxial anatase thin films embedded with rutile nanocrystals, a model system for the study of heterocatalysis on mixed-phase TiO2. Both excitation sources show distinct contrast between the two TiO2 phases, however, the contrast is reversed. Rutile nanocrystals appear darker than the anatase film in X-ray PEEM images but brighter in UV-PEEM images. Topography-induced contrast is dominant X-ray PEEM imaging, whereas work function contrast, dominates for UV-PEEM. Work function contrast results from the differences in work function and surface defect state densities between the two phases near the Fermi level. This assertion is confirmed by UPS data that shows the rutile work function to be 0.2 eV lower and a greater occupied valence band density-of-states in rutile (100) than in anatase (001). Since the boundaries between rutile nanocrystals and the anatase film are clearly resolved, these results indicate that PEEM studies of excited state dynamics and heterocatalysis are possible at chemically intriguing mixed-phase TiO2 interfaces and grain boundaries.

  19. The synthesis of rutile nano-structured TiO2 composite under low temperature

    NASA Astrophysics Data System (ADS)

    Zhang, Lei; Zheng, Yibo; Dong, Mofei; Li, Simian

    2012-11-01

    In this paper, in order to improve the photocatalytic application of TiO2, the low-density material such as Ps and TiCl4 is proposed to be the raw carrier, and the nana-structured TiO2 composite is obtained by combining the sol-gel technology and layer-by-layer self-assembly methods; The pure rutile nano-structured TiO2 whose diameter is about 0.25mm are prepared under different conditions at low temperature. By being calcined under 450 ℃ the hollow sphere TiO2 is prepared and its composition, size, structure analysis and characterization are studied by using X ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and thermal gravimetric analysis (DSC-TG) respectively.

  20. Dense and high-hydrophobic rutile TiO2 nanorod arrays

    NASA Astrophysics Data System (ADS)

    Peng, X.; Chen, A.

    2005-02-01

    Dense and well-oriented rutile TiO2 nanorod arrays were synthesized on a titanium substrate using the organic compound dibutyltin dilaurate as the oxygen source in the oxidation of Ti at 850 °C. The influence of temperature on the nanostructured TiO2 formation and the effect of the TiO2 structures on their wettability were also investigated. Polycrystalline TiO2 grains were formed at 800 °C; in contrast, TiO2 micro-whiskers were grown on the Ti substrate at 900 °C. The measurement of the water contact angle shows that the wetting property of the TiO2 films strongly depends on their surface structure. The surface of the dense well-oriented nanorod arrays is highly hydrophobic with a water contact angle of 130 °C. This study has demonstrated that the direct oxidation of Ti substrate using an organic oxygen source is a promising method for fabrication of large scale, uniform and well-aligned TiO2 nanorod arrays on titanium substrates.

  1. New understanding of the difference of photocatalytic activity among anatase, rutile and brookite TiO2.

    PubMed

    Zhang, Jinfeng; Zhou, Peng; Liu, Jianjun; Yu, Jiaguo

    2014-10-14

    In general, anatase TiO2 exhibits higher photocatalytic activities than rutile TiO2. However, the reasons for the differences in photocatalytic activity between anatase and rutile are still being debated. In this work, the band structure, density of states, and effective mass of photogenerated charge carriers for anatase, rutile and brookite TiO2 are investigated by the first-principle density functional theory calculation. The results indicate that anatase appears to be an indirect band gap semiconductor, while rutile and brookite belong to the direct band gap semiconductor category. Indirect band gap anatase exhibits a longer lifetime of photoexcited electrons and holes than direct band gap rutile and brookite because the direct transitions of photogenerated electrons from the conduction band (CB) to valence band (VB) of anatase TiO2 is impossible. Furthermore, anatase has the lightest average effective mass of photogenerated electrons and holes as compared to rutile and brookite. The lightest effective mass suggests the fastest migration of photogenerated electrons and holes from the interior to surface of anatase TiO2 particle, thus resulting in the lowest recombination rate of photogenerated charge carriers within anatase TiO2. Therefore, it is not surprising that anatase usually shows a higher photocatalytic activity than rutile and brookite. This investigation will provide some new insight into understanding the difference of photocatalytic activity among anatase, rutile and brookite.

  2. 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.

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

    SciTech Connect

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

    2007-03-15

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

  4. Mechanism of Li+/electron conductivity in rutile and anatase TiO2 nanoparticles

    SciTech Connect

    Sushko, Maria L.; Rosso, Kevin M.; Liu, Jun

    2010-11-08

    Concurrent Li-ion and electron conductivity in rutile and anatase TiO2 nanoparticles was studied using multiscale simulations. We show that charge transport in titania nanoparticles is determined by the competition of charge redistribution towards the particle boundaries and constant Li+ and electron fluxes. In nanoparticles smaller than the Debye length the constant flux prevails and the conductivity has a dual ionic and electronic character, while for larger nanoparticles conductivity becomes predominately ionic. Simulations revealed that the temperature dependence of Li-ion conductivity in anatase is very weak, while in rutile the conductivity decreases with temperature in small nanoparticles and increases in large nanoparticles.

  5. Low temperature self-assembled growth of rutile TiO2/manganese oxide nanocrystalline films

    NASA Astrophysics Data System (ADS)

    Sun, Zhenya; Zhou, Daokun; Du, Jianhua; Xie, Yuxing

    2017-10-01

    We report formation of rutile TiO2 nanocrystal at low temperature range in the presence of α-MnO2 which self-assembled onto sulfanyl radical activated silicon oxide substrate. SEM, HRTEM, XPS and Raman spectroscopy were used to study the morphology and oxidation state of synthesised crystals. The results showed that when the α-MnO2 was reduced to Mn3O4, it induced the formation of rutile instead of anatase phase in the TiCl4-HCl aqueous system. The finding will promote the understanding of phase transformation mechanism when manganese oxide and titanium oxide co-exist in soil and water environment.

  6. Ordered Single-Crystalline Anatase TiO2 Nanorod Clusters Planted on Graphene for Fast Charge Transfer in Photoelectrochemical Solar Cells.

    PubMed

    Wang, Yang; Liu, Xueqin; Li, Zhen; Cao, Ya; Li, Yinchang; Liu, Xupo; Jia, Songru; Zhao, Yanli

    2017-07-01

    Achieving efficient charge transport is a great challenge in nanostructured TiO2 -electrode-based photoelectrochemical cells. Inspired by excellent directional charge transport and the well-known electroconductibility of 1D anatase TiO2 nanostructured materials and graphene, respectively, planting ordered, single-crystalline anatase TiO2 nanorod clusters on graphene sheets (rGO/ATRCs) via a facial one-pot solvothermal method is reported. The hierarchical rGO/ATRCs nanostructure can serve as an efficient light-harvesting electrode for dye-sensitized solar cells. In addition, the obtained high-crystallinity anatase TiO2 nanorods in rGO/ATRCs possess a lower density of trap states, thus facilitating diffusion-driven charge transport and suppressing electron recombination. Moreover, the novel architecture significantly enhances the trap-free charge diffusion coefficient, which contributes to superior electron mobility properties. By virtue of more efficient charge transport and higher energy conversion efficiency, the rGO/ATRCs developed in this work show significant advantages over conventional rGO-TiO2 nanoparticle counterparts in photoelectrochemical cells. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. A fast-reliable methodology to estimate the concentration of rutile or anatase phases of TiO2

    NASA Astrophysics Data System (ADS)

    Zanatta, A. R.

    2017-07-01

    Titanium-dioxide (TiO2) is a low-cost, chemically inert material that became the basis of many modern applications ranging from, for example, cosmetics to photovoltaics. TiO2 exists in three different crystal phases - Rutile, Anatase and, less commonly, Brookite - and, in most of the cases, the presence or relative amount of these phases are essential to decide the TiO2 final application and its related efficiency. Traditionally, X-ray diffraction has been chosen to study TiO2 and provides both the phases identification and the Rutile-to-Anatase ratio. Similar information can be achieved from Raman scattering spectroscopy that, additionally, is versatile and involves rather simple instrumentation. Motivated by these aspects this work took into account various TiO2 Rutile+Anatase powder mixtures and their corresponding Raman spectra. Essentially, the method described here was based upon the fact that the Rutile and Anatase crystal phases have distinctive phonon features, and therefore, the composition of the TiO2 mixtures can be readily assessed from their Raman spectra. The experimental results clearly demonstrate the suitability of Raman spectroscopy in estimating the concentration of Rutile or Anatase in TiO2 and is expected to influence the study of TiO2-related thin films, interfaces, systems with reduced dimensions, and devices like photocatalytic and solar cells.

  8. Hydrophobic rutile phase TiO2 nanostructure and its properties for self-cleaning application

    NASA Astrophysics Data System (ADS)

    Shamsudin, S.; Ahmad, M. K.; Aziz, A. N.; Fakhriah, R.; Mohamad, F.; Ahmad, N.; Nafarizal, N.; Soon, C. F.; Ameruddin, A. S.; Faridah, A. B.; Shimomura, M.; Murakami, K.

    2017-09-01

    The nanostructured hydrophobic rutile phase titanium dioxide TiO2 and its properties for self-cleaning application were directly synthesized from titanium butoxide (TBOT) precursor deposited on the fluorine doped tin oxide (FTO) substrate through the hydrothermal treatment with different volume of TBOT and adding of Cetyl Trimethylammonium Bromide (CTAB). The samples were characterized respectively by way of field-emission scanning electron microscopy (FE-SEM), water contact angle measurement and Raman spectroscopy for surface analysis system. The FE-SEM results revealed a layer of nanoparticles were growth on the FTO substrate. The surface properties of the samples were studied with a water contact angle measurement. The water contact angle measurement results revealed the hydrophobic of samples as the angle of water droplet on the sample increased. The rutile phase and surface of TiO2 were confirmed using a Raman spectroscopy.

  9. 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

  10. Hydrogen shallow donors in ZnO and rutile TiO2

    NASA Astrophysics Data System (ADS)

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

    2012-05-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-09-01

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

  12. Modification of cellulose and rutile welding electrode coating by infiltrated TiO2 nanoparticles

    NASA Astrophysics Data System (ADS)

    Balos, Sebastian; Sidjanin, Leposava; Dramicanin, Miroslav; Labus, Danka; Pilic, Branka; Jovicic, Mirjana

    2016-05-01

    In this paper, a novel method of infiltration of TiO2 nanoparticles into the coating of the cellulose and rutile shielded metal arc welding electrode is shown. Tensile properties and strength of weld metals were correlated to the chemical composition of the weld metals, ferrite type, and non-metallic inclusion type, size and composition. As infiltration time is increased in the cellulose electrodes, the non-metallic inclusion count increases and their size decreases. They act as inoculants and lead to the replacement of Widmanstaetten with the finegrained acicular ferrite which increases the mechanical properties of the welds. The modification of rutile electrodes with low and medium infiltration time also refines the microstructure and increases the mechanical properties. Specimens welded with rutile electrodes infiltrated at maximum duration exhibited the lowest mechanical properties due to the relatively large non-metallic inclusions that act as void nucleation sites and the appearance of large grain allotriomorphic ferrite in the weld metal.

  13. Hydrothermal fabrication of quasi-one-dimensional single-crystalline anatase TiO2 nanostructures on FTO glass and their applications in dye-sensitized solar cells.

    PubMed

    Liao, Jin-Yun; Lei, Bing-Xin; Wang, Yu-Fen; Liu, Jun-Min; Su, Cheng-Yong; Kuang, Dai-Bin

    2011-01-24

    One-dimensional and quasi-one-dimensional semiconductor nanostructures are desirable for dye-sensitized solar cells (DSSCs), since they can provide direct pathways for the rapid collection of photogenerated electrons, which could improve the photovoltaic performance of the device. Quasi-1D single-crystalline anatase TiO(2) nanostructures have been successfully prepared on transparent, conductive fluorine-doped tin oxide (FTO) glass with a growth direction of [101] through a facile hydrothermal approach. The influences of the initial titanium n-butoxide (TBT) concentration, hydrothermal reaction temperature, and time on the length of quasi-1D anatase TiO(2) nanostructures and on the photovoltaic performance of DSSCs have been investigated in detail. A power conversion efficiency of 5.81% has been obtained based on the prepared TiO(2) nanostructure photoelectrode 6.7 μm thick and commercial N719 dye, with a short-circuit current density of 13.3 mA cm(-2) , an open-circuit voltage of 810 mV, and a fill factor of 0.54. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Effect of highly ordered single-crystalline TiO2 nanowire length on the photovoltaic performance of dye-sensitized solar cells.

    PubMed

    Zhou, Zheng-ji; Fan, Jun-qi; Wang, Xia; Zhou, Wen-hui; Du, Zu-liang; Wu, Si-xin

    2011-11-01

    One-dimensional semiconductor nanostructures grown directly onto transparent conducting oxide substrates with a high internal surface area are most desirable for high-efficiency dye-sensitized solar cells (DSSCs). Herein, we present a multicycle hydrothermal synthesis process to produce vertically aligned, single crystal rutile TiO(2) nanowires with different lengths between 1 and 8 μm for application as the working electrode in DSSCs. Optimum performance was obtained with a TiO(2) nanowire length of 2.0 μm, which may be ascribed to a smaller nanowire diameter with a high internal surface area and better optical transmittance with an increase in the incident light intensity on the N719 dye; as well as a firm connection at the FTO/TiO(2) nanowire interface.

  15. Graphene Oxide-Assisted Synthesis of Microsized Ultrathin Single-Crystalline Anatase TiO2 Nanosheets and Their Application in Dye-Sensitized Solar Cells.

    PubMed

    Chen, Biao; Sha, Junwei; Li, Wei; He, Fang; Liu, Enzuo; Shi, Chunsheng; He, Chunnian; Li, Jiajun; Zhao, Naiqin

    2016-02-03

    High-quality microsized ultrathin single-crystalline anatase TiO2 nanosheets (MS-TiO2) with exposed {001} facets were synthesized by a facile and low-cost two-step process that combines a graphene oxide (GO)-assisted hydrothermal method with calcination. Both GO and HF play an important role in the formation of well dispersed MS-TiO2. As a novel microsized (1-4 μm) ultrathin two-dimensional (2D) material, MS-TiO2 possesses much higher lateral size and aspect ratio compared to common 2D nanosized (30-60 nm) ultrathin TiO2 nanosheets (NS-TiO2), resulting in excellent electronic conductivity and superior electron transfer and diffusion properties. Here, we fabricated MS-TiO2 and NS-TiO2, both of which were incorporated with the TiO2 nanoparticles (P25) to constitute the hybrid photoanode of dye-sensitized solar cells (DSSCs), and explored the effect of the lateral size (nano- and micro-) of ultrathin TiO2 nanosheets on their electron transfer and diffusion properties. Benefiting from the faster electron transfer rate and short diffusion path of the MS-TiO2, the MS-TiO2/P25 gains the more superior performance compared to pure P25 and NS-TiO2/P25 in the application of DSSCs. Moreover, it is expected that the novel high aspect ratio MS-TiO2 may be applied in diverse fields including photocatalysis, photodetectors, lithium-ion batteries and others concerning the environment and energy.

  16. Photocatalytic degradation characteristics of different organic compounds at TiO2 nanoporous film electrodes with mixed anatase/ rutile phases.

    PubMed

    Jiang, Dianlu; Zhang, Shanqing; Zhao, Huijun

    2007-01-01

    Nanoporous TiO2 film electrodes with a mixed anatase/ rutile phase were prepared by dip-coating TiO2 nanoparticle colloid onto Indium Tin Oxide (ITO) conducting glass substrates and a subsequent calcination process at 700 degrees C for 16 h. The photocatalytic oxidation of a wide range of organic compounds has been studied using the photoelectrochemical method under the conditions that the photohole capturing step controls the overall photocatalytic processes. The characteristics of the mixed anatase/ rutile phase TiO2 film electrodes were compared with pure anatase phase TiO2 film electrodes to identify the key differences between them. The results revealed that different organic compounds, despite their difference in chemical entities, can be stoichiometrically mineralized at the mixed-phase TiO2 electrode under diffusion-controlled conditions, which is in great contrast to the situation at the pure anatase phase TiO2 electrode. The exceptional ability of the mixed-phase TiO2 electrodes for mineralization of organic compounds and their remarkable resistance to the inhibition by aromatic compounds at higher concentration has been explained by the synergetic effect of the rutile and anatase phases. For this type of mixed phase electrodes, upon absorption of UV light, the electron-transfer pathway from anatase phase to rutile phase facilitates the separation of photoelectron and photohole, extending the lifetime of the photoelectron and photohole.

  17. 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.

  18. 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. Copyright © 2012 Elsevier B.V. All rights reserved.

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

    PubMed

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

    2012-05-16

    In this study, we present a combined density functional theory and many-body perturbation theory study on the electronic and optical properties of TiO(2) 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 TiO(2) 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.

  20. Wet chemically prepared rutile TiO2(110) and TiO2(011): Substrate preparation for surface studies under non-UHV conditions

    NASA Astrophysics Data System (ADS)

    Ahmed, M. H. M.; Lydiatt, F. P.; Chekulaev, D.; Wincott, P. L.; Vaughan, D. J.; Jang, J. H.; Baldelli, S.; Thomas, A. G.; Walters, W. S.; Lindsay, R.

    2014-12-01

    A procedure for wet chemical preparation of TiO2 single crystal surfaces is detailed. The potential of this procedure is demonstrated through application to rutile-TiO2(110) and rutile-TiO2(011) substrates. Characterisation with atomic force microscopy, low energy electron diffraction, auger electron spectroscopy, and vibrational sum frequency spectroscopy indicates that flat, well-ordered, carbon-free surfaces can be generated. Notably, in contrast to the (2 × 1) low energy electron diffraction pattern observed for TiO2(011) prepared in ultra-high vacuum, wet chemical preparation results in a (4 × 1) unit cell; wet chemically prepared TiO2(110) displays an unreconstructed (1 × 1) surface.

  1. 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.

  2. Negative reflection in absorbing uniaxial media. Rutile TiO2

    NASA Astrophysics Data System (ADS)

    Diñeiro, J. M.; Alberdi, C.; Hernández, B.; Sáenz, C.

    2017-07-01

    We study the negative reflection of the extraordinary wave inside a slab of an uniaxial anisotropic absorbing material placed between two isotropic materials. The optic axis is contained in the plane of incidence. We particularize for Rutile TiO2 that possesses a high refractive index that makes it suitable for many applications. We show the existence of negative reflection in the ray and study its dependence with the orientation of the optic axis. We also compute the limiting angle for the occurrence of this phenomenon. It is found that negative reflection occurs for almost all values of the angle of incidence.

  3. Field-programmable rectification in rutile TiO2 crystals

    NASA Astrophysics Data System (ADS)

    Jameson, John R.; Fukuzumi, Yoshiaki; Wang, Zheng; Griffin, Peter; Tsunoda, Koji; Meijer, G. Ingmar; Nishi, Yoshio

    2007-09-01

    The authors report "field-programmable rectification" in crystals of rutile TiO2. A "programming" voltage is applied between two Pt electrodes on the surface of a crystal. Afterwards, current can pass in the direction of the programming voltage, but not in the reverse direction. The polarity of the rectification can be reversed by applying a programming voltage of opposite sign. The effect was observed on the (110) and (100) surfaces, but not the (001) surface. The proposed mechanism is field-induced motion of oxygen vacancies, which pile up under the negative terminal, eliminating a Schottky barrier, but leaving one at the positive terminal intact.

  4. 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

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

    PubMed Central

    2013-01-01

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

  6. Low-temperature preparation of rutile-type TiO2 thin films for optical coatings by aluminum doping

    NASA Astrophysics Data System (ADS)

    Ishii, Akihiro; Kobayashi, Kosei; Oikawa, Itaru; Kamegawa, Atsunori; Imura, Masaaki; Kanai, Toshimasa; Takamura, Hitoshi

    2017-08-01

    A rutile-type TiO2 thin film with a high refractive index (n), a low extinction coefficient (k) and small surface roughness (Ra) is required for use in a variety of optical coatings to improve the controllability of the reflection spectrum. In this study, Al-doped TiO2 thin films were prepared by pulsed laser deposition, and the effects of Al doping on their phases, optical properties, surface roughness and nanoscale microstructure, including Al distribution, were investigated. By doping 5 and 10 mol%Al, rutile-type TiO2 was successfully prepared under a PO2 of 0.5 Pa at 350-600 °C. The nanoscale phase separation in the Al-doped TiO2 thin films plays an important role in the formation of the rutile phase. The 10 mol%Al-doped rutile-type TiO2 thin film deposited at 350 °C showed excellent optical properties of n ≈ 3.05, k ≈ 0.01 (at λ = 400 nm) and negligible surface roughness, at Ra ≈ 0.8 nm. The advantages of the superior optical properties and small surface roughness of the 10 mol%Al-doped TiO2 thin film were confirmed by fabricating a ten-layered dielectric mirror.

  7. 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.

  8. Formation of swift heavy ion tracks on a rutile TiO2 (001) surface.

    PubMed

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

    2016-10-01

    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.

  9. 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

  10. The acute proinflammatory and prothrombotic effects of pulmonary exposure to rutile TiO2 nanorods in rats.

    PubMed

    Nemmar, Abderrahim; Melghit, Khaled; Ali, Badreldin H

    2008-05-01

    Nanotechnology is extensively used in industry and is widely explored for possible applications in medicine. However, its potential respiratory and systemic adverse effects remain unknown. Here pure titanium dioxide (TiO2) nanorods with rutile structure were prepared at room temperature by using a soft chemistry technique. The structure of the TiO2 rutile nanorods was confirmed by powder X-ray diffraction, and the size was revealed by transmission electron microscopy. Thereafter, we investigated, in Wistar rats, the acute (24-hr) effects of intratracheal instillation of these rutile TiO2 nanorods (1 and 5 mg/kg) on lung inflammation (assessed by bronchoalveolar lavage), systemic inflammation, and platelet aggregation in whole blood. Compared with vehicle-exposed rats, rats that underwent intratracheal instillation of TiO2 nanorods experienced a dose-dependent increase in macrophage numbers at 1 (+50%) and 5 mg/kg (+81%; P < 0.05) and an influx of neutrophils at 1 (+294%) and 5 mg/kg (+4117%; P < 0.01) in their bronchoalveolar lavage fluid. Both doses of rutile TiO2 nanorods caused pulmonary and cardiac edema, assessed by analysis of the wet weight-to-dry weight ratios. Similarly, the numbers of monocytes and granulocytes in the blood were increased in a dose-dependent manner after exposure to rutile TiO2 nanorods. In contrast, the number of platelets was significantly reduced after pulmonary exposure to 5 mg/kg TiO2 nanorods; this result indicated the occurrence of platelet aggregation in vivo. The direct addition of TiO2 nanorods (0.4-10 microg/ml) to untreated rat blood significantly induced platelet aggregation in a dose-dependent fashion in vitro. It is concluded that the intratracheal instillation of rutile TiO2 nanorods caused upregulation of lung inflammation, pulmonary and cardiac edema, and systemic inflammation. Rutile TiO2 nanorods also triggered platelet aggregation in vivo and in vitro.

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

    NASA Astrophysics Data System (ADS)

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

    2016-01-01

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

  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. 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.

  14. Adsorption of Nucleic Acid Components on Rutile (TiO2) Surfaces

    NASA Astrophysics Data System (ADS)

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

    2010-04-01

    Nucleic acids, the storage molecules of genetic information, are composed of repeating polymers of ribonucleotides (in RNA) or deoxyribonucleotides (in DNA), which are themselves composed of a phosphate moiety, a sugar moiety, and a nitrogenous base. The interactions between these components and mineral surfaces are important because there is a tremendous flux of nucleic acids in the environment due to cell death and horizontal gene transfer. The adsorption of mono-, oligo-, and polynucleotides and their components on mineral surfaces may have been important for the origin of life. We have studied here interactions of nucleic acid components with rutile (TiO2), a mineral common in many terrestrial crustal rocks. Our results suggest roles for several nucleic acid functional groups (including sugar hydroxyl groups, the phosphate group, and extracyclic functional groups on the bases) in binding, in agreement with results obtained from studies of other minerals. In contrast with recent studies of nucleotide adsorption on ZnO, aluminum oxides, and hematite, our results suggest a different preferred orientation for the monomers on rutile surfaces. The conformations of the molecules bound to rutile surfaces appear to favor specific interactions, which in turn may allow identification of the most favorable mineral surfaces for nucleic acid adsorption.

  15. Rutile TiO2 nanobundles on reduced graphene oxides as anode materials for Li ion batteries.

    PubMed

    Zhen, Mengmeng; Guo, Xuejing; Gao, Guandao; Zhou, Zhen; Liu, Lu

    2014-10-14

    A simple and steerable method was adopted to synthesize well-distributed rutile TiO2 nanobundles on reduced graphene oxides through two-step hydrothermal methods. The rutile TiO2-RGO composites were used as the anode materials in lithium ion batteries for investigation, which had an original morphology and a reversible capacity of 300 mA h g(-1) at 0.6 C and 200 mA h g(-1) at 1.2 C after 500 cycles.

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

    NASA Astrophysics Data System (ADS)

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

    2010-07-01

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

  17. TiO2 single crystalline nanorod compact layer for high-performance CH3NH3PbI3 perovskite solar cells with an efficiency exceeding 17%

    NASA Astrophysics Data System (ADS)

    He, Xin; Wu, Jihuai; Tu, Yongguang; Xie, Yiming; Dong, Jia; Jia, Jinbiao; Wei, Yuelin; Lan, Zhang

    2016-11-01

    A TiO2 compact layer is crucial to a high-performance perovskite solar cell (PSC). Interestingly, there is a severe paucity of research on using one-dimensional nanostructure to fabricate the compact layer. In this study, anatase TiO2 single-crystalline nanorods (NRs) with a length of 30 ± 10 nm and a diameter of 4 ± 1 nm are synthesized via a one-pot solvothermal approach. A pinhole-free and thickness-controllable compact layer on PSC is fabricated by spin-coating the TiO2 nanorods on transparent conductive oxide substrate. Thanks to good electronic transport channel and less defects and interfaces, one-dimensional TiO2 NRs, with longer electron lifetime, shorter transport time and higher charge collection efficiency than TiO2 quantum dots (QDs) and TiO2 nanoparticles (NPs), can improve the photovoltaic performance of the PSC based on TiO2-NR compact layer. As a result, the PSC based on TiO2 NRs shows the best photovoltaic performance with a power conversion efficiency of 17.58%, which is enhanced by a factor of 1.16 and 1.30 respectively compared with the PSCs based on TiO2-QDs and TiO2-NPs.

  18. 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.

  19. The effect of Fe segregation on the photocatalytic growth of Ag nanoparticles on rutile TiO2(001)

    NASA Astrophysics Data System (ADS)

    Busiakiewicz, Adam; Kisielewska, Aneta; Piwoński, Ireneusz; Batory, Damian

    2017-04-01

    The photocatalytic growth of silver nanoparticles (AgNPs) on rutile TiO2(001) and Fe-modified rutile TiO2(001) monocrystals was investigated. Various amount of Fe was segregated in a controlled way from the doped TiO2 substrates in ultra-high vacuum conditions resulting in low- medium- and high- content of Fe on TiO2 substrates. AgNPs were grown on pristine TiO2 and substrates containing Fe by photoreduction of Ag+ ions under UV illumination. It was found that the size of AgNPs was larger on Fe/TiO2 than on TiO2 while the surface density exhibited the opposite behavior - a large number of AgNPs were present on the TiO2 surface but only a few AgNPs were visible on the Fe/TiO2 substrates. The reason for the differences in size and number of AgNPs on TiO2 and Fe/TiO2 is the limited access of Ag+ to the TiO2 surface caused by the large number of Fe grains segregated onto the TiO2 surface. Another possible reason for the various AgNPs morphologies is alteration in the mechanism of Ag+ photoreduction caused by iron present as Fe3+ ions and by newly formed AgNPs playing the role of electron traps. The surface elemental analysis of the investigated materials was performed with the use of X-ray photoelectron spectroscopy (XPS) and confirmed the composition of AgNPs/Fe/TiO2 systems. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) revealed sizes, morphology and distribution of the nanostructures.

  20. Surface-Electronic-State-Modulated, Single-Crystalline (001) TiO2 Nanosheets for Sensitive Electrochemical Sensing of Heavy-Metal Ions.

    PubMed

    Zhou, Wen-Yi; Liu, Jin-Yun; Song, Jie-Yao; Li, Jin-Jin; Liu, Jin-Huai; Huang, Xing-Jiu

    2017-03-21

    Intrinsically low conductivity and poor reactivity restrict many semiconductors from electrochemical detection. Usually, metal- and carbon-based modifications of semiconductors are necessary, making them complex, expensive, and unstable. Here, for the first time, we present a surface-electronic-state-modulation-based concept applied to semiconductors. This concept enables pure semiconductors to be directly available for ultrasensitive electrochemical detection of heavy-metal ions without any modifications. As an example, a defective single-crystalline (001) TiO2 nanosheet exhibits high electrochemical performance toward Hg(II), including a sensitivity of 270.83 μA μM(-1) cm(-2) and a detection limit of 0.017 μM, which is lower than the safety standard (0.03 μM) of drinking water established by the World Health Organization (WHO). It has been confirmed that the surface oxygen vacancy adsorbs an O2 molecule while the Ti(3+) donates an electron, forming the O2(•-) species that facilitate adsorption of Hg(II) and serve as active sites for electron transfer. These findings not only extend the electrochemical sensing applications of pure semiconductors but also stimulate new opportunities for investigating atom-level electrochemical behaviors of semiconductors by surface electronic-state modulation.

  1. Niobium doped TiO2: Intrinsic transparent metallic anatase versus highly resistive rutile phase

    NASA Astrophysics Data System (ADS)

    Zhang, S. X.; Kundaliya, D. C.; Yu, W.; Dhar, S.; Young, S. Y.; Salamanca-Riba, L. G.; Ogale, S. B.; Vispute, R. D.; Venkatesan, T.

    2007-07-01

    We report on the structural, electrical, and optical properties of 5% niobium doped TiO2 thin films grown on various substrates by pulsed laser deposition. The epitaxial anatase Nb:TiO2 film on LaAlO3 is shown to be an intrinsic transparent metal and its metallic property arises from Nb substitution into Ti site as evidenced by the Rutherford backscattering channeling result. In contrast, the rutile Nb:TiO2 thin films show insulating behaviors with 2-3 orders higher room temperature electrical resistivity and ˜30 times lower mobility. A blueshift in the optical absorption edge is observed in both phases, though of differing magnitude.

  2. Muonium donor in rutile TiO2 and comparison with hydrogen

    NASA Astrophysics Data System (ADS)

    Vilão, R. C.; Vieira, R. B. L.; Alberto, H. V.; Gil, J. M.; Weidinger, A.; Lichti, R. L.; Baker, B. B.; Mengyan, P. W.; Lord, J. S.

    2015-08-01

    Muonium, a positive muon and an electron, is often used as an experimentally accessible substitute for hydrogen in materials research. In semiconductors and insulators, a large amount of information on the hydrogen behavior is deduced from this analogy; however, it is seldom demonstrated that this procedure is justified. We show here, via a comparison of the hyperfine interactions, that in TiO2 muonium and hydrogen form the same configuration with the same basic electronic structure. A detailed description of the bonding characteristics of the muon to the Ti3 + polaron is presented. The special role of muon motion within the so-called oxygen channel in the rutile structure, which occurs at a lower temperature than for hydrogen, is emphasized.

  3. Photoinduced small polarons bound to hydrogen defects in rutile TiO2

    NASA Astrophysics Data System (ADS)

    Hupfer, A.; Vines, L.; Monakhov, E. V.; Svensson, B. G.; Herklotz, F.

    2017-08-01

    Photoinduced absorption in rutile TiO2 has been studied by means of Fourier transform infrared spectroscopy. It is shown that near-band-gap illumination results in a charge-state transition of a hydrogen defect with an O-H stretch mode at 3500 cm-1, as evidenced by the appearance of an anticorrelated vibrational mode with a blueshift of ˜1.3 cm-1 . The charge-state transition is accompanied by a broad near-infrared absorption band with maximum intensity at ˜7000 cm-1 . Our data on both the photoinduced vibrational mode and the near-infrared absorption can be conclusively explained in the framework of a model of small electron polarons bound to a Ti atom adjacent to the O-H group of the hydrogen defect.

  4. Anomalous anisotropic exciton temperature dependence in rutile TiO2

    NASA Astrophysics Data System (ADS)

    Baldini, Edoardo; Dominguez, Adriel; Chiodo, Letizia; Sheveleva, Evgeniia; Yazdi-Rizi, Meghdad; Bernhard, Christian; Rubio, Angel; Chergui, Majed

    2017-07-01

    Elucidating the details of electron-phonon coupling in semiconductors and insulators is a topic of pivotal interest, as it governs the transport mechanisms and is responsible for various phenomena such as spectral-weight transfers to phonon sidebands and self-trapping. Here, we investigate the influence of the electron-phonon interaction on the excitonic peaks of rutile TiO2, revealing a strong anisotropic polarization dependence with increasing temperature, namely, an anomalous blue shift for light polarized along the a axis and a conventional red shift for light polarized along the c axis. By employing many-body perturbation theory, we identify two terms in the electron-phonon interaction Hamiltonian that contribute to the anomalous blue shift of the a -axis exciton. Our approach paves the way to a complete ab initio treatment of the electron-phonon interaction and of its influence on the optical spectra of polar materials.

  5. Effect of rutile phase on V2O5 supported over TiO2 mixed phase for the selective catalytic reduction of NO with NH3

    NASA Astrophysics Data System (ADS)

    Zhang, Shule; Zhong, Qin; Wang, Yining

    2014-09-01

    A series of V2O5/TiO2 catalysts with different ratios of TiO2 rutile phase was prepared. Focusing on the effect of TiO2 rutile phase on V2O5/TiO2 catalyst for the selective catalytic reduction (SCR) of NO with NH3, the NO conversion for the different catalysts was investigated. The experimental results showed that a small amount of TiO2 rutile phase could improve the NO conversion significantly below 270 °C. Analysis by XRD, NH3-TPD, UV-vis, EPR and DFT calculation showed that the rutile phase of TiO2 supporter decreased the band gap, especially, the conduction band level. It improved the formation of reduced V species and superoxide ions that were important to the low-temperature SCR reaction.

  6. Weathering Performance of Wood Coated with a Combination of Alkoxysilanes and Rutile TiO2 Heirarchical Nanostructures

    Treesearch

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

    2015-01-01

    The weathering performance of wood coated with a combination of rutile TiO2 hierarchicalnanostructures and a sol-gel deposit of alkoxysilanes was determined by exposing three sets of specimens to UV light and water spray. The first set consisted of specimens coated with a mixture of methyltrimethoxysilane (MTMOS) and hexadecyltrimethoxysilane (...

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  8. Nb-Doped Rutile TiO2 Mesocrystals with Enhanced Lithium Storage Properties for Lithium Ion Battery.

    PubMed

    Lan, Tongbin; Zhang, Weifeng; Wu, Nae-Lih; Wei, Mingdeng

    2017-04-11

    A homogeneous Nb-doped rutile TiO2 mesocrystal material was synthesized successfully through a facile hydrothermal route. The incorporation of Nb(5+) not only promotes the crystallization of the building subunits of the rutile TiO2 mesocrystal, but also improves the electrochemical performance at higher current rates. A capacity of 96.3 mAh g(-1) at a current density as high as 40 C and an excellent long-term cycling stability with a capacity loss of approximately 0.006 % per cycle at 5 C could be achieved when an appropriate amount of Nb(5+) was doped into rutile TiO2 mesocrystal. The reasons for the improvement of rate capability may be attributed to the enhancement of electronic conductivity, Li-ion diffusion kinetics, and the surface storage property for the Nb-doped rutile TiO2 mesocrystal. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    NASA Astrophysics Data System (ADS)

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

    2010-03-01

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

  10. Semiconductor-to-metal transition in rutile TiO2 induced by tensile strain

    DOE PAGES

    Benson, Eric E.; Miller, Elisa M.; Nanayakkara, Sanjini U.; ...

    2017-02-10

    Here, we report the first observation of a reversible, degenerate doping of titanium dioxide with strain, which is referred to as a semiconductor-to-metal transition. Application of tensile strain to a ~50 nm film of rutile TiO2 thermally grown on a superelastic nitinol (NiTi intermetallic) substrate causes reversible degenerate doping as evidenced by electrochemistry, X-ray photoelectron spectroscopy (XPS), and conducting atomic force microscopy (CAFM). Cyclic voltammetry and impedance measurements show behavior characteristic of a highly doped n-type semiconductor for unstrained TiO2 transitioning to metallic behavior under tensile strain. The transition reverses when strain is removed. Valence band XPS spectra show thatmore » samples strained to 5% exhibit metallic-like intensity near the Fermi level. Strain also induces a distinct transition in CAFM current-voltage curves from rectifying (typical of an n-type semiconductor) to ohmic (metal-like) behavior. We propose that strain raises the energy distribution of oxygen vacancies (n-type dopants) near the conduction band and causes an increase in carrier concentration. As the carrier concentration is increased, the width of the depletion region is reduced, which then permits electron tunneling through the space charge barrier resulting in the observed metallic behavior.« less

  11. 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.

  12. Dehydration and dehydrogenation of ethylene glycol on rutile TiO2(110).

    PubMed

    Li, Zhenjun; Kay, Bruce D; Dohnálek, Zdenek

    2013-08-07

    The interactions of ethylene glycol with a partially reduced rutile TiO2(110) surface have been studied using temperature programmed desorption (TPD). The saturation coverage on surface Ti rows is determined to be 0.43 monolayer (ML), slightly less than one ethylene glycol per two Ti sites. Most of the adsorbed ethylene glycol (∼80%) undergoes further reactions to yield 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 those of water and hydrogen, respectively. Dehydration dominates at lower ethylene glycol coverages (<0.2 ML) and plateaus as the coverage is increased to saturation. Dehydrogenation is observed primarily at higher ethylene glycol coverages (>0.2 ML). Our results suggest that the observed dehydration and dehydrogenation reactions proceed via different surface intermediates.

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

    SciTech Connect

    Shen, Mingmin; Henderson, Michael A.

    2012-08-07

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

  14. 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.

  15. 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).

  16. Electronic structure of Mu-complex donor state in rutile TiO2

    NASA Astrophysics Data System (ADS)

    Shimomura, K.; Kadono, R.; Koda, A.; Nishiyama, K.; Mihara, M.

    2015-08-01

    The hyperfine structure of the interstitial muonium (Mu) in rutile (TiO2, weakly n -type) has been identified by means of a muon-spin-rotation technique. The angle-resolved hyperfine parameters exhibit a tetragonal anisotropy within the a b plane and axial anisotropy with respect to the <001 > (c ̂) axis. This strongly suggests that the Mu is bound to O (forming an OH bond) at an off-center site within a channel along the c ̂ axis, while the unpaired Mu electron is localized around the neighboring Ti site. The hyperfine parameters are quantitatively explained by a model that considers spin polarization of the unpaired electron at both the Ti and O sites, providing evidence for the formation of Mu as a Ti-O-Mu-complex paramagnetic state. The disappearance of the Mu signal above ˜10 K suggests that the energy necessary for the promotion of the unpaired electron to the conduction band by thermal activation is of the order of 101 meV. These observations suggest that, while the electronic structure of Mu (and hence H) differs considerably from that of the conventional shallow level donor described by the effective mass model, Mu supplies a loosely bound electron, and thus, serves as a donor in rutile.

  17. Oxygen-vacancy driven electron localization and itinerancy in rutile-based TiO2

    NASA Astrophysics Data System (ADS)

    Lechermann, Frank; Heckel, Wolfgang; Kristanovski, Oleg; Müller, Stefan

    2017-05-01

    Oxygen-deficient TiO2 in the rutile structure as well as the Ti3O5 Magnéli phase is investigated within the charge self-consistent combination of density functional theory with dynamical mean-field theory. It is shown that an isolated oxygen vacancy (VO) in titanium dioxide is not sufficient to metallize the system at low temperatures. In a semiconducting phase, an in-gap state is identified at ɛIG˜-0.75 eV in excellent agreement with experimental data. Bandlike impurity levels, resulting from a threefold VO-Ti coordination as well as entangled (t2 g,eg) states, become localized due to site-dependent electronic correlations. Charge localization and strong orbital polarization occur in the VO-near Ti ions, the details of which can be modified by a variation of the correlated subspace. At higher oxygen vacancy concentration, a correlated metal is stabilized in the Magnéli phase. A VO-defect rutile structure of identical stoichiometry shows key differences in the orbital-resolved character and the spectral properties. Charge disproportionation is vital in the oxygen-deficient compounds, but obvious metal-insulator transitions driven or sustained by charge order are not identified.

  18. Hydrothermal synthesis of a crystalline rutile TiO2 nanorod based network for efficient dye-sensitized solar cells.

    PubMed

    Yu, Hua; Pan, Jian; Bai, Yang; Zong, Xu; Li, Xinyong; Wang, Lianzhou

    2013-09-27

    One-dimensional (1D) TiO2 nanostructures are desirable as photoanodes in dye-sensitized solar cells (DSSCs) due to their superior electron-transport capability. However, making use of the DSSC performance of 1D rutile TiO2 photoanodes remains challenging, mainly due to the small surface area and consequently low dye loading. Herein, a new type of photoanode with a three-dimensional (3D) rutile-nanorod-based network structure directly grown on fluorine-doped tin oxide (FTO) substrates was developed by using a facile two-step hydrothermal process. The resultant photoanode possesses oriented rutile nanorod arrays for fast electron transport as the bottom layer and radially packed rutile head-caps with an improved large surface area for efficient dye adsorption. The diffuse reflectance spectra showed that with the radially packed top layer, the light-harvesting efficiency was increased due to an enhanced light-scattering effect. A combination of electrochemical impedance spectroscopy (EIS), dark current, and open-circuit voltage decay (OCVD) analyses confirmed that the electron-recombiantion rate was reduced on formation of the nanorod-based 3D network for fast electron transport. As a resut, a light-to-electricity conversion efficiency of 6.31% was achieved with this photoanode in DSSCs, which is comparable to the best DSSC efficiencies that have been reported to date for 1D rutile TiO2 .

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

    PubMed

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

    2014-02-10

    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.

  20. Photoluminescence and Raman spectroscopy studies of Eu3+-doped rutile TiO2 nanocrystals at high pressures

    NASA Astrophysics Data System (ADS)

    Zeng, Q. G.; Ding, Z. J.; Lei, B. F.; Sheng, Y. Q.; Zhang, Z. M.

    2012-09-01

    Nanocrystal samples (particle size about 90 nm) of Eu3+-doped rutile titanium dioxide (TiO2) nanocrystals (rutile Eu3+/TiO2 nanocrystals) were synthesized by the sol-gel method with hydrothermal treatment. The pressure effect on photoluminescence (PL) and Raman spectra of the rutile Eu3+/TiO2 nanocrystals was investigated with a diamond anvil cell under hydrostatic pressure condition. Raman spectra of the samples at high pressures indicated that the critical pressure for the transition from the rutile phase to a new baddeleyite-type phase was between 10 and 14.2 GPa. The position of Raman bands shifted to high wavenumbers and the PL intensity of 5D 0→7F 2 transition of Eu3+ decreased down to zero with the increase of pressure before the phase transition occurred. After releasing the pressure, the rutile phase was not recovered and a α-PbO2-type phase was observed at ambient pressure.

  1. Photoelectrocatalytic treatment of pentachlorophenol in aqueous solution using a rutile nanotube-like TiO2/Ti electrode.

    PubMed

    Yang, Shaogui; Quan, Xie; Li, Xinyong; Sun, Cheng

    2006-09-01

    Taking pentachlorophenol (PCP) as a reference, we investigated the photoelectrocatalytic degradation of organic pollutants using a rutile nanotube-like TiO(2)/Ti film electrode. The nanotube-like TiO2 electrode was prepared by first oxidizing the surface of a titanium sheet to form rutile TiO2 and then treating it to form the tubular structure in NaOH aqueous solution. The occurrence of PCP degradation was indicated by the decrease in pH, concentration of PCP and TOC, and by the formation of chloride ions. The photoelectrochemical (PEC) efficiency of the nanotube-like TiO2/Ti electrode has been determined in terms of degradation of PCP and the incident photo-to-current conversion efficiency (IPCE). The experimental results showed that PCP could be degraded more efficiently by a photoelectrocatalytic process than by a photocatalytic or electrochemical oxidation alone. A significant photoelectrochemical synergetic effect was observed. The kinetic constant of PEC degradation of PCP using a nanotube-like TiO2 electrode was over 60% higher than that using a TiO2 film electrode. It is noted that chloride ion and hydrogen ion concentration increased with irradiation time in the PEC degradation of PCP; PCP was gradually mineralized and the complete minimization of PCP took more time than its degradation.

  2. 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

  3. Cytotoxicity Evaluation of Anatase and Rutile TiO2 Thin Films on CHO-K1 Cells in Vitro

    PubMed Central

    Cervantes, Blanca; López-Huerta, Francisco; Vega, Rosario; Hernández-Torres, Julián; García-González, Leandro; Salceda, Emilio; Herrera-May, Agustín L.; Soto, Enrique

    2016-01-01

    Cytotoxicity of titanium dioxide (TiO2) thin films on Chinese hamster ovary (CHO-K1) cells was evaluated after 24, 48 and 72 h of culture. The TiO2 thin films were deposited using direct current magnetron sputtering. These films were post-deposition annealed at different temperatures (300, 500 and 800 °C) toward the anatase to rutile phase transformation. The root-mean-square (RMS) surface roughness of TiO2 films went from 2.8 to 8.08 nm when the annealing temperature was increased from 300 to 800 °C. Field emission scanning electron microscopy (FESEM) results showed that the TiO2 films’ thickness values fell within the nanometer range (290–310 nm). Based on the results of the tetrazolium dye and trypan blue assays, we found that TiO2 thin films showed no cytotoxicity after the aforementioned culture times at which cell viability was greater than 98%. Independently of the annealing temperature of the TiO2 thin films, the number of CHO-K1 cells on the control substrate and on all TiO2 thin films was greater after 48 or 72 h than it was after 24 h; the highest cell survival rate was observed in TiO2 films annealed at 800 °C. These results indicate that TiO2 thin films do not affect mitochondrial function and proliferation of CHO-K1 cells, and back up the use of TiO2 thin films in biomedical science. PMID:28773740

  4. H2O-EG-assisted synthesis of uniform urchinlike rutile TiO2 with superior lithium storage properties.

    PubMed

    Chen, Jun Song; Liang, Yen Nan; Li, Yongmei; Yan, Qingyu; Hu, Xiao

    2013-10-23

    A facile green method to synthesize uniform nanostructured urchinlike rutile TiO2 is demonstrated. Titanium trichloride was selected as the TiO2 precursor, and a mixed solvent containing H2O and ethylene glycol was used. By using this binary medium, the nucleation and crystal growth of rutile TiO2 can be regulated, giving rise to very uniform urchinlike structures with tailorable sizes. As confirmed by the SEM and TEM analysis, large particles with dense aggregation of needle-like building blocks or small ones with loosely packed subunits could be obtained at different reaction conditions. The as-prepared samples were applied as the anode material for lithium-ion batteries, and they were shown to have superior properties with a high reversible capacity of 140 mA h g(-1) at a high current rate of 10 C for up to 300 cycles, which is almost unmatched by other rutile TiO2-based electrodes. A stable capacity of 88 mA h g(-1) can also be delivered at an extremely high rate of 50 C, suggesting the great potential of the as-prepared product for high-rate lithium-ion batteries.

  5. Synthesis, phase to phase deposition and characterization of rutile nanocrystalline titanium dioxide (TiO2) thin films

    NASA Astrophysics Data System (ADS)

    Gupta, Sanjeev K.; Singh, Jitendra; Anbalagan, K.; Kothari, Prateek; Bhatia, Ravi Raj; Mishra, Pratima K.; Manjuladevi, V.; Gupta, Raj K.; Akhtar, J.

    2013-01-01

    In this work the preparation, deposition and structural properties of titanium oxide (TiO2) thin films were investigated. The films were deposited by means of the e-beam physical vapor deposition (EBPVD) method in high vacuum (10-7 Torr). A controlled deposition rate in the range of 0.1-0.3 Å/s was monitored in situ employing quartz crystal. The films were deposited on the oxidized Si (1 0 0) wafer, glass micro slides. These films were analyzed using Grazing Angle X-ray diffraction (GA-XRD), Fourier Transform Infrared Spectroscopy (FTIR), Raman Spectroscopy (RAMAN), Atomic Force Microscopy (AFM) and UV-visible Spectroscopy (UV-vis). Structural characterization results showed mainly presence of the crystalline rutile phase, however an interfacial SiO2 layer between TiO2 and the substrate and the minor anatase crystalline phase of TiO2 was also identified in FTIR analysis. Grain size was found to be in the range of 100-125 nm while grain boundary was estimated to be 20 nm. Direct and indirect optical band gap was estimated to be 3.64 and 3.04 eV, respectively. A process induced self annealing of deposited film shows a strong effect on the structural, morphological and optical properties. Furthermore, low deposition rate and high vacuum allows rutile to rutile phase transformation from indigenously prepared TiO2 target to thin film.

  6. One-step electrospinning route of SrTiO3-modified Rutile TiO2nanofibers and its photocatalytic properties

    NASA Astrophysics Data System (ADS)

    Zhao, Weijie; Zhang, Jing; Pan, Jiaqi; Qiu, Jianfeng; Niu, Jiantao; Li, Chaorong

    2017-05-01

    The SrTiO3 modified rutile TiO2 composite nanofibers were synthesized by a simple electrospinning technique. The result of XRD, SEM and TEM indicate that the SrTiO3/TiO2 heterojuction has been prepared successfully. Compared with the TiO2 and SrTiO3, the photocatalytic activity of the SrTiO3/TiO2 (rutile) for the degradation of methyl orange exhibits an obvious enhancement under UV illumination. which is almost 2 times than that of bare TiO2 (rutile) nanofiber. Further, the high crystallinity and photon-generated carrier separation of the SrTiO3/TiO2 heterojuction are considered as the main reason for this enhancement.

  7. 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.

  8. 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.

  9. 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

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

    NASA Astrophysics Data System (ADS)

    Ishida, Nobuyuki; Iwasaki, Tamaki; Fujita, Daisuke

    2011-04-01

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

  11. 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.

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

    SciTech Connect

    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 with 1 - 4 carbon atoms 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 an 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 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.

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

    DOE PAGES

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

    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

  14. Threshold displacement energies in rutile TiO 2: A molecular dynamics simulation study

    NASA Astrophysics Data System (ADS)

    Thomas, B. S.; Marks, N. A.; Corrales, L. R.; Devanathan, R.

    2005-09-01

    Threshold displacement energies are determined for Ti and O in rutile TiO 2 using molecular dynamics simulations with an empirical model. The simulations involve the introduction of a primary knock-on atom (PKA) with a range of energies (30-150 eV) in various crystallographic directions at 160 K. We observe the formation of stable Frenkel defects, as well as defect recovery via low-energy interstitial migration mechanisms. The latter causes significant statistical variation between simulation outcomes, which leads to the definition of a defect formation probability. This probability is characterized as a function of PKA energy in order to define the threshold displacement energy and compare with experimental results. Using a probability of 10%, the average threshold displacement energy is around 40 eV for oxygen (comparable to experiment) and 105 eV for titanium. Using a probability of 50%, the values are 65 eV and 130 eV respectively, which may be more appropriate for use in TRIM calculations. In addition, we run a parallel set of calculations using a second empirical model, finding that the detailed results are highly model-dependent, particularly the oxygen defect structures and energies, which are compared to new ab initio data.

  15. 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.

  16. 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.

  17. 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.

  18. Epitaxial growth of thin films of rutile (TiO 2) on {100} surfaces of rutile single crystals reacted with Ga 2O 3 in air

    NASA Astrophysics Data System (ADS)

    Iguchi, E.; Tilley, R. J. D.

    1982-08-01

    Epitaxial films of rutile (TiO 2) were found to form on the {100} surface of rutile single crystals heated on Ga 2O 3 pellets in air at temperatures from 1373 to 1573 K. The nucleation and growth of the new oxide layer were observed by optical microscopy. The incubation period for the nucleation of the new layer, t0, was found to be t0=5.81×10 -5 exp[(163±41)/ RT](h), and the rate of th growth of the new layer, {dl }/{dt }, as {dl }/{dt }=1.48×10 5exp[-(196±14)/RT] ( mm/h) . The activation energies of these processes are 163 and 196 kJ mol -1, respectively. The kinetics for the nucleation and growth of the layers are discussed in terms of a vapour-solid reaction between a volatile gallium oxide species and the rutile crystal.

  19. IR and quantum-chemical studies of carboxylic acid and glycine adsorption on rutile TiO2 nanoparticles.

    PubMed

    Ojamäe, Lars; Aulin, Christian; Pedersen, Henrik; Käll, Per-Olov

    2006-04-01

    Nanocrystalline TiO2 powders of the rutile polymorph, synthesized by a sol-gel method, were treated with water solutions containing, respectively, formic, acetic, and citric acid and glycine in order to study the adsorption properties of these organic species. The samples were characterized by FTIR, Raman, powder XRD, and TEM. It was found that HCOOH, CH3COOH and HOC(COOH)(CH2COOH)2--but not NH2CH2COOH--adsorbed onto TiO2. The adsorption of HCOOH, CH3COOH and NH2CH2COOH onto the (110) surface of rutile was also studied by quantum-chemical periodic density functional theory (DFT) calculations. The organic molecules were from the computations found to adsorb strongly to the surfaces in a bridge-coordinating mode, where the two oxygens of the deprotonated carboxylic acid bind to two surface titanium ions. Surface relaxation is found to influence adsorption geometries and energies significantly. The results from DFT calculations and ab initio molecular-dynamics simulations of formic acid adsorption onto TiO2 are compared and match well with the experimental IR measurements, supporting the bridge-binding geometry of carboxylic-acid adsorption on the TiO2 nanoparticles.

  20. Controlling the Al-doping profile and accompanying electrical properties of rutile-phased TiO2 thin films.

    PubMed

    Jeon, Woojin; Rha, Sang Ho; Lee, Woongkyu; Yoo, Yeon Woo; An, Cheol Hyun; Jung, Kwang Hwan; Kim, Seong Keun; Hwang, Cheol Seong

    2014-05-28

    The role of Al dopant in rutile-phased TiO2 films in the evaluation of the mechanism of leakage current reduction in Al-doped TiO2 (ATO) was studied in detail. The leakage current of the ATO film was strongly affected by the Al concentration at the interface between the ATO film and the RuO2 electrode. The conduction band offset of the interface increased with the increase in the Al dopant concentration in the rutile TiO2, which reduced the leakage current in the voltage region pertinent to the next-generation dynamic random access memory application. However, the Al doping in the anatase TiO2 did not notably increase the conduction band offset even with a higher Al concentration. The detailed analyses of the leakage conduction mechanism based on the quantum mechanical transfer-matrix method showed that Schottky emission and Fowler-Nordheim tunneling was the dominant leakage conduction mechanism in the lower and higher voltage regions, respectively. The chemical analyses using X-ray photoelectron spectroscopy corroborated the electrical test results.

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

    NASA Astrophysics Data System (ADS)

    Yener, H. Banu; Helvacı, Şerife Ş.

    2015-09-01

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

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

    DOE PAGES

    Kim, Boseong; Dohnalek, Zdenek; Szanyi, Janos; ...

    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

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

    SciTech Connect

    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 byproduct 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.

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

    PubMed

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

    2015-01-01

    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.

  5. Chemical bath deposited rutile TiO2 compact layer toward efficient planar heterojunction perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Liang, Chao; Wu, Zhenhua; Li, Pengwei; Fan, Jiajie; Zhang, Yiqiang; Shao, Guosheng

    2017-01-01

    TiO2 is a best choice of electron transport layers in perovskite solar cells, due to its high electron mobility and stability. However, traditional TiO2 processing method requires rather high annealing temperature (>500 °C), preventing it from application to flexible devices. Here, we show that TiO2 thin films can be synthesized via chemical bath deposition below 100 °C. Typically, a compact layer of rutile TiO2 is deposited onto fluorine-doped tin oxide (FTO) coated substrates, in an aqueous TiCl4 solution at 70 °C. Through the optimization of precursor concentration and ultraviolet-ozone surface modification, over 12% power conversion efficiency can be achieved for CH3NH3PbI3 based perovskite solar cells. These findings offer a potential low-temperature technical solution in using TiO2 thin film as an effective transport layer for flexible perovskite 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. Anatase (101)-like Structural Model Revealed for Metastable Rutile TiO2(011) Surface.

    PubMed

    Xu, Meiling; Shao, Sen; Gao, Bo; Lv, Jian; Li, Quan; Wang, Yanchao; Wang, Hui; Zhang, Lijun; Ma, Yanming

    2017-03-08

    Titanium dioxide has been widely used as an efficient transition metal oxide photocatalyst. However, its photocatalytic activity is limited to the ultraviolet spectrum range due to the large bandgap beyond 3 eV. Efforts to reduce the bandgap to achieve a broader spectrum range of light absorption have been successfully attempted via the experimental synthesis of dopant-free metastable surface structures of rutile-type TiO2 (011) 2 × 1. This new surface phase possesses a reduced bandgap of ∼2.1 eV, showing great potential for an excellent photocatalyst covering a wide range of visible light. There is a need to establish the atomistic structure of this metastable surface to understand the physical cause for the bandgap reduction and to improve the future design of photocatalysts. Here, we report computational investigations in an effort to unravel this surface structure via swarm structure-searching simulations. The established structure adopts the anatase (101)-like structure model, where the topmost 2-fold O atoms form a quasi-hexagonal surface pattern and bond with the unsaturated 5-fold and 4-fold Ti atoms in the next layer. The predicted anatase (101)-like surface model can naturally explain the experimental observation of the STM images, the electronic bandgap, and the oxidation state of Ti(4+). Dangling bonds on the anatase (101)-like surface are abundant making it a superior photocatalyst. First-principles molecular dynamics simulations have supported the high photocatalytic activity by showing that water and formic acid molecules dissociate spontaneously on the anatase (101)-like surface.

  8. Ultrathin single-crystalline TiO2 nanosheets anchored on graphene to be hybrid network for high-rate and long cycle-life sodium battery electrode application

    NASA Astrophysics Data System (ADS)

    Shoaib, Anwer; Huang, Yongxin; Liu, Jia; Liu, Jiajia; Xu, Meng; Wang, Ziheng; Chen, Renjie; Zhang, Jiatao; Wu, Feng

    2017-02-01

    In view of the growing concern about energy management issues, sodium ion batteries (SIBs) as cheap and environmentally friendly devices have increasingly received wide research attentions. The high current rate and long cycle-life of SIBs are considered as two key parameters determining its potential for practical applications. In this work, the rigid single-crystalline anatase TiO2 nanosheets (NSs) with a thickness of ∼4 nm has been firstly prepared, based on which a stable nanostructured network consisting of ultrathin anatase TiO2 NSs homogeneously anchored on graphene through chemical bonding (TiO2 NSs-G) has fabricated by hydrothermal process and subsequent calcination treatment. The morphology, crystallization, chemical compositions and the intimate maximum contact between TiO2 NSs and graphene are confirmed by TEM, SEM, XRD, XPS and Raman characterizations. The results of electrochemical performance tests indicated that the TiO2 NSs-G hybrid network could be consider as a promising anode material for SIBs, in assessment of its remarkably high current rate and long cycle-life aside from the improved specific capacity, rate capability and cycle stability.

  9. Rapid charge transport in dye-sensitized solar cells made from vertically aligned single-crystal rutile TiO(2) nanowires.

    PubMed

    Feng, Xinjian; Zhu, Kai; Frank, Arthur J; Grimes, Craig A; Mallouk, Thomas E

    2012-03-12

    A rapid solvothermal approach was used to synthesize aligned 1D single-crystal rutile TiO(2) nanowire (NW) arrays on transparent conducting substrates as electrodes for dye-sensitized solar cells. The NW arrays showed a more than 200 times faster charge transport and a factor four lower defect state density than conventional rutile nanoparticle films.

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

    SciTech Connect

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

    2012-03-12

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

  11. Visible Light-Driven H2 Production over Highly Dispersed Ruthenia on Rutile TiO2 Nanorods

    DOE PAGES

    Nguyen-Phan, Thuy-Duong; Luo, Si; Vovchok, Dimitriy; ...

    2015-12-02

    The immobilization of miniscule quantities of RuO2 (~0.1%) onto one-dimensional (1D) TiO2 nanorods (NRs) allows H2 evolution from water under visible light irradiation. In addition, rod-like rutile TiO2 structures, exposing preferentially (110) surfaces, are shown to be critical for the deposition of RuO2 to enable photocatalytic activity in the visible region. The superior performance is rationalized on the basis of fundamental experimental studies and theoretical calculations, demonstrating that RuO2(110) grown as 1D nanowires on rutile TiO2(110), which occurs only at extremely low loads of RuO2, leads to the formation of a heterointerface that efficiently adsorbs visible light. The surface defects,more » band gap narrowing, visible photoresponse, and favorable upward band bending at the heterointerface drastically facilitate the transfer and separation of photogenerated charge carriers.« less

  12. First-principles study of relative stability of rutile and anatase TiO2 using the random phase approximation.

    PubMed

    Cui, Zhi-Hao; Wu, Feng; Jiang, Hong

    2016-11-02

    The relative stability of TiO2 in the rutile and anatase structure is wrongly described by density functional theory in various local, semilocal, or even hybrid functional approximations. In this work, we have found that by considering high-order correlations in the adiabatic connection fluctuation-dissipation theory with the random phase approximation (ACFDT-RPA), rutile is correctly predicted to be more stable than anatase, which can be physically attributed to different characters in the electronic band structure of rutile and anatase, including, in particular, that rutile has a smaller band gap than anatase. We further consider the zero-point energy and finite-temperature effects based on the harmonic approximation, and we found that the inclusion of the zero-point energy correction can further increase the relative stability of rutile, and leads to a better quantitative agreement with available experimental measurements. Our study indicates the importance of considering high-order dynamical correlation effects to correctly predict the relative phase stability of polymorphic materials, especially for those systems in which the less stable phase as predicted by conventional local, semilocal or even hybrid density functional approximations has a smaller band gap than the more stable one.

  13. Effect of Cr3+ concentration on structural and optical properties of TiO2:Cr3+ anatase and rutile phases

    NASA Astrophysics Data System (ADS)

    Loan, Trinh Thi; Bang, Ngac An; Huong, Vu Hoang; Long, Nguyen Ngoc

    2017-07-01

    TiO2 powders doped with different amounts of Cr3+ions (from 0 to 10 mol%) have been prepared by hydrothermal technique. TiO2:Cr3+ powders were characterized by X-ray diffraction, Raman spectroscopy, transmission electron microscopy, diffuse reflection, absorption, photoluminescence and photoluminescence excitation spectra. The results showed that the Cr3+ dopant concentrations did not affect on the lattice constants of TiO2 crystal, but affected on shift and broadening of the Raman modes for both anatase and rutile phases. The band gap of both the anatase and rutile TiO2 host lattice was strongly decreased with increasing Cr3+ dopant concentration. The photoluminescence spectra of TiO2:Cr3+ anatase phase exhibited a weak narrow peak (the so-called R-line) at 698 nm, meanwhile those of TiO2:Cr3+ rutile phase consisted of a very intense narrow zero-phonon R-line at 695 nm assigned to the 2E(2G) → 4A2(4F) transition of Cr3+ ions in strong octahedral field and its phonon-sidebands. In particular, in the PL spectrum of TiO2:Cr3+ rutile phase is also observed an abroad emission band centered at 813 nm assigned to the 4T2(4F) → 4A2(4F) transition of ions Cr3+ in weak octahedral field.

  14. Eu(III) sorption to TiO2 (anatase and rutile): batch, XPS, and EXAFS studies.

    PubMed

    Tan, Xiaoli; Fan, Qiaohui; Wang, Xiangke; Grambow, Bernd

    2009-05-01

    The sorption of Eu(III) on anatase and rutile was studied as a function of ionic strength, humic acid (HA, 7.5 mg/L), and electrolyte anions over a large range of pH (2-12). The presence of HA significantly affected Eu(III) sorption to anatase and rutile. The sorption of Eu(III) on anatase and rutile was independent of ionic strength. Results of an X-ray photoelectron spectroscopy (XPS) analysis showed that Eu(III) was chemically present within the near-surface of TiO2 due to the formation of triple bond SOEu and triple bond SOHAEu complexes. An extended X-ray absorption fine structure (EXAFS) technique was applied to characterize the local structural environment of the adsorbed Eu(III), and the results indicated that Eu(III) was bound to about seven or eight O atoms at a distance of about 2.40 A. The functional groups of surface-bound HA were expected to be involved in the sorption process. The measured Eu-Ti distance confirmed the formation of inner-sphere sorption complexes on a TiO2 surface.

  15. Localized Excitation of Ti(3+) Ions in the Photoabsorption and Photocatalytic Activity of Reduced Rutile TiO2.

    PubMed

    Wang, Zhiqiang; Wen, Bo; Hao, Qunqing; Liu, Li-Min; Zhou, Chuanyao; Mao, Xinchun; Lang, Xiufeng; Yin, Wen-Jin; Dai, Dongxu; Selloni, Annabella; Yang, Xueming

    2015-07-22

    In reduced TiO2, electronic transitions originating from the Ti(3+)-induced states in the band gap are known to contribute to the photoabsorption, being in fact responsible for the material's blue color, but the excited states accessed by these transitions have not been characterized in detail. In this work we investigate the excited state electronic structure of the prototypical rutile TiO2(110) surface using two-photon photoemission spectroscopy (2PPE) and density functional theory (DFT) calculations. Using 2PPE, an excited resonant state derived from Ti(3+) species is identified at 2.5 ± 0.2 eV above the Fermi level (EF) on both the reduced and hydroxylated surfaces. DFT calculations reveal that this excited state is closely related to the gap state at ∼1.0 eV below EF, as they both result from the Jahn-Teller induced splitting of the 3d orbitals of Ti(3+) ions in reduced TiO2. Localized excitation of Ti(3+) ions via 3d → 3d transitions from the gap state to this empty resonant state significantly increases the TiO2 photoabsorption and extends the absorbance to the visible region, consistent with the observed enhancement of the visible light induced photocatalytic activity of TiO2 through Ti(3+) self-doping. Our work reveals the physical origin of the Ti(3+) related photoabsorption and visible light photocatalytic activity in prototypical TiO2 and also paves the way for the investigation of the electronic structure and photoabsorption of other metal oxides.

  16. Morphologically tuned 3D/1D rutile TiO2 hierarchical hybrid microarchitectures engineered by one-step surfactant free hydrothermal method

    NASA Astrophysics Data System (ADS)

    Maria John, Maria Angelin Sinthiya; Ramamurthi, K.; Sethuraman, K.; Ramesh Babu, R.

    2017-05-01

    Present investigation reports on the surfactant free hydrothermal synthesize of the morphologically tuned hierarchical hybrid rutile titanium oxide (TiO2) microarchitectures showing three dimensional microflower structures and cook pine tree like structures on the one dimensional nanorods formed over TiO2 seed layer coated glass substrates by tuning growth temperature. TiO2 seed layer of ∼100 nm thick was coated on the glass substrates employing sol-gel spin coating method and then rutile TiO2 microarchitectures were synthesized on the TiO2 seed layer by one-step surfactant free hydrothermal method. Deposited samples were characterized by X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, UV-vis spectroscopy and photoluminescence spectroscopy techniques. Influence of the growth temperature on the crystallinity, morphology and optical properties along with the growth mechanism to achieve hierarchical microarchitectures was investigated. Present work revealed that the structural, morphological and optical properties of the TiO2 hierarchical microarchitectures strongly depend on the growth temperature. Further we proposed a model for the cause to effect possible morphological changes of rutile TiO2 microarchitectures as a function of growth temperatures on the TiO2 seeded glass substrates.

  17. 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.

  18. Rapid (∼10 min) synthesis of single-crystalline, nanorice TiO2 mesoparticles with a high photovoltaic efficiency of above 8%.

    PubMed

    Parmar, K P S; Ramasamy, Easwaramoorthi; Lee, Jinwoo; Lee, Jae Sung

    2011-08-14

    A novel rapid (∼10 min) microwave-hydrothermal synthesis is demonstrated for nanorice TiO(2) mesoparticles as an anode of a dye-sensitized solar cell with an excellent photovoltaic efficiency of above 8%.

  19. Rutile TiO2 nano-branched arrays on FTO for dye-sensitized solar cells.

    PubMed

    Wang, Hua; Bai, Yusong; Wu, Qiong; Zhou, Wei; Zhang, Hao; Li, Jinghong; Guo, Lin

    2011-04-21

    Hierarchical TiO(2) nanostructures would be desirable for preparing dye-sensitized solar cells because of their large amount of dye adsorption and superior light harvesting efficiency, as well as efficient charge separation and transport properties. In this study, rutile TiO(2) nano-branched arrays grown directly on transparent conductive glass (FTO) were prepared by a facile two-step wet chemical synthesis process, using a simple aqueous chemical growth method involving immersing the TiO(2) nanorod arrays in an aqueous TiCl(4) solution as seeds, which were prepared by a hydrothermal method. The dye-sensitized solar cells based on the TiO(2) nano-branched arrays which were only about 3 μm in length show a short-circuit current intensity of 10.05 mA cm(-2) and a light-to-electricity conversion efficiency of 3.75%, which is nearly three times as high as that of bare nanorod arrays, due to the preferable nanostructure, which not only retains the efficient charge separation and transport properties of the nanorod arrays, but also can improve the amount of dye adsorption due to the increased specific surface area from the nanobranches.

  20. 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

  1. 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.

  2. 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.

  3. 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.

  4. Hierarchical rutile TiO2 flower cluster-based high efficiency dye-sensitized solar cells via direct hydrothermal growth on conducting substrates.

    PubMed

    Ye, Meidan; Liu, Hsiang-Yu; Lin, Changjian; Lin, Zhiqun

    2013-01-28

    Dye-sensitized solar cells (DSSCs) based on hierarchical rutile TiO(2) flower clusters prepared by a facile, one-pot hydrothermal process exhibit a high efficiency. Complex yet appealing rutile TiO(2) flower films are, for the first time, directly hydrothermally grown on a transparent conducting fluorine-doped tin oxide (FTO) substrate. The thickness and density of as-grown flower clusters can be readily tuned by tailoring growth parameters, such as growth time, the addition of cations of different valence and size, initial concentrations of precursor and cation, growth temperature, and acidity. Notably, the small lattice mismatch between the FTO substrate and rutile TiO(2) renders the epitaxial growth of a compact rutile TiO(2) layer on the FTO glass. Intriguingly, these TiO(2) flower clusters can then be exploited as photoanodes to produce DSSCs, yielding a power conversion efficiency of 2.94% despite their rutile nature, which is further increased to 4.07% upon the TiCl(4) treatment.

  5. 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.

  6. Solvothermal synthesis of hedgehog-like mesoporous rutile TiO2 with improved lithium storage properties

    NASA Astrophysics Data System (ADS)

    Wang, Dongdong; Shan, Zhongqiang; Na, Ren; Huang, Wenlong; Tian, Jianhua

    2017-01-01

    Hedgehog-like mesoporous rutile TiO2 (HLR-TiO2) composed of well-defined nanoneedles is fabricated in a solvothermal system containing tetrabutyl titanate, hydrochloric acid aqueous solution and diethylene glycol with a proper volume ratio. A possible formation mechanism of the HLR-TiO2 is proposed on the basis of different experimental results and three different morphologies are obtained by changing the solvent with other conditions unchanged. Given its unique hierarchical mesoporous nanostructures, the HLR-TiO2 shows superior lithium storage properties with excellent discharge specific capacity of 243.3 mA h g-1 obtained after 100 cycles at a current rate of 1 C among the three samples, which is almost unparalleled to other rutile TiO2-based electrodes. In particular, a specific capacity of 80.2 mA h g-1 is still maintained after 2000 cycles even at a high current rate of 20 C, indicating that great potential of HLR-TiO2 as an electrode material for lithium-ion batteries (LIBs).

  7. Optical properties of rutile and anatase phases of TiO2 thin films grown by RF magnetron sputtering

    NASA Astrophysics Data System (ADS)

    Naik, V. M.; Haddad, D.; Naik, R.; Benci, J.; Auner, G. W.

    2002-03-01

    There has been a great interest in preparing both rutile (R) and anatase (A) forms of TiO2 films for various optical, electrical, photocatalysis, photovoltaics, and biosensor applications. The R-TiO2 is superior in optical properties and thermodynamically more stable than A-TiO_2. However, the latter has attracted much attention recently as the most promising photocatalytic material. In general, the formation of R-phase of TiO2 films requires a higher substrate temperature (> 300 ^circC), whereas a lower substrate temperature results in either A-phase or an amorphous structure. In the present work, we have prepared A- and R-TiO2 films ( ~ 500 nm thick) on unheated glass substrates by RF magnetron sputtering by controlling the total pressure of sputtering gases (Ar + O_2). The crystal structures of the films were confirmed by x-ray diffraction and Raman scattering. The analysis of optical transmission and reflection data measured in the UV-Visible region (175 nm- 2500 nm) show an optical bandgap of ~ 3.1 eV (direct) for R-phase, and ~ 3.2 eV (indirect) for A-phase of TiO2 films.

  8. Correlation between Bonding Geometry and Band Gap States at Organic -- inorganic interfaces: Catechol on Rutile TiO2 (110)

    NASA Astrophysics Data System (ADS)

    Diebold, Ulrike; Li, Shao-Chun; Wang, Jian-Guo; Jacobson, Peter; Gong, Xue-Qing; Selloni, Annabella

    2009-03-01

    Adsorbate-induced band gap states in semiconductors are of particular interest due to the potential of increased light absorption and photoreactivity. A combined theoretical (DFT) and experimental (STM, photoemission) study of the molecular-scale factors involved in the formation of gap states in TiO2 is presented. Using the organic catechol on rutile TiO2(110) as a model system it is found that the bonding geometry strongly affects the molecular electronic structure. At saturation catechol forms an ordered 4 x 1 overlayer. This structure is attributed to catechol adsorbed on rows of surface Ti atoms with the molecular plane tilted from the surface normal by about ±27 in an alternating fashion. In the lowest-energy structure one of the two terminal OH groups at each catechol dissociates and the O binds to a surface Ti atom in a monodentate configuration, while the other OH group forms a H-bond to the next catechol neighbor. Through proton exchange with the surface this structure transforms into one where both OH groups dissociate and the catechol is bound to two surface Ti in a bidentate configuration. Only bidendate catechol introduces states in the band gap of TiO2.

  9. 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) .

  10. Low temperature chemically synthesized rutile TiO2 photoanodes with high electron lifetime for organic dye-sensitized solar cells.

    PubMed

    Ambade, Swapnil B; Ambade, Rohan B; Mane, Rajaram S; Lee, Go-Woon; Shaikh, ShoyebMohamad F; Patil, Supriya A; Joo, Oh-Shim; Han, Sung-Hwan; Lee, Soo-Hyoung

    2013-04-11

    Electron lifetime in mesoporous nanostructured rutile TiO2 photoanodes, synthesized via a simple, cost-effective, low temperature (50-55 °C) wet chemical process, annealed at 350 °C for 1 h and not employing any sprayed TiO2 compact layer, was successfully tailored with 0.2 mM TiCl4 surface treatment that resulted in light to electric power conversion efficiency up to 4.4%.

  11. Ethanol photocatalysis on rutile TiO2(110): the role of defects and water

    PubMed Central

    Walenta, Constantin A.; Kollmannsberger, Sebastian L.; Kiermaier, Josef; Winbauer, Andreas; Tschurl, Martin

    2015-01-01

    In this work we present a stoichiometric reaction mechanism for the photocatalytic ethanol oxidation on TiO2(110). The reaction products are analyzed either under reaction conditions or after irradiation at lower temperatures. Water is identified as a quantitative by-product, which resides in a defect site. These water molecules cause a blocking of the defect sites which results in poisoning of the catalyst. By different preparation techniques of the TiO2(110) surface, the role of surface defects is further elucidated and the role of molecular oxygen is investigated. Based on the investigation, a complete photochemical reaction mechanism is given, which provides insights into general photon driven oxidation mechanisms on TiO2. PMID:26264863

  12. First-principles real-space study of electronic and optical excitations in rutile TiO2 nanocrystals

    DOE PAGES

    Hung, Linda; Baishya, Kopinjol; Öğüt, Serdar

    2014-10-17

    We model rutile titanium dioxide nanocrystals (NCs) up to ~1.5 nm in size to study the effects of quantum confinement on their electronic and optical properties. Ionization potentials (IPs) and electron affinities (EAs) are obtained via the perturbative GW approximation (G0W0) and ΔSCF method for NCs up to 24 and 64 TiO2 formula units, respectively. These demanding GW computations are made feasible by using a real-space framework that exploits quantum confinement to reduce the number of empty states needed in GW summations. Time-dependent density functional theory (TDDFT) is used to predict the optical properties of NCs up to 64 TiO2more » units. For a NC containing only 2 TiO2 units, the offsets of the IP and the EA from the corresponding bulk limits are of similar magnitude. However, as NC size increases, the EA is found to converge more slowly to the bulk limit than the IP. The EA values computed at the G0W0 and ΔSCF levels of theory are found to agree fairly well with each other, while the IPs computed with ΔSCF are consistently smaller than those computed with G0W0 by a roughly constant amount. TDDFT optical gaps exhibit weaker size dependence than GW quasiparticle gaps, and result in exciton binding energies on the order of eV. Finally, altering the dimensions of a fixed-size NC can change electronic and optical excitations up to several tenths of an eV. The largest NCs modeled are still quantum confined and do not yet have quasiparticle levels or optical gaps at bulk values. Nevertheless, we find that classical Mie-Gans theory can quite accurately reproduce the line shape of TDDFT absorption spectra, even for (anisotropic) TiO2 NCs of subnanometer size.« less

  13. First-principles real-space study of electronic and optical excitations in rutile TiO2 nanocrystals

    NASA Astrophysics Data System (ADS)

    Hung, Linda; Baishya, Kopinjol; Ã-ǧüt, Serdar

    2014-10-01

    We model rutile titanium dioxide nanocrystals (NCs) up to ˜1.5 nm in size to study the effects of quantum confinement on their electronic and optical properties. Ionization potentials (IPs) and electron affinities (EAs) are obtained via the perturbative GW approximation (G0W0) and ΔSCF method for NCs up to 24 and 64 TiO2 formula units, respectively. These demanding GW computations are made feasible by using a real-space framework that exploits quantum confinement to reduce the number of empty states needed in GW summations. Time-dependent density functional theory (TDDFT) is used to predict the optical properties of NCs up to 64 TiO2 units. For a NC containing only 2 TiO2 units, the offsets of the IP and the EA from the corresponding bulk limits are of similar magnitude. However, as NC size increases, the EA is found to converge more slowly to the bulk limit than the IP. The EA values computed at the G0W0 and ΔSCF levels of theory are found to agree fairly well with each other, while the IPs computed with ΔSCF are consistently smaller than those computed with G0W0 by a roughly constant amount. TDDFT optical gaps exhibit weaker size dependence than GW quasiparticle gaps, and result in exciton binding energies on the order of eV. Altering the dimensions of a fixed-size NC can change electronic and optical excitations up to several tenths of an eV. The largest NCs modeled are still quantum confined and do not yet have quasiparticle levels or optical gaps at bulk values. Nevertheless, we find that classical Mie-Gans theory can quite accurately reproduce the line shape of TDDFT absorption spectra, even for (anisotropic) TiO2 NCs of subnanometer size.

  14. UV and visible light synergetic photodegradation using rutile TiO2 nanorod arrays based on a p-n Junction.

    PubMed

    Ji, Tao; Cui, Ze; Zhang, Wenlong; Cao, Yunjiu; Zhang, Yongfang; He, Shu-Ang; Xu, Mingdong; Sun, Yangang; Zou, Rujia; Hu, Junqing

    2017-03-27

    Herein, we report a photocatalytic heterojunction device of rutile TiO2 nanorod arrays based on a p-n silicon junction (TiO2@PN) and its full absorption of ultraviolet and visible light for synergistic photodegradation. The fabricated TiO2@PN had excellent photocatalytic degradation of methyl orange (MO) under irradiation of a 300 W Xe lamp, and its pseudo-first-order rate constant k was 0.221 h(-1), which was greatly higher than that for TiO2 nanorod arrays based on an n-p silicon junction (TiO2@NP, 0.078 h(-1)) and glass (TiO2@G, 0.032 h(-1)). The higher photocatalytic performance of TiO2@PN could be attributed to the fact that the photovoltage (PV) of the p-n junction promotes separation of the electron-hole pairs of the TiO2, and the holes are thus left within the TiO2 nanorods to produce a strong oxidant of hydroxyl radicals (˙OH). Moreover, this heterojunction device could be easily fabricated in a large size for easy recovery and recycling, which shows its promise in the solar-driven degradation of environmental pollution.

  15. DFT computational study of the RGD peptide interaction with the rutile TiO2 (110) surface

    NASA Astrophysics Data System (ADS)

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

    2014-06-01

    Planewave DFT calculations including ab initio molecular dynamics (AIMD) were used to model the adsorption of a biologically relevant peptide sequence, arginine-glycine-aspartic acid (RGD), upon a rutile TiO2 (110) surface. It was found that binding is solely through the aspartic acid end of the RGD. The carboxy groups bind through dissociative bridging and molecular forms, similar to formic acid. The energy of adsorption is much smaller (0.5-0.77 eV) than seen for formic acid and the molecular adsorption is the strongest adsorption mode. Neutral adsorption is favoured over zwitterionic adsorption and adsorption through the carboxy group of the aspartic acid side chain rather than the terminal carboxy group is favoured due to a configuration allowing an additional surface-carbonyl bond. The RGD backbone is not significantly disrupted upon adsorption.

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

    PubMed Central

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

    2015-01-01

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

  17. Rutile TiO2(011)-2 × 1 Reconstructed Surfaces with Optical Absorption over the Visible Light Spectrum.

    PubMed

    Zhou, Rulong; Li, Dongdong; Qu, Bingyan; Sun, Xiaorui; Zhang, Bo; Zeng, Xiao Cheng

    2016-10-12

    The stable structures of the reconstructed rutile TiO2(011) surface are explored based on an evolutionary method. In addition to the well-known "brookite(001)-like" 2 × 1 reconstruction model, three 2 × 1 reconstruction structures are revealed for the first time, all being more stable in the high Ti-rich condition. Importantly, the predicted Ti4O4-2 × 1 surface model not only is in excellent agreement with the reconstructed metastable surface detected by Tao et al. [Nat. Chem. 3, 296 (2011)] from their STM experiment but also gives a consistent formation mechanism and electronic structures with the measured surface. The computed imaginary part of the dielectric function suggests that the newly predicted reconstructed surfaces are capable of optical absorption over the entire visible light spectrum, thereby offering high potential for photocatalytic applications.

  18. 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.

  19. Theoretical investigation of the uranyl ion sorption on the rutile TiO2(110) face.

    PubMed

    Perron, Hadrien; Roques, Jérôme; Domain, Christophe; Drot, Romuald; Simoni, Eric; Catalette, Hubert

    2008-12-01

    Canister integrity and radionuclide retention is of first importance for assessing the long-term safety of nuclear waste stored in engineered geologic depositories. Uranyl ion sorption on the TiO(2) rutile (110) face is investigated using periodic density functional theory (DFT) calculations. From experimental observations, only two uranyl surface complexes are observed and characterized. When the pH increases (from 1.5 to 4.5), the relative ratios of these two surface complexes are modified. From a crystallographic point of view, three sorption sites can be considered and have been studied with different protonation states of the surface to account for very acidic and low acidic conditions. The two surface complexes experimentally observed were calculated as the most stable ones, while the evolution of their sorption energies agrees with experimental data.

  20. 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.

  1. 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.

  2. A density functional theory study of atomic steps on stoichiometric rutile TiO2(110).

    PubMed

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

    2013-12-21

    We present a detailed theoretical study of the energetics of stoichiometric steps on the (110) surface of rutile TiO2. Step structures running along the <001>, <111>, and <110> directions including bulk-terminations and possible reconstructions have been considered. A robust method for extracting surface and step energies of vicinal surfaces, where the surface energies converge slowly with respect to slab thickness, is outlined and used. Based on the calculated step energies a 2D Wulff-construction is presented from which it can be concluded that in equilibrium only oxygen terminated steps running along the <001> directions and reconstructed steps along the <111> directions should be present. Finally it is found that under conditions of stoichiometry the reconstructed <111> steps should be more than twice as abundant as oxygen terminated <001> steps.

  3. 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.

  4. 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...

  5. 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...

  6. 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...

  7. 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...

  8. Magnetic, specific heat and electrical transport properties of oxygen-deficient nanosized rutile TiO2‑δ

    NASA Astrophysics Data System (ADS)

    Tran, Vinh Hung; Thi Quynh Hoa, Nguyen

    2017-03-01

    An oxygen-deficient nanosized {{TiO}}2-δ , δ ∼ 0.7 sample was synthesized by a solvothermal method, and was characterized to have both ∼3 nm amorphous solid and ∼36–46 nm diameter rutile nanowires. Physical properties of the sample were investigated by measuring magnetic, specific heat, electrical resistance and magnetoresitance properties. DC magnetization M(H) data confirm ferromagnetic behavior previously reported for undoped TiO2. Furthermore, M(T) dependence follows the power-law relation M{(T)\\propto (1-T/{T}C)}β in the near-critical regime, yielding Curie temperature {T}C ∼ 415 K and critical exponent β = 0.2. Moreover, our results of AC magnetic susceptibility measurements suggest an additional phase transition at {T}* ∼ 310 K, presumably due to spin orientation. The metallic-like electrical resistance exhibits a distinct drop below {T}* with a strong thermal hysteresis in the temperature range 225–275 K. Specific heat in the temperature range 20–300 K is well described by the sum of contributions from acoustic phonons with Debye temperature 605 K and optical phonons with Einstein temperature 113 K. Below 10 K the specific heat divulges a large excess, which can be interpreted as an additional contribution originating from soft potentials.

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

    PubMed

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

    2015-09-07

    Functionalized materials consisting of inorganic substrates with organic adsorbates play an increasing role in emerging technologies like molecular electronics or hybrid photovoltaics. For such applications, the adsorption geometry of the molecules under operating conditions, e.g., ambient temperature, is crucial because it influences the electronic properties of the interface, which in turn determine the device performance. So far detailed experimental characterization of adsorbates at room temperature has mainly been done using a combination of complementary methods like photoelectron spectroscopy together with scanning tunneling microscopy. However, this approach is limited to ensembles of adsorbates. In this paper, we show that the characterization of individual molecules at room temperature, comprising the determination of the adsorption configuration and the electrostatic interaction with the surface, can be achieved experimentally by atomic force microscopy (AFM) and Kelvin probe force microscopy (KPFM). We demonstrate this by identifying two different adsorption configurations of isolated copper(ii) meso-tetra (4-carboxyphenyl) porphyrin (Cu-TCPP) on rutile TiO2 (110) in ultra-high vacuum. The local contact potential difference measured by KPFM indicates an interfacial dipole due to electron transfer from the Cu-TCPP to the TiO2. The experimental results are verified by state-of-the-art first principles calculations. We note that the improvement of the AFM resolution, achieved in this work, is crucial for such accurate calculations. Therefore, high resolution AFM at room temperature is promising for significantly promoting the understanding of molecular adsorption.

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

    NASA Astrophysics Data System (ADS)

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

    2015-09-01

    Functionalized materials consisting of inorganic substrates with organic adsorbates play an increasing role in emerging technologies like molecular electronics or hybrid photovoltaics. For such applications, the adsorption geometry of the molecules under operating conditions, e.g., ambient temperature, is crucial because it influences the electronic properties of the interface, which in turn determine the device performance. So far detailed experimental characterization of adsorbates at room temperature has mainly been done using a combination of complementary methods like photoelectron spectroscopy together with scanning tunneling microscopy. However, this approach is limited to ensembles of adsorbates. In this paper, we show that the characterization of individual molecules at room temperature, comprising the determination of the adsorption configuration and the electrostatic interaction with the surface, can be achieved experimentally by atomic force microscopy (AFM) and Kelvin probe force microscopy (KPFM). We demonstrate this by identifying two different adsorption configurations of isolated copper(ii) meso-tetra (4-carboxyphenyl) porphyrin (Cu-TCPP) on rutile TiO2 (110) in ultra-high vacuum. The local contact potential difference measured by KPFM indicates an interfacial dipole due to electron transfer from the Cu-TCPP to the TiO2. The experimental results are verified by state-of-the-art first principles calculations. We note that the improvement of the AFM resolution, achieved in this work, is crucial for such accurate calculations. Therefore, high resolution AFM at room temperature is promising for significantly promoting the understanding of molecular adsorption.

  11. 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.

  12. Growth and characterization of rutile TiO2 nanorods on various substrates with fabricated fast-response metal-semiconductor-metal UV detector based on Si substrate

    NASA Astrophysics Data System (ADS)

    Selman, Abbas M.; Hassan, Z.

    2015-07-01

    Rutile-phase titanium dioxide nanorods (NRs) were synthesized successfully on p-type silicon (Si) (1 1 1), c-plane sapphire (Al2O3), glass coated with fluorine-doped tin oxide (FTO), glass, and quartz substrates via chemical bath deposition method. All substrates were seeded with a TiO2 seed layer synthesized with a radio frequency reactive magnetron sputtering system prior to NRs growth. The effect of substrate type on structural, morphological, and optical properties of rutile TiO2 NRs was studied. X-ray diffraction, Raman spectroscopy, and field-emission scanning electron microscopy analyses showed the tetragonal rutile structure of the synthesized TiO2 NRs. Optical properties were examined with photoluminescence (PL) spectroscopy of the grown rutile NRs on all substrates, with the spectra exhibiting one strong ultraviolet emission peak intensity compared with broad visible peak. The optimal sample of rutile NRs was grown on Si substrate. Thus, a fast-response metal-semiconductor-metal ultraviolet (UV) detector was fabricated. Upon exposure to 365 nm light (2.3 mW/cm2) at 5 V bias, the device displays 2.62 × 10-5 A photocurrent, and the response and recovery times are calculated as 18.5 and 19.1 ms, respectively. These results demonstrate that the fabricated high-quality photodiode is a promising candidate as a low-cost UV photodetector for commercially integrated photoelectronic applications.

  13. 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.

  14. 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

  15. The influence of anatase-rutile mixed phase and ZnO blocking layer on dye-sensitized solar cells based on TiO2nanofiberphotoanodes

    NASA Astrophysics Data System (ADS)

    Ding, Jianning; Li, Yan; Hu, Hongwei; Bai, Li; Zhang, Shuai; Yuan, Ningyi

    2013-01-01

    High performance is expected in dye-sensitized solar cells (DSSCs) that utilize one-dimensional (1-D) TiO2 nanostructures owing to the effective electron transport. However, due to the low dye adsorption, mainly because of their smooth surfaces, 1-D TiO2 DSSCs show relatively lower efficiencies than nanoparticle-based ones. Herein, we demonstrate a very simple approach using thick TiO2 electrospun nanofiber films as photoanodes to obtain high conversion efficiency. To improve the performance of the DSCCs, anatase-rutile mixed-phase TiO2 nanofibers are achieved by increasing sintering temperature above 500°C, and very thin ZnO films are deposited by atomic layer deposition (ALD) method as blocking layers. With approximately 40-μm-thick mixed-phase (approximately 15.6 wt.% rutile) TiO2 nanofiber as photoanode and 15-nm-thick compact ZnO film as a blocking layer in DSSC, the photoelectric conversion efficiency and short-circuit current are measured as 8.01% and 17.3 mA cm-2, respectively. Intensity-modulated photocurrent spectroscopy and intensity-modulated photovoltage spectroscopy measurements reveal that extremely large electron diffusion length is the key point to support the usage of thick TiO2 nanofibers as photoanodes with very thin ZnO blocking layers to obtain high photocurrents and high conversion efficiencies.

  16. The influence of anatase-rutile mixed phase and ZnO blocking layer on dye-sensitized solar cells based on TiO2nanofiberphotoanodes.

    PubMed

    Ding, Jianning; Li, Yan; Hu, Hongwei; Bai, Li; Zhang, Shuai; Yuan, Ningyi

    2013-01-03

    High performance is expected in dye-sensitized solar cells (DSSCs) that utilize one-dimensional (1-D) TiO2 nanostructures owing to the effective electron transport. However, due to the low dye adsorption, mainly because of their smooth surfaces, 1-D TiO2 DSSCs show relatively lower efficiencies than nanoparticle-based ones. Herein, we demonstrate a very simple approach using thick TiO2 electrospun nanofiber films as photoanodes to obtain high conversion efficiency. To improve the performance of the DSCCs, anatase-rutile mixed-phase TiO2 nanofibers are achieved by increasing sintering temperature above 500°C, and very thin ZnO films are deposited by atomic layer deposition (ALD) method as blocking layers. With approximately 40-μm-thick mixed-phase (approximately 15.6 wt.% rutile) TiO2 nanofiber as photoanode and 15-nm-thick compact ZnO film as a blocking layer in DSSC, the photoelectric conversion efficiency and short-circuit current are measured as 8.01% and 17.3 mA cm-2, respectively. Intensity-modulated photocurrent spectroscopy and intensity-modulated photovoltage spectroscopy measurements reveal that extremely large electron diffusion length is the key point to support the usage of thick TiO2 nanofibers as photoanodes with very thin ZnO blocking layers to obtain high photocurrents and high conversion efficiencies.

  17. The influence of anatase-rutile mixed phase and ZnO blocking layer on dye-sensitized solar cells based on TiO2nanofiberphotoanodes

    PubMed Central

    2013-01-01

    High performance is expected in dye-sensitized solar cells (DSSCs) that utilize one-dimensional (1-D) TiO2 nanostructures owing to the effective electron transport. However, due to the low dye adsorption, mainly because of their smooth surfaces, 1-D TiO2 DSSCs show relatively lower efficiencies than nanoparticle-based ones. Herein, we demonstrate a very simple approach using thick TiO2 electrospun nanofiber films as photoanodes to obtain high conversion efficiency. To improve the performance of the DSCCs, anatase-rutile mixed-phase TiO2 nanofibers are achieved by increasing sintering temperature above 500°C, and very thin ZnO films are deposited by atomic layer deposition (ALD) method as blocking layers. With approximately 40-μm-thick mixed-phase (approximately 15.6 wt.% rutile) TiO2 nanofiber as photoanode and 15-nm-thick compact ZnO film as a blocking layer in DSSC, the photoelectric conversion efficiency and short-circuit current are measured as 8.01% and 17.3 mA cm−2, respectively. Intensity-modulated photocurrent spectroscopy and intensity-modulated photovoltage spectroscopy measurements reveal that extremely large electron diffusion length is the key point to support the usage of thick TiO2 nanofibers as photoanodes with very thin ZnO blocking layers to obtain high photocurrents and high conversion efficiencies. PMID:23286741

  18. Comment on ``Structure and dynamics of liquid water on rutile TiO2(110)''

    NASA Astrophysics Data System (ADS)

    Wesolowski, David J.; Sofo, Jorge O.; Bandura, Andrei V.; Zhang, Zhan; Mamontov, Eugene; Předota, Milan; Kumar, Nitin; Kubicki, James D.; Kent, Paul R. C.; Vlcek, Lukas; Machesky, Michael L.; Fenter, Paul A.; Cummings, Peter T.; Anovitz, Lawrence M.; Skelton, Adam A.; Rosenqvist, Jörgen

    2012-04-01

    Liu and co-workers [Phys. Rev. B1098-012110.1103/PhysRevB.82.161415 82, 161415 (2010)] discussed the long-standing debate regarding whether H2O molecules on the defect-free (110) surface of rutile (α-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 published work, 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.

  19. Growth of anatase and rutile phase TiO2 nanoparticles using pulsed laser ablation in liquid: Influence of surfactant addition and ablation time variation

    NASA Astrophysics Data System (ADS)

    Chaturvedi, Amita; Joshi, M. P.; Mondal, P.; Sinha, A. K.; Srivastava, A. K.

    2017-02-01

    Titanium dioxide (TiO2) nanoparticles were grown using nanosecond pulsed laser ablation of Ti target in DI water and in 0.001 M sodium dodecyl sulfate (SDS) surfactant aqueous solution. Growth was carried out with varying ablation times i. e. 30 min, 60 min and 90 min. The objective of our study was to investigate the influence of variations in liquid ambience conditions on the growth of the nanoparticles in a pulsed laser ablation in liquid (PLAL) process. Size, composition and optical properties of the grown TiO2 nanoparticles were investigated using transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), optical absorption, photoluminescence (PL) spectroscopy and X-ray diffraction (XRD) studies. The obtained nanoparticles of TiO2 were found almost spherical in shape and polycrystalline in nature in both the liquid mediums i.e. DI water and aqueous solution of surfactant. Nanoparticles number density was also found to increase with increasing ablation time in both the liquid mediums. However crystalline phase of the grown TiO2 nanoparticles differs with the change in liquid ambience conditions. Selected area electron diffraction (SAED), PL and XRD studies suggest that DI water ambience is favorable for the growth of anatase phase TiO2 nanoparticles for all ablation times. While Surfactant added water ambience is favorable for the growth of rutile phase TiO2 nanoparticles but for shorter ablation times of 30 min and 60 min only, for longer ablation time of 90 min anatase phase was also observed along with the rutile phase TiO2 nanoparticles. The formation of anatase phase in DI water and rutile and anatase phase in aqueous solution of surfactant is explained on the basis of varying thermodynamic conditions with the two different liquid ambiences and different ablation times.

  20. 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.

  1. 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.

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

    DOE PAGES

    Jiang, Bin; Zuo, Jian -Min; Friis, Jesper; ...

    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

  3. 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.

  4. Density functional theory study on the structural and electronic properties of low index rutile surfaces for TiO2/SnO2/TiO2 and SnO2/TiO2/SnO2 composite systems.

    PubMed

    Beltrán, A; Andrés, J; Sambrano, J R; Longo, E

    2008-09-25

    The present study is concerned with the structural and electronic properties of the TiO2/SnO2/TiO2 and SnO2/TiO2/SnO2 composite systems. Periodic quantum mechanical method with density functional theory at the B3LYP level has been carried out. Relaxed surface energies, structural characteristics and electronic properties of the (110), (010), (101) and (00) low-index rutile surfaces for TiO2/SnO2/TiO2 and SnO2/TiO2/SnO2 models are studied. For comparison purposes, the bare rutile TiO2 and SnO2 structures are also analyzed and compared with previous theoretical and experimental data. The calculated surface energy for both rutile TiO2 and SnO2 surfaces follows the sequence (110) < (010) < (101) < (001) and the energy increases as (010) < (101) < (110) < (001) and (010) approximately = (110) < (101) < (001) for SnO2/TiO2/SnO2 and TiO2/SnO2/TiO2 composite systems, respectively. SnO2/TiO2/SnO2 presents larger values of surface energy than the individual SnO2 and TiO2 metal oxides and the TiO2/SnO2/TiO2 system renders surface energy values of the same order that the TiO2 and lower than the SnO2. An analysis of the electronic structure of the TiO2/SnO2/TiO2 and SnO2/TiO2/SnO2 systems shows that the main characteristics of the upper part of the valence bands for all the studied surfaces are dominated by the external layers, i.e., by the TiO2 and the SnO2, respectively, and the topology of the lower part of the conduction bands looks like the core layers. There is an energy stabilization of both valence band top and conduction band bottom for (110) and (010) surfaces of the SnO2/TiO2/SnO2 composite system in relation to their core TiO2, whereas an opposite trend is found for the same surfaces of the TiO2/SnO2/TiO2 composite system in relation to the bare SnO2. The present theoretical results may explain the growth of TiO2@SnO2 bimorph composite nanotape.

  5. 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.

  6. 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.

  7. High-pressure polymorphic transformation of rutile to alpha-PbO2-type TiO2 at {011}R twin boundaries.

    PubMed

    Meng, D W; Wu, X L; Sun, F; Huang, L W; Liu, F; Han, Y J; Zheng, J P; Meng, X; Mason, R

    2008-01-01

    The presence of nano-scale lamellae of the alpha-PbO2-type polymorph of TiO2 sandwiched between twinned rutile inclusions in jadeite has been confirmed by electron diffraction and high-resolution transmission electron microscopy, backed up by image simulation techniques, from ultrahigh-pressure jadeite quartzite at Shuanghe in the Dabie Mountains, China. The crystal structure is orthorhombic with lattice parameters a=4.58 A, b=5.42 A, c=5.02 A and space group Pbcn. A three-dimensional structural model has been constructed for the rutile to alpha-PbO2-type TiO2 phase transformation based on high-resolution electron microscopic images. Computer image simulation and structural model analysis reveal that rutile {011}R twin interface is a basic structural unit of alpha-PbO2-type TiO2. Nucleation of alpha-PbO2-type TiO2 lamellae 1-2 nm thick is caused by the displacement of one half of the titanium cations within the {011}R twin slab. This displacement reduces the Ti-O-Ti distance and is favored by high pressure.

  8. Effect of rutile TiO2 on the photocatalytic performance of g-C3N4/brookite-TiO2-xNy photocatalyst for NO decomposition

    NASA Astrophysics Data System (ADS)

    Li, Huihui; Wu, Xiaoyong; Yin, Shu; Katsumata, Kenichi; Wang, Yuhua

    2017-01-01

    Novel g-C3N4/rutile-brookite TiO2-xNy composite photocatalysts were fabricated through a facile solvothermal approach. The effect of rutile phase TiO2 with brookite TiO2 and g-C3N4 on the photocatalytic activity of g-C3N4/nitrogen-doped TiO2 composite was studied. The photocatalytic performance of the photocatalyst was evaluated by measuring the degradation of NO gas under visible and UV light irradiation. It is suggested that g-C3N4/rutile-brookite TiO2-xNy forms a Z-scheme photocatalytic system, which shows improvement on the photocatalytic activity than that of g-C3N4/single brookite TiO2-xNy. By importing rutile phase TiO2-xNy, the photogenerated electrons can efficiently transfer from rutile TiO2 to g-C3N4, which results in the separation of electron and hole pairs, enhancing the photocatalytic ability. However, single brookite TiO2-xNy can not remove the photogenerated electrons efficiently and the photocatalytic performances of composites decrease with g-C3N4 amount increase.

  9. 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.

  10. Probing the charge recombination in rGO decorated mixed phase (anatase-rutile) TiO2 multi-leg nanotubes

    NASA Astrophysics Data System (ADS)

    Rambabu, Y.; Jaiswal, Manu; Roy, Somnath C.

    2016-11-01

    Recombination of photo-generated charges is one of the most significant challenges in designing efficient photo-anode for photo electrochemical water oxidation. In the case of TiO2, mixed phase (anatase-rutile) junctions often shown to be more effective in suppressing electron-hole recombination compared to a single (anatase or rutile) phase. Here, we report the study of bulk and surface recombination process in TiO2 multi-leg nanotube (MLNTs) anatase-rutile (A-R) junctions decorated with reduced graphene oxide (rGO) layers, through an analysis of the photo-current and impedance characteristics. To quantify the charge transport/transfer process involved in these junctions, holes arriving at the interface of semiconductor/electrolyte were collected by adding H2O2 to the electrolyte. This enabled us to interpret the bulk and surface recombination process involved in anatase/rutile/rGO junctions for photo-electrochemical water oxidation. We correlated this quantification to the electrochemical impedance spectroscopy (EIS) measurements, and showed that in anatase/rutile junction the increase in PEC performance was due to suppression in electron-hole recombination rate at the surface states that effectively enhances the hole transfer rate to the electrolyte. On the other hand, in rGO wrapped A-R MLNTs junction it was due to both phenomenon i.e decrease in bulk recombination rate as well as increase in hole transfer rate to the electrolyte at the semiconductor/electrolyte interface.

  11. DFT + U investigation on the adsorption and initial decomposition of methylamine by a Pt single-atom catalyst supported on rutile (110) TiO2

    NASA Astrophysics Data System (ADS)

    Lv, Cun-Qin; Liu, Jian-Hong; Guo, Yong; Li, Xue-Mei; Wang, Gui-Chang

    2016-12-01

    The adsorption and initial decomposition for methylamine catalyzed by a single Pt atom supported on rutile (110) titania (namely, Pt1/TiO2-R(110)) surface have been investigated by the density functional theory slab calculations with Hubbard corrections (DFT + U). The main purpose of the work is to better understand the role of dispersed platinum metal on the surface of rutile (110) titania in the initial decomposition of methylamine. Our calculated results show that the barriers increased with the order of Csbnd H < Nsbnd H < Csbnd N, which indicates that the Csbnd H bond is the easiest to decompose and the Csbnd N bond is the most difficult to break.

  12. 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.

  13. Dielectric relaxation and localized electron hopping in colossal dielectric (Nb,In)-doped TiO2 rutile nanoceramics.

    PubMed

    Tsuji, Kosuke; Han, HyukSu; Guillemet-Fritsch, Sophie; Randall, Clive A

    2017-03-28

    Dielectric spectroscopy was performed on a Nb and In co-doped rutile TiO2 nano-crystalline ceramic (n-NITO) synthesized by a low-temperature spark plasma sintering (SPS) technique. The dielectric properties of the n-NITO were not largely affected by the metal electrode contacts. Huge dielectric relaxation was observed at a very low temperature below 35 K. Both the activation energy and relaxation time suggested that the electronic hopping motion is the underlying mechanism responsible for the colossal dielectric permittivity (CP) and its relaxation, instead of the internal barrier layer effect or a dipolar relaxation. With Havriliak-Negami (H-N) fitting, a relaxation time with a large distribution of dielectric relaxations was revealed. The broad distributed relaxation phenomena indicated that Nb and In were involved, controlling the dielectric relaxation by modifying the polarization mechanism and localized states. The associated distribution function is calculated and presented. The frequency-dependent a.c. conductance is successfully explained by a hopping conduction model of the localized electrons with the distribution function. It is demonstrated that the dielectric relaxation is strongly correlated with the hopping electrons in the localized states. The CP in SPS n-NITO is then ascribed to a hopping polarization.

  14. Low temperature EPR investigation of Co2+ ion doped into rutile TiO2 single crystal: Experiments and simulations

    NASA Astrophysics Data System (ADS)

    Zerentürk, A.; Açıkgöz, M.; Kazan, S.; Yıldız, F.; Aktaş, B.

    2017-02-01

    In this paper, we present the results of X-band EPR spectra of Co2+ ion doped rutile (TiO2) which is one of the most promising memristor material. We obtained the angular variation of spectra in three mutually perpendicular planes at liquid helium (7-13 K) temperatures. Since the impurity ions have ½ effective spin and 7/2 nuclear spin, a relatively simple spin Hamiltonian containing only electronic Zeeman and hyperfine terms was utilized. Two different methods were used in theoretical analysis. Firstly, a linear regression analysis of spectra based on perturbation theory was studied. However, this approach is not sufficient for analyzing Co+2 spectra and leads to complex eigenvectors for G and A tensors due to large anisotropy of eigenvalues. Therefore, all spectra were analyzed again with exact diagonalization of spin Hamiltonian and the high accuracy eigenvalues and eigenvectors of G and A tensors were obtained by taking into account the effect of small sample misalignment from the exact crystallographic planes due to experimental conditions. Our results show that eigen-axes of g and A tensors are parallel to crystallographic directions. Hence, our EPR experiments proves that Co2+ ions substitute for Ti4+ ions in lattice. The obtained principal values of g tensor are gx=2.110(6), gy=5.890(2), gz=3.725(7) and principal values of hyperfine tensor are Ax=42.4, Ay=152.7, Az=26 (in 10-4/cm).

  15. Fabrication of nanosized Pt on rutile TiO2 using a standing wave sonochemical reactor (SWSR)--observation of an enhanced catalytic oxidation of CO.

    PubMed

    Sivakumar, Manickam; Towata, Atsuya; Yasui, Kyuichi; Tuziuti, Toru; Kozuka, Teruyuki; Tsujimoto, Masahiko; Zhong, Ziyi; Iida, Yasuo

    2010-01-01

    Fine particles of rutile TiO2 supporting nanosized particles of Pt were prepared by a simultaneous in situ sonochemical reduction and deposition method using a standing wave sonochemical reactor (SWSR). The mean diameter of sonochemically obtained Pt particles are of 2 nm. Following this sonochemical technique, rutile TiO2 was also deposited with different weight percentages of Pt. Catalytic function of the prepared composite catalysts were tested by the oxidation of CO to CO(2). From the catalytic activity results, it has been found out that the catalysts prepared by the sonochemical method exhibited higher catalytic activity for CO oxidation, probably attributed to the higher Pt particle distribution achieved under sonication. Transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS), and diffuse reflectance spectroscopy (DRS) were employed to characterize the resulting material.

  16. 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.

  17. 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.

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

    PubMed

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

    2014-08-26

    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 Ti(3+) 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.

  19. 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

  20. Effect of N and F doping on the electronic properties of rutile TiO2 quantum dot solar cells: A first principle study

    NASA Astrophysics Data System (ADS)

    Salehi-Abar, Parvin; Kazempour, Amir

    2017-04-01

    Titanium dioxide phases are important due to their special potential for use in a broad range of applications particularly low-cost solar cells. However, this potential is actually restricted by the wide band gaps of TiO2 phases. A way to overcome this limitation is to reduce the band gap by incorporating nonmetal dopants into TiO2. For this purpose, in this paper, the effect of F and N doping on different sizes of rutile TiO2 quantum dots (QDs) was investigated using density functional theory (DFT) calculations. The results indicated that unlike nitrogen, doping of fluorine increases the efficiency of the quantum dot solar cells as a consequence of reducing auger recombination. Moreover, it was observed that when the size of QDs increases, shifting of the Fermi level towards the conduction band occurs as a favorable effect for solar cells.

  1. Functionalization of cotton fabrics with rutile TiO2 nanoparticles: Applications for superhydrophobic, UV-shielding and self-cleaning properties

    NASA Astrophysics Data System (ADS)

    Zhang, Ye; Li, Shikuo; Huang, Fangzhi; Wang, Fang; Duan, Wei; Li, Jialin; Shen, Yuhua; Xie, Anjian

    2012-03-01

    The superhydrophobic cotton fabrics were prepared by combining the coating of titanium dioxide (TiO2) with the subsequent dodecafluoroheptyl-propyl-trimethoxysilane (DFTMS) modification. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) measurements revealed that the nanosized TiO2 sphere consisted of granular rutile. The TiO2 layer coated on the cotton altered both the surface roughness for enhancing the hydrophobicity and UV-shielding property. The cotton fabric samples showed excellent water repellency with a water contact angle as high as 162°. The UV-shielding was characterized by UV-vis spectrophotometry, and the results indicated that the fabrics could dramatically reduce the UV radiation. The photocatalytic progress showed that organic stains were successfully degraded by exposure of the stained fabric to UV radiation. Such multifunctional cotton fabrics may have potentials for commercial applications.

  2. Vibrational relaxation dynamics of catalysts on TiO2 Rutile (1 1 0) single crystal surfaces and anatase nanoporous thin films

    NASA Astrophysics Data System (ADS)

    Ricks, Allen M.; Anfuso, Chantelle L.; Rodríguez-Córdoba, William; Lian, Tianquan

    2013-08-01

    Time-resolved vibrational sum frequency generation (VSFG) spectroscopy has been used to investigate the vibrational relaxation dynamics of the rhenium bipyridyl CO2-reduction catalyst Re(CO)3Cl(dcbpy) [dcbpy = 4,4‧-dicarboxy-2,2‧-bipyridine] adsorbed onto the (1 1 0) surface of a Rutile TiO2 single crystal. IR pump-VSFG probe spectra of the a‧(1) CO stretching mode indicate a ultrafast population equilibration between three CO stretching modes followed by their population relaxation via intramolecular vibrational energy transfer. Similar vibational relaxation dynamics was also observed for the same complex on anatase TiO2 nanocrystalline thin films measured by IR pump-IR probe transient absorption spectroscopy. The relaxation dynamics of ReCOA on TiO2, in DMF solution, and immobilized on Au through alkane thiol linkers were compared to examine possible effects of adsorbate-TiO2 interaction.

  3. CO2 Capture and Conversion on Rutile TiO2(110) in the Water Environment: Insight by First-Principles Calculations.

    PubMed

    Yin, Wen-Jin; Krack, Matthias; Wen, Bo; Ma, Shang-Yi; Liu, Li-Min

    2015-07-02

    The conversion of CO2 by the virtue of sunlight has the great potential to produce useful fuels or valuable chemicals while decreasing CO2 emission from the traditional fossil fuels. Here, we use the first-principles calculations combined with the periodic continuum solvation model (PCSM) to explore the adsorption and reactivity of CO2 on rutile TiO2(110) in the water environment. The results exhibit that both adsorption structures and reactivity of CO2 are greatly affected by water coadsorption on rutile TiO2(110). In particular, the solvation effect can change the most stable adsorption configuration of CO2 and H2O on rutile TiO2(110). In addition, the detailed conversion mechanism of CO2 reduction is further explored in the water environment. The results reveal that the solvation effect cannot only greatly decrease the energy barrier of CO2 reduction but also affect the selectivity of the reaction processes. These results presented here show the importance of the aqueous solution, which should be helpful to understand the detailed reaction processes of photocatalysts.

  4. Facile oxidative conversion of TiH2 to high-concentration Ti(3+)-self-doped rutile TiO2 with visible-light photoactivity.

    PubMed

    Grabstanowicz, Lauren R; Gao, Shanmin; Li, Tao; Rickard, Robert M; Rajh, Tijana; Liu, Di-Jia; Xu, Tao

    2013-04-01

    TiO2, in the rutile phase with a high concentration of self-doped Ti(3+), has been synthesized via a facile, all inorganic-based, and scalable method of oxidizing TiH2 in H2O2 followed by calcinations in Ar gas. The material was shown to be photoactive in the visible-region of the electromagnetic spectrum. Powdered X-ray diffraction (PXRD), transmission electron microscopy (TEM), ultraviolet-visible-near-infrared (UV-vis-NIR), diffuse reflectance spectroscopy (DRS), and Brunauer-Emmett-Teller (BET) methods were used to characterize the crystalline, structural, and optical properties and specific surface area of the as-synthesized Ti(3+)-doped rutile, respectively. The concentration of Ti(3+) was quantitatively studied by electron paramagnetic resonance (EPR) to be as high as one Ti(3+) per ~4300 Ti(4+). Furthermore, methylene blue (MB) solution and an industry wastewater sample were used to examine the photocatalytic activity of the Ti(3+)-doped TiO2 which was analyzed by UV-vis absorption, Fourier transform infrared spectroscopy (FT-IR), and electrospray ionization mass spectrometry (ESI-MS). In comparison to pristine anatase TiO2, our Ti(3+) self-doped rutile sample exhibited remarkably enhanced visible-light photocatalytic degradation on organic pollutants in water.

  5. Locating structures and evolution pathways of reconstructed rutile TiO2(011) using genetic algorithm aided density functional theory calculations.

    PubMed

    Ding, Pan; Gong, Xue-Qing

    2016-05-01

    Titanium dioxide (TiO2) is an important metal oxide that has been used in many different applications. TiO2 has also been widely employed as a model system to study basic processes and reactions in surface chemistry and heterogeneous catalysis. In this work, we investigated the (011) surface of rutile TiO2 by focusing on its reconstruction. Density functional theory calculations aided by a genetic algorithm based optimization scheme were performed to extensively sample the potential energy surfaces of reconstructed rutile TiO2 structures that obey (2 × 1) periodicity. A lot of stable surface configurations were located, including the global-minimum configuration that was proposed previously. The wide variety of surface structures determined through the calculations performed in this work provide insight into the relationship between the atomic configuration of a surface and its stability. More importantly, several analytical schemes were proposed and tested to gauge the differences and similarities among various surface structures, aiding the construction of the complete pathway for the reconstruction process.

  6. 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.

  7. Comparison between sol-gel-derived anatase- and rutile-structured TiO2 coatings in soft-tissue environment.

    PubMed

    Rossi, S; Moritz, N; Tirri, T; Peltola, T; Areva, S; Jokinen, M; Happonen, R-P; Närhi, T

    2007-09-15

    The bioactivity of the surface reactive TiO(2) coatings for medical implants can be locally modified by CO(2) laser processing to match with the properties of surrounding tissues. The TiO(2) coatings heat-treated at 500 degrees C exhibit in vitro bioactivity. With further CO(2) laser treatment they exhibit enhanced in vitro bioactivity. The aim of this in vivo study was to compare the performance of heat-treated anatase-structured TiO(2) coatings with preheat-treated and CO(2) laser-treated rutile-structured coatings in terms of their ability to attach soft connective tissues. The coatings were characterized with TF-XRD and AFM. TiO(2)-coated discs were implanted in rats. The samples were analyzed with routine histology, SEM-EDS, and TEM. In both groups, already at 3 days, soft connective tissues were in immediate contact with the surface. No thick crystalline CaP layer was detected by SEM-EDS, but a thin amorphous CaP layer was detected by XPS. No gap between the cell membrane and the coating could be observed in TEM pictures. No differences were observed between the anatase- and rutile-structured coatings in terms of tissue responses. Further studies are needed to verify if the tissues are adherent to the surface of the implant.

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

    NASA Astrophysics Data System (ADS)

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

    2015-08-01

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

  9. 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.

  10. Ab initio study of the atomic level structure of the rutile TiO2 (110) - titanium nitride (TiN) interface.

    PubMed

    Gutierrez Moreno, Jose Julio; Nolan, Michael

    2017-09-22

    Titanium nitride (TiN) is widely used in industry as a protective coating due to its hardness and resistance to corrosion and can spontaneously form a thin oxide layer when it is exposed to air, which could modify the properties of the coating. With limited understanding of the TiO2 - TiN interfacial system at present, this work aims to describe the structural and electronic properties of oxidized TiN based on a density functional theory (DFT) study of the rutile TiO2 (110) - TiN (100) interface model system, also including Hubbard +U correction on Ti 3d states. The small lattice mismatch gives a good stability to the TiO2 - TiN interface after depositing the oxide onto TiN through the formation of interfacial Ti - O bonds. Our DFT+U study shows the presence of Ti(3+) cations in the TiO2 region, which are preferentially located next to the interface region as well as the rotation of the rutile TiO2 octahedra in the interface structure. Although the vacancy formation energies for Ti in TiN (Evac (Ti) ≥ 4.03 eV) or O in the oxide (Evac (O) ≥ 3.40 eV) are quite high relative to perfect TiO2 - TiN, defects are known to form during the oxide growth and can therefore be present after TiO2 formation. Our results show that a structure with exchanged O and N can lie 0.82 eV higher in energy than the perfect system, suggesting the stability of structures with interdiffused O and N anions at ambient conditions. The presence of N in TiO2 introduces N 2p states localized between the top edge of the O 2p valence states and the mid-gap Ti(3+) 3d states, thus reducing the bandgap in the TiO2 region for the exchanged O/N interface EDOS. The outcomes of these simulations give us a most comprehensive insight on the atomic level structure and the electronic properties of oxidised TiN surfaces.

  11. Carbon as amorphous shell and interstitial dopant in mesoporous rutile TiO2: Bio-template assisted sol-gel synthesis and photocatalytic activity

    NASA Astrophysics Data System (ADS)

    Mohamed, Mohamad Azuwa; Wan Salleh, Wan Norharyati; Jaafar, Juhana; Rosmi, Mohamad Saufi; Mohd. Hir, Zul Adlan; Abd Mutalib, Muhazri; Ismail, Ahmad Fauzi; Tanemura, Masaki

    2017-01-01

    Regenerated cellulose membrane was used as bio-template nanoreactor for the formation of rutile TiO2 mesoporous, as well as in-situ carbon dopant in acidified sol-gel system. The effects of calcination temperature on the physicochemical characteristic of core-shell nanostructured of bio-templated C-doped mesoporous TiO2 are highlighted in this study. By varying the calcination temperature, the thickness of the carbon shell coating on TiO2, crystallinity, surface area, and optical properties could be tuned as confirmed by HRTEM, nitrogen adsorption/desorption measurement, XRD and UV-vis-NIR spectroscopy. The results suggested that increment in the calcination temperature would lead to the band gap narrowing from 2.95 to 2.80 eV and the thickness of carbon shell increased from 0.40 to 1.20 nm. The x-ray photoelectron spectroscopy showed that the visible light absorption capability was mainly due to the incorporation of carbon dopant at interstitial position in the TiO2 to form Osbnd Tisbnd C or Tisbnd Osbnd C bond. In addition, the formation of the carbon core-shell nanostructured was due to carbonaceous layer grafted onto the surface of TiO2 via Tisbnd Osbnd C and Tisbnd OCO bonds. The result indicated that bio-templated C-doped core-shell mesoporous TiO2 prepared at 300 °C exhibited the highest photocatalytic activity. It is worthy to note that, the calcination temperature provided a huge impact towards improving the physicochemical and photocatalytic properties of the prepared bio-templated C-doped core-shell mesoporous TiO2.

  12. Moving into advanced nanomaterials. Toxicity of rutile TiO2 nanoparticles immobilized in nanokaolin nanocomposites on HepG2 cell line.

    PubMed

    Bessa, Maria João; Costa, Carla; Reinosa, Julian; Pereira, Cristiana; Fraga, Sónia; Fernández, José; Bañares, Miguel A; Teixeira, João Paulo

    2017-02-01

    Immobilization of nanoparticles on inorganic supports has been recently developed, resulting in the creation of nanocomposites. Concerning titanium dioxide nanoparticles (TiO2 NPs(1)), these have already been developed in conjugation with clays, but so far there are no available toxicological studies on these nanocomposites. The present work intended to evaluate the hepatic toxicity of nanocomposites (C-TiO2(2)), constituted by rutile TiO2 NPs immobilized in nanokaolin (NK(3)) clay, and its individual components. These nanomaterials were analysed by means of FE-SEM(4) and DLS(5) analysis for physicochemical characterization. HepG2 cells were exposed to rutile TiO2 NPs, NK clay and C-TiO2 nanocomposite, in the presence and absence of serum for different exposure periods. Possible interferences with the methodological procedures were determined for MTT,(6) neutral red uptake, alamar blue (AB), LDH,(7) and comet assays, for all studied nanomaterials. Results showed that MTT, AB and alkaline comet assay were suitable for toxicity analysis of the present materials after slight modifications to the protocol. Significant decreases in cell viability were observed after exposure to all studied nanomaterials. Furthermore, an increase in HepG2 DNA damage was observed after shorter periods of exposure in the absence of serum proteins and longer periods of exposure in their presence. Although the immobilization of nanoparticles in micron-sized supports could, in theory, decrease the toxicity of single nanoparticles, the selection of a suitable support is essential. The present results suggest that NK clay is not the appropriate substrate to decrease TiO2 NPs toxicity. Therefore, for future studies, it is critical to select a more appropriate substrate for the immobilization of TiO2 NPs. Copyright © 2016 Elsevier Inc. All rights reserved.

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

    PubMed

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

    2015-01-01

    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 Tm(3+). 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 Tm(3+) was confirmed by X-ray photoelectron spectroscopy and UV-vis spectroscopy: the incorporation of Tm(3+) was confirmed by the generation of new absorption bands that could be assigned to Tm(3+) 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.

  14. 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

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

    DOE PAGES

    Lan, Tian; Li, Chen W.; Hellman, O.; ...

    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

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

    NASA Astrophysics Data System (ADS)

    Lan, Tian; Li, C. W.; Hellman, O.; Kim, D. S.; Muñoz, J. A.; Smith, H.; Abernathy, D. L.; Fultz, B.

    2015-08-01

    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. Inelastic neutron scattering was used to measure the temperature dependence of the phonon density of states (DOS) of rutile TiO2 from 300 to 1373 K. Surprisingly, these anomalous acoustic phonons were found to increase in frequency with temperature. First-principles calculations showed that with lattice expansion, the potentials for the anomalous acoustic phonons transform from quadratic to quartic, stabilizing the rutile phase at high temperatures. In these modes, the vibrational displacements of adjacent Ti and O atoms cause variations in hybridization of 3 d electrons of Ti and 2 p electrons of O atoms. 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.

  17. A comparative study of optical absorption and photocatalytic properties of nanocrystalline single-phase anatase and rutile TiO2 doped with transition metal cations

    NASA Astrophysics Data System (ADS)

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

    2013-02-01

    The effect of nanocrystalline TiO2 doping with transition metal cations (Cu2+, Fe3+, Co2+, Cr3+) on their optical absorption and photocatalytic properties was investigated. The obtained metal-doped TiO2 samples were characterized by X-ray diffraction, scanning electron microscopy, and UV-vis absorption spectroscopy. It is shown that doping effect on anatase (A) and rutile (R) properties is quite different, being much stronger and complicated on A than on R. Contrary to doped R, doped A revealed a significant red shift of the absorption edge along with the band gap narrowing. Photocatalytic activity of anatase increases upon doping in the order: Arutile samples decreases upon doping in the series R>R/Co>R/Cu>R/Fe>R/Cr, indicating the inhibitory effect of impurity cations. This fact correlates with the decrease in the UV absorption of the doped rutile in the region of the Hg-lamp irradiation at 4.88 eV.

  18. 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.

  19. 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.

  20. High-permittivity metal-insulator-metal capacitors with TiO2 rutile dielectric and RuO2 bottom electrode

    NASA Astrophysics Data System (ADS)

    Hudec, B.; Husekova, K.; Dobrocka, E.; Lalinsky, T.; Aarik, J.; Aidla, A.; Frohlich, K.

    2010-02-01

    We describe properties of MIM capacitor structures with the RuO2 bottom electrode, TiO2 dielectric film and various top electrodes. The TiO2 films were grown by atomic layer deposition (ALD) at temperature 425 °C on metal organic chemical vapour deposited (MOCVD) RuO2 bottom electrodes grown at 300 °C. Due to local epitaxial growth on the RuO2 rutile structure, TiO2 films with the permittivity 135 and equivalent oxide thickness 0.58 nm were obtained. Capacitance density as high as 60 fF/μm2 was achieved. Au and Ni films for top electrodes were prepared by evaporation at room temperature. RuO2 films for top electrodes were grown by MOCVD. Strong effect of top electrode material on capacitance and leakage currents was observed. In addition, the stacks with TiO2 dielectric were found to be very sensitive to oxygen post-deposition treatment.

  1. Structural properties of rutile TiO2 nanoparticles accumulated in a model of gastrointestinal epithelium elucidated by micro-beam x-ray absorption fine structure spectroscopy

    NASA Astrophysics Data System (ADS)

    Veronesi, G.; Brun, E.; Fayard, B.; Cotte, M.; Carrière, M.

    2012-05-01

    Micro-beam x-ray absorption fine structure spectroscopy was used to investigate rutile TiO2 nanoparticles internalized into gastrointestinal cells during their crossing of a gut model barrier. Nanoparticles diluted in culture medium tend to accumulate in cells after 48 h exposure; however, no spectral differences arise between particles in cellular and in acellular environments, as corroborated by quantitative analysis. This finding establishes that no modification of the lattice properties of the nanoparticles occurs upon interaction with the barrier. These measurements demonstrate the possibility of interrogating nanoparticles in situ within cells, suggesting a way to investigate their fate when incorporated in biological hosts.

  2. 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

  3. 3D hierarchical rutile TiO2 and metal-free organic sensitizer producing dye-sensitized solar cells 8.6% conversion efficiency.

    PubMed

    Lin, Jianjian; Heo, Yoon-Uk; Nattestad, Andrew; Sun, Ziqi; Wang, Lianzhou; Kim, Jung Ho; Dou, Shi Xue

    2014-08-29

    Three-dimensional (3D) hierarchical nanoscale architectures comprised of building blocks, with specifically engineered morphologies, are expected to play important roles in the fabrication of 'next generation' microelectronic and optoelectronic devices due to their high surface-to-volume ratio as well as opto-electronic properties. Herein, a series of well-defined 3D hierarchical rutile TiO2 architectures (HRT) were successfully prepared using a facile hydrothermal method without any surfactant or template, simply by changing the concentration of hydrochloric acid used in the synthesis. The production of these materials provides, to the best of our knowledge, the first identified example of a ledgewise growth mechanism in a rutile TiO2 structure. Also for the first time, a Dye-sensitized Solar Cell (DSC) combining a HRT is reported in conjunction with a high-extinction-coefficient metal-free organic sensitizer (D149), achieving a conversion efficiency of 5.5%, which is superior to ones employing P25 (4.5%), comparable to state-of-the-art commercial transparent titania anatase paste (5.8%). Further to this, an overall conversion efficiency 8.6% was achieved when HRT was used as the light scattering layer, a considerable improvement over the commercial transparent/reflector titania anatase paste (7.6%), a significantly smaller gap in performance than has been seen previously.

  4. 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.

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

    PubMed

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

    2016-07-20

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

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

    PubMed

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

    2016-02-24

    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.

  7. 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.

  8. The mechanism of emerging catalytic activity of gold nano-clusters on rutile TiO2(110) in CO oxidation reaction

    NASA Astrophysics Data System (ADS)

    Mitsuhara, K.; Tagami, M.; Matsuda, T.; Visikovskiy, A.; Takizawa, M.; Kido, Y.

    2012-03-01

    This paper reveals the fact that the O adatoms (Oad) adsorbed on the 5-fold Ti rows of rutile TiO2(110) react with CO to form CO2 at room temperature and the oxidation reaction is pronouncedly enhanced by Au nano-clusters deposited on the above O-rich TiO2(110) surfaces. The optimum activity is obtained for 2D clusters with a lateral size of ˜1.5 nm and two-atomic layer height corresponding to ˜50 Au atoms/cluster. This strong activity emerging is attributed to an electronic charge transfer from Au clusters to O-rich TiO2(110) supports observed clearly by work function measurement, which results in an interface dipole. The interface dipoles lower the potential barrier for dissociative O2 adsorption on the surface and also enhance the reaction of CO with the Oad atoms to form CO2 owing to the electric field of the interface dipoles, which generate an attractive force upon polar CO molecules and thus prolong the duration time on the Au nano-clusters. This electric field is screened by the valence electrons of Au clusters except near the perimeter interfaces, thereby the activity is diminished for three-dimensional clusters with a larger size.

  9. 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)

  10. Growth of nitrogen-doped rutile TiO2 nanorod arrays and their improved performance in all-solid-state solar cells

    NASA Astrophysics Data System (ADS)

    Sun, Qiong; Hong, Yong; Liu, Qiuhong; Zhang, Min; Yu, Liyan; Dong, Lifeng

    2017-07-01

    In this study, nitrogen-doped rutile TiO2 nanorod arrays (N-TiO2) were prepared through a facile hydrothermal process for the first time, using ammonia and butyl titanate as nitrogen and titanium source, respectively. The crystal structure and morphology of N-TiO2 were investigated by x-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM), which showed that the length and diameter of the nanorods as well as the intensity of (0 0 2) diffraction peak increased sharply with doping concentration. According to the x-ray photoelectron spectroscopy (XPS), only a small amount of nitrogen in reactants was deposited on the surface of TiO2 nanorods, and even less could enter into bulk TiO2 and form O-Ti-N structure. With the increase of doped nitrogen content, photoelectrical conversion efficiency of all-solid-state dye-sensitized solar cells first increased and then decreased, with the highest value of 2.88%, which was much higher than that of un-doped samples (1.57%). The improvement of the solar cells could be mainly attributed to vertical growth of the nanorod caused by the addition of nitrogen. After sintering treatment, the growth of (1 0 1) crystal face further increased the photoelectrical conversion efficiency to about 3.86%. Meanwhile, commercial liquid iodic electrolyte was also chosen to fabricate solar cells for comparison, and an efficiency of 5.36% was reached.

  11. Correlation between bonding geometry and band gap states at organic-inorganic interfaces: catechol on rutile TiO2(110).

    PubMed

    Li, Shao-Chun; Wang, Jian-guo; Jacobson, Peter; Gong, X-Q; Selloni, Annabella; Diebold, Ulrike

    2009-01-28

    Adsorbate-induced band gap states in semiconductors are of particular interest due to the potential of increased light absorption and photoreactivity. A combined theoretical and experimental (STM, photoemission) study of the molecular-scale factors involved in the formation of gap states in TiO(2) is presented. Using the organic catechol on rutile TiO(2)(110) as a model system, it is found that the bonding geometry strongly affects the molecular electronic structure. At saturation catechol forms an ordered 4 x 1 overlayer. This structure is attributed to catechol adsorbed on rows of surface Ti atoms with the molecular plane tilted from the surface normal in an alternating fashion. In the computed lowest-energy structure, one of the two terminal OH groups at each catechol dissociates and the O binds to a surface Ti atom in a monodentate configuration, whereas the other OH group forms an H-bond to the next catechol neighbor. Through proton exchange with the surface, this structure can easily transform into one where both OH groups dissociate and the catechol is bound to two surface Ti in a bidentate configuration. Only bidendate catechol introduces states in the band gap of TiO(2).

  12. The mechanism of emerging catalytic activity of gold nano-clusters on rutile TiO2(110) in CO oxidation reaction.

    PubMed

    Mitsuhara, K; Tagami, M; Matsuda, T; Visikovskiy, A; Takizawa, M; Kido, Y

    2012-03-28

    This paper reveals the fact that the O adatoms (O(ad)) adsorbed on the 5-fold Ti rows of rutile TiO(2)(110) react with CO to form CO(2) at room temperature and the oxidation reaction is pronouncedly enhanced by Au nano-clusters deposited on the above O-rich TiO(2)(110) surfaces. The optimum activity is obtained for 2D clusters with a lateral size of ∼1.5 nm and two-atomic layer height corresponding to ∼50 Au atoms∕cluster. This strong activity emerging is attributed to an electronic charge transfer from Au clusters to O-rich TiO(2)(110) supports observed clearly by work function measurement, which results in an interface dipole. The interface dipoles lower the potential barrier for dissociative O(2) adsorption on the surface and also enhance the reaction of CO with the O(ad) atoms to form CO(2) owing to the electric field of the interface dipoles, which generate an attractive force upon polar CO molecules and thus prolong the duration time on the Au nano-clusters. This electric field is screened by the valence electrons of Au clusters except near the perimeter interfaces, thereby the activity is diminished for three-dimensional clusters with a larger size.

  13. 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

    2013-10-09

    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.

  14. Phosphate modified N/Si co-doped rutile TiO2 nanorods for photoelectrochemical water oxidation

    NASA Astrophysics Data System (ADS)

    Zhang, Xiaofan; Zhang, Bingyan; Luo, Yanping; Lv, Xiaowei; Shen, Yan

    2017-01-01

    Surface modification of TiO2 film provides possibilities to improve photoelectrochemical (PEC) activity. In this study, we report on phosphate modified N/Si co-doped TiO2 nanorods films (Pi-N/Si-TiO2 NRs) for PEC water oxidation. Compared to the pristine TiO2 NRs, the Pi-N/Si-TiO2 NRs photoanode shows a 4.65-fold enhanced photocurrent density (1.44 mA cm-2) under light illumination. This significant improvement can be attributed to the synergistic effect of phosphate modification and the N and Si co-dopants. In addition to the improvement of ultraviolet and visible light response by N and Si co-dopants, phosphate modification is mainly responsible for charge transfer at the interface of the photoanode/electrolyte.

  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. 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...

  17. 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...

  18. 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...

  19. Effect of subsurface Ti-interstitials on the bonding of small gold clusters on rutile TiO(2)(110).

    PubMed

    Madsen, Georg K H; Hammer, Bjørk

    2009-01-28

    The density functional theory is used to examine the electronic structure of small Au clusters, supported on rutile TiO(2)(110) surfaces having subsurface Ti-interstitials. The interstitials reduce the surface and we find that negatively charged gold clusters are stabilized with respect to the stoichiometric surface. The behavior of the open-shell gold clusters can be rationalized in terms of the highest occupied molecular orbitals and the resulting electron affinities. The relative stabilities of closed-shell gold clusters led to recent disagreements in the literature. We show that they are very dependent on the density functional used. As expected, a redshift in the CO stretch vibration is calculated for CO adsorbed on a negatively charged cluster. Somewhat surprisingly a larger redshift is found for CO adsorbed on an overall positively charged Au(3) cluster. This is explained by CO being a local probe of the individual Au charges and one Au atom having an electron accumulation.

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

    PubMed

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

    2016-03-03

    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.

  1. First-principles study of anatase and rutile TiO2 doped with Eu ions: A comparison of GGA and LDA+U calculations

    NASA Astrophysics Data System (ADS)

    Rubio-Ponce, A.; Conde-Gallardo, A.; Olguín, D.

    2008-07-01

    Here, we study some changes on the electronic band structure of anatase and rutile TiO2 doped with Eu ions using first-principles calculations. This work presents a comparison of a GGA and LDA+U calculations. It was found that the GGA calculations show better agreement with experimental data than LDA+U calculations. From our study a series of highly localized states in the host matrix band gap was found. According to our calculations, and as it is widely known, these states are mainly Eu4f character. However, contrary to the common idea that Eu orbitals should be localized as atom-free-like states, our calculations show that Eu orbitals hybridize with the host oxygen and titanium orbitals; the same occurs in the valence band, as well as in the conduction band region.

  2. 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

  3. 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.

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

    EPA Science Inventory

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

  5. 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...

  6. 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...

  7. 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...

  8. Covalent O-H bonds as electron traps in proton-rich rutile TiO2 nanoparticles.

    PubMed

    Zhang, Jing; Steigerwald, Michael; Brus, Louis; Friesner, Richard A

    2014-01-01

    The cation in the electrolyte of the dye-sensitized solar cell (DSSC) has a profound effect on electron trapping and transport behavior in TiO2 nanocrystalline film; this is one of the important factors that determines the overall efficiency of DSSCs. Here, we present a quantum mechanical investigation on the structures and energetics of proton-induced electron trap states and the thermodynamical barrier heights for the ambipolar diffusion of proton/electron pair using a large cluster model for the computations. Our calculations indicate that protons react with TiO2 to form covalent O-H bonds. This is in contrast to the reaction of Li(+) with TiO2, in which case the alkali metal is more accurately described as a simple coordinating cation. The covalent O-H bonding leads both to deeper electron trap states and to significantly higher barriers for the diffusion of carriers. These results are qualitatively consistent with experimental observations, and they extend our understanding of the cation effect in DSSCs at an atomic level of detail.

  9. Effect of Ar ion irradiation on the room temperature ferromagnetism of undoped and Cu-doped rutile TiO2 single crystals

    NASA Astrophysics Data System (ADS)

    Xu, Nan-Nan; Li, Gong-Ping; Lin, Qiao-Lu; Liu, Huan; Bao, Liang-Man

    2016-11-01

    Remarkable room-temperature ferromagnetism was observed both in undoped and Cu-doped rutile TiO2 single crystals (SCs). To tune their magnetism, Ar ion irradiation was quantitatively performed on the two crystals in which the saturation magnetizations for the samples were enhanced distinctively. The post-irradiation led to a spongelike layer in the near surface of the Cu-doped TiO2. Meanwhile, a new CuO-like species present in the sample was found to be dissolved after the post-irradiation. Analyzing the magnetization data unambiguously reveals that the experimentally observed ferromagnetism is related to the intrinsic defects rather than the exotic Cu ions, while these ions are directly involved in boosting the absorption in the visible region. Project supported by the National Natural Science Foundation of China (Grant No. 11575074), the Open Project of State Key laboratory of Crystal Material, Shandong University, China (Grant No. KF1311), the Open Project of Key Laboratory for Magnetism and Magnetic Materials of the Ministry of Education, Lanzhou University, China (Grant No. LZUMMM2012003), the Open Project of Key Laboratory of Beam Technology and Material Modification of Ministry of Education, Beijing Normal University, China (Grant No. 201204), and the Fundamental Research Funds for the Central Universities, China (Grant No. lzujbky-2015-240).

  10. 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.

  11. Modification of the microstructure and electronic properties of rutile TiO2 thin films with 79 MeV Br ion irradiation

    NASA Astrophysics Data System (ADS)

    Rath, Haripriya; Dash, P.; Singh, U. P.; Avasthi, D. K.; Kanjilal, D.; Mishra, N. C.

    2015-12-01

    Modifications induced by 79 MeV Br ions in rutile titanium dioxide thin films, synthesized by dc magnetron sputtering are presented. Irradiations did not induce any new XRD peak corresponding to any other phase. The area and the width of the XRD peaks were considerably affected by irradiation, and peaks shifted to lower angles. But the samples retained their crystallinity at the highest fluence (1 × 1013 ions cm-2) of irradiation even though the electronic energy loss of 79 MeV Br ions far exceeds the reported threshold value for amorphization of rutile TiO2. Fitting of the fluence dependence of the XRD peak area to Poisson equation yielded the radius of ion tracks as 2.4 nm. Ion track radius obtained from the simulation based on the thermal spike model matches closely with that obtained from the fluence dependence of the area under XRD peaks. Williamson-Hall analysis of the XRD spectra indicated broadening and shifting of the peaks are a consequence of irradiation induced defect accumulation leading to microstrains, as was also indicated by Raman and UV-Visible absorption study.

  12. 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.

  13. Formation of surface nanostructures on rutile (TiO2): comparative study of low-energy cluster ion and high-energy monoatomic ion impact

    NASA Astrophysics Data System (ADS)

    Popok, V. N.; Jensen, J.; Vučković, S.; Mackova, A.; Trautmann, C.

    2009-10-01

    The formation of nanostructures on rutile (TiO2) surfaces formed after the implantation of kiloelectronvolt-energy Ar_n^+ cluster ions and megaelectronvolt- to gigaelectronvolt-energy multiply charged heavy ions (Iq+, Taq+ and Uq+) is studied. Despite the differences in stopping and energy transfer mechanisms between the kiloelectronvolt-energy cluster ions and megaelectronvolt-energy monoatomic ions, their impacts lead to a similar type of surface damage, namely craters. For the cluster ion implantation the craters are caused by the multiple-collision effect (dominated by nuclear stopping) and the high density of energy and momentum transferred to the target, while for the case of megaelectronvolt multiply charged ions the craters are probably formed due to the Coulomb explosion and fast energy transfer caused by the electronic stopping. At ion energies in the gigaelectronvolt range, nanosize protrusions, so-called hillocks, are observed on the surface. It is suggested that electronic stopping leads to the formation of continuous tracks and the transferred energy is high enough to melt the material along the whole projectile path. Elastic rebound of the tension between the molten and solid state phases leads to liquid flow, expansion and quenching of the melt, thus forming the hillocks. Atomic force microscopy measurements carried out under different environmental conditions (temperature and atmosphere) suggest that the damaged material at the nanosize impact spots has very different water affinity properties (higher hydrophilicity or water adsorption) compared with the non-irradiated rutile surface.

  14. Direct Low-Temperature Growth of Single-Crystalline Anatase TiO2 Nanorod Arrays on Transparent Conducting Oxide Substrates for Use in PbS Quantum-Dot Solar Cells.

    PubMed

    Chung, Hyun Suk; Han, Gill Sang; Park, So Yeon; Shin, Hee-Won; Ahn, Tae Kyu; Jeong, Sohee; Cho, In Sun; Jung, Hyun Suk

    2015-05-20

    We report on the direct growth of anatase TiO2 nanorod arrays (A-NRs) on transparent conducting oxide (TCO) substrates that can be directly applied to various photovoltaic devices via a seed layer mediated epitaxial growth using a facile low-temperature hydrothermal method. We found that the crystallinity of the seed layer and the addition of an amine functional group play crucial roles in the A-NR growth process. The A-NRs exhibit a pure anatase phase with a high crystallinity and preferred growth orientation in the [001] direction. Importantly, for depleted heterojunction solar cells (TiO2/PbS), the A-NRs improve both electron transport and injection properties, thereby largely increasing the short-circuit current density and doubling their efficiency compared to TiO2 nanoparticle-based solar cells.

  15. 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.

  16. Influence of hydroxyls on Pd atom mobility and clustering on rutile TiO(2)(011)-2 × 1.

    PubMed

    Addou, Rafik; Senftle, Thomas P; O'Connor, Nolan; Janik, Michael J; van Duin, Adri C T; Batzill, Matthias

    2014-06-24

    Understanding agglomeration of late transition metal atoms, such as Pd, on metal oxide supports, such as TiO2, is critical for designing heterogeneous catalysts as well as for controlling metal/oxide interfaces in general. One approach for reducing particle sintering is to modify the metal oxide surface with hydroxyls that decrease adatom mobility. We study by scanning tunneling microscopy experiments, density functional theory (DFT) calculations, and Monte Carlo (MC) computer simulations the atomistic processes of Pd sintering on a hydroxyl-modified TiO2(011)-2 × 1 surface. The formation of small 1-3 atom clusters that are stable at room temperature is achieved on the hydroxylated surface, while much larger clusters are formed under the same conditions on a hydroxyl-free surface. DFT shows that this is a consequence of stronger binding of Pd atoms adjacent to hydroxyls and increased surface diffusion barriers for Pd atoms on the hydroxylated surface. DFT, kinetic MC, and ReaxFF-based NVT-MC simulations show that Pd clusters larger than single Pd monomers can adsorb the hydrogen from the oxide surface and form Pd hydrides. This depletes the surface hydroxyl coverage, thus allowing Pd to more freely diffuse and agglomerate at room temperature. Experimentally, this causes a bimodal cluster size distribution with 1-3 atom clusters prevalent at low Pd coverage, while significantly larger clusters become dominant at higher Pd concentrations. This study demonstrates that hydroxylated oxide surfaces can significantly reduce Pd cluster sizes, thus enabling the preparation of surfaces populated with metal clusters composed of single to few atoms.

  17. Co-adsorption of oxygen and formic acid on rutile TiO2 (110) studied by infrared reflection-absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Mattsson, Andreas; Österlund, Lars

    2017-09-01

    Adsorption of formic acid and co-adsorption with oxygen have been investigated on the rutile TiO2(110) surface using p- and s-polarized infrared reflection-absorption spectroscopy (IRRAS) at O2 exposures between 45 L to 8100 L and at temperatures between 273 K and 343 K. On the clean surface formic acid dissociates into a formate ion (formate) and a proton. Formate binds to two five-fold coordinated Ti atoms in the troughs along the [001] direction, and the proton binds to neighboring bridging O atoms. Exposure of adsorbed formate to O2 leads to a decrease in the asymmetric νas(OCO) band at 1532 cm-1 and to the concomitant formation of a new vibration band at 1516 cm-1. From the s-and p-polarized IRRAS measurements performed at different O2 exposures, surface pre-treatments and substrate temperatures, and by comparisons with previous reports, we conclude that the new species is a bidentate surface hydrogen carbonate, which is formed by reaction between formate and oxygen adatoms on the surface. The σv reflection plane of the surface hydrogen carbonate molecule is oriented along the [001] direction, i.e. the same direction as the adsorbed formate molecule. On the clean TiO2(110) surface exposed to O2 prior to formic acid adsorption, similar results are obtained. The reaction rate to form surface hydrogen carbonate from formate is found to follow first-order kinetics, with an apparent activation energy of Er=0.25 eV.

  18. Effect of 17β-estradiol on stability and mobility of TiO2 rutile nanoparticles.

    PubMed

    Lee, Jaewoong; Bartelt-Hunt, Shannon L; Li, Yusong; Morton, Martha

    2015-04-01

    Contaminants including titanium dioxide nanoparticles (n-TiO2), as well as organic wastewater contaminants (OWCs), have been detected in wastewater treatment plant effluents, however, no information is yet available on how OWCs may modify the surface properties of TiO2 nanoparticles, or influence their stability in water and subsequent mobility in porous media. In this study, 17β-estradiol (E2) was chosen as a representative OWC to investigate the interaction between OWCs and n-TiO2. Batch and kinetic sorption experiments and Fourier Transform Infrared (FTIR) Spectrometer measurements confirmed that E2 was quickly sorbed onto the surface of n-TiO2 aggregates in water. Aggregation experiments showed that the presence of E2 has a minor influence on the size of n-TiO2 aggregates under lower ionic strength conditions at natural pH. In high ionic strength solution, the presence of E2 led to an increased average hydrodynamic diameter and a wider distribution of n-TiO2 aggregate sizes. Interaction energy analyses indicated that steric repulsion likely contributed to the stability of the n-TiO2 suspension in the presence of E2. Mobility analysis based on the clean bed filtration theory indicated that the impact of E2 on the mobility of n-TiO2 in porous media is minimal in comparison to the influence of solution ionic strength.

  19. The Adsorption and Reactions of the Amino Acid Proline on Rutile TiO2(110) Surfaces

    SciTech Connect

    Fleming,G.; Adib, K.; Rodriquez, J.; Barteau, M.; White, J.; Idriss, H.

    2008-01-01

    The reaction of the amino acid dl-proline is studied over stoichiometric and Ar-ions sputtered (reduced) TiO2(1 1 0) single crystal surfaces by synchrotron High Resolution X-ray Photoelectron Spectroscopy (HRXPS). On the stoichiometric surface proline gives two different species at 300 K: dissociated and zwitterionic. Upon heating the zwitterionic structure is removed first from the surface followed by the dissociated form. The C1s signal for the COO function is found close to 288.5 eV for both forms while the N 1s for the dissociated form is found at 400.0 eV and that of the zwitterionic from close to 401.8 eV. From the attenuation of the Ti 2p signal the surface coverage was estimated less than 1/2 (about 0.35). This smaller coverage than dissociatively adsorbed carboxylic acids on this surface (usually close to 1/2), is attributed to lateral repulsion caused by the ring of adjacent proline molecules adsorbed on five-fold coordinated Ti cations along the [0 0 1] direction. On the reduced surface the amount of zwitterion structure is found two times higher than that on the stoichiometric surface, at 300 K, most likely due to the considerable decrease of the amount of surface oxygen available. The stability of the zwitterionic structure on this surface is however found similar to that found on the stoichiometric surface. In addition, evidence of oxidation of reduced Ti cations upon adsorption at 300 K is noticed and explained as breaking of the carbon-oxygen bond of a fraction of adsorbed proline. Variable temperature HRXPS has been collected and results indicated that proline is more stable on the reduced surface compared to the stoichiometric surface.

  20. 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.

  1. A building blocks strategy for preparing photocatalytically active anatase TiO2/rutile SnO2 heterostructures by hydrothermal annealing.

    PubMed

    de Mendonça, Vagner Romito; Avansi, Waldir; Arenal, Raul; Ribeiro, Caue

    2017-11-01

    Effective heterostructures for photocatalysis need to present good electron-hole mobility among phases, a feature that is only attained with satisfactory interface quality. For very small sizes and with a stable colloidal state, the oriented attachment mechanism can be used to prepare suitable structures by means of a building blocks strategy, whereby preformed nanoparticles are used to control the desired amount of each phase in the heterostructure. Here, we show the success of this strategy for anatase TiO2/rutile SnO2 heterostructures, applying conventional hydrothermal annealing, where successive collisions among particles increase the probability of oriented attachment. The photodegradation of Rhodamine B in water under UV radiation was used as a probe reaction to evaluate formation of the heterostructure, as indicated by an increase in photoactivity. Increased heterostructure photoactivity was related to heterojunction formation and charge separation. The increased lifetimes of the photogenerated charges, due to heterojunction formation, enabled them to reach the oxides surface and promote photocatalytic reactions. The insights presented here may be used in a rationalized synthesis method to obtain heterostructures from preformed nanocrystals. Copyright © 2017 Elsevier Inc. All rights reserved.

  2. 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.

  3. Adsorption of CO2 on oxidized, defected, hydrogen and oxygen covered rutile (1 x 1)-TiO2(110).

    PubMed

    Funk, S; Burghaus, U

    2006-11-07

    Presented are initial, S(0) and coverage, Theta, dependent S(Theta), adsorption probability measurements of CO(2) as a function of impact energy, E(i) = 0.12-1.3 eV, adsorption temperature, T(s) = 85-300 K, hydrogen and oxygen pre-exposure, as well as density of defects, Gamma, as varied by annealing (T = 600-900 K) and Ar(+) ion sputtering (dose chi(Ar) at 600 eV at 85 K) of a rutile (1 x 1) TiO(2)(110) surface. The defect densities were qualitatively characterized by thermal desorption spectroscopy (TDS) of CO(2). The CO(2) TDS curves consisted of two structures that can be assigned to adsorption on pristine and oxygen vacancy sites, in agreement with earlier studies. S(0) decreased linearly with E(i) and was independent of T(s). The adsorption dynamics were dominated by the effect of precursor states leading to Kisliuk-like shapes over the E(i) and T(s) range studied. Oxygen vacancy sites reduced S(0) of CO(2). Preadsorbed oxygen blocked preferentially defect sites, which led to an increase in S(0). Hydrogen preadsorption results in physical site blocking with decreased S(0) as H-preexposure increased, while the shape of S(Theta) curves was conserved. In contrast to oxygen, hydrogen does not adsorb preferentially on defect sites. The adsorption probability data were parameterized by analytic functions (Kisliuk model) and by Monte Carlo simulations (MCSs).

  4. Adsorption of CO on the rutile TiO2(110) surface: a dispersion-corrected density functional theory study.

    PubMed

    Prates Ramalho, João P; Illas, Francesc; Gomes, José R B

    2017-01-18

    The geometry, energy and stretching frequency of carbon monoxide on the rutile TiO2(110) surface for coverages between 0.125 and 1.5 ML are investigated by means of density functional theory calculations. Four different approaches were considered, namely, the PBE exchange-correlation functional and the PBE-D2, vdW-DF and vdW-DF2 methods incorporating van der Waals dispersion interactions of different theoretical complexity and empiricism. It is found that upon the increase of the surface coverage, the adsorption becomes less favorable due to lateral destabilizing interactions between adsorbed molecules. The preferred geometry for CO changes from an upright configuration at 0.125 ML to tilted configurations at 1.5 ML and the tilting of the C-O axis from the surface normal increases with the increase of the surface coverage. At 1 ML, all computational approaches predict alternate tilted configurations which contradict the interpretation of recent experimental infrared reflection-absorption spectroscopic findings suggesting upright CO geometries. Encouragingly, a very good agreement between calculated and experimental shifts of the C-O stretching frequency of adsorbed CO at different coverages with respect to gaseous CO species was reached.

  5. 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.

  6. Study of paramagnetic defect centers in as-grown and annealed TiO2 anatase and rutile nanoparticles by a variable-temperature X-band and high-frequency (236 GHz) EPR

    PubMed Central

    Misra, S.K.; Andronenko, S.I.; Tipikin, D.; Freed, J. H.; Somani, V.; Prakash, Om

    2016-01-01

    Detailed EPR investigations on as-grown and annealed TiO2 nanoparticles in the anatase and rutile phases were carried out at X-band (9.6 GHz) at 77, 120–300 K and at 236 GHz at 292 K. The analysis of EPR data for as-grown and annealed anatase and rutile samples revealed the presence of several paramagnetic centers: Ti3+, O−, adsorbed oxygen (O2−) and oxygen vacancies. On the other hand, in as-grown rutile samples, there were observed EPR lines due to adsorbed oxygen (O2−) and the Fe3+ ions in both Ti4+ substitutional positions, with and without coupling to an oxygen vacancy in the near neighborhood. Anatase nanoparticles were completely converted to rutile phase when annealed at 1000° C, exhibiting EPR spectra similar to those exhibited by the as-grown rutile nanoparticles. The high-frequency (236 GHz) EPR data on anatase and rutile samples, recorded in the region about g = 2.0 exhibit resolved EPR lines, due to O− and O2− ions enabling determination of their g-values with higher precision, as well as observation of hyperfine sextets due to Mn2+ and Mn4+ ions in anatase. PMID:27041794

  7. Comparison of photovoltaic properties of TiO2 electrodes prepared with nanoparticles and nanorods.

    PubMed

    Nam, Sang-Hun; Ju, Dong-Woo; Boo, Jin-Hyo

    2014-12-01

    In this report, single crystalline rutile TiO2 nanoparticles and nanorods were synthesized via the hydrothermal method using titanium tetra-isopropoxide as a precursor then, these were coated on top of a fluorine-doped tin oxide (FTO) substrate by using a doctor blade and direct deposition, respectively. Consequently, TiO2 nanorods-based dye-sensitized solar cells (DSSC) exhibit a J(sc) of 3.37 mA/cm2, a V(oc) of 0.82 V and fill factor of 60.1% with an overall conversion efficiency of 1.66%. This result shows an increase of around 38% for current density and 35% for conversion efficiency. Also, with respect to the impedance data, TiO2 nanorods-based DSSCs had smaller semicircles than did the nanoparticles-based DSSCs. These results demonstrate that the nanorod structure can have fast electron transport and reduced charge recombination.

  8. Polarizable Site Charge Model at Liquid/Solid Interfaces for Describing Surface Polarity: Application to Structure and Molecular Dynamics of Water/Rutile TiO2(110) Interface.

    PubMed

    Nakamura, Hisao; Ohto, Tatsuhiko; Nagata, Yuki

    2013-02-12

    We present a novel scheme to construct a polarizable force field for liquid/solid interfaces, which takes into account the effect of the surface polarity induced by liquid-solid interactions explicitly. We extend the charge response kernel (CRK) method for molecules to solid surfaces by introducing the surface CRK. The CRK parameters are systematically determined by the first-principles calculations in the slab model with the dipole-correction method. Our methodology is applied to the water/clean rutile TiO2(110) interface. Structures and induced charges of a single water molecule attached to the TiO2 surface optimized by our polarizable force field show good agreement with those predicted by the first-principles calculations. Further, we carried out MD simulations for the liquid water/TiO2 interface and found three stable structures of water attached to the TiO2 surface. Two of them are predicted by both the polarizable and the nonpolarizable force fields, while the polarizable force field model predicts a structure of water with the hydrogen and oxygen atoms interacting with the oxygen atom of the surface TiO2 and the hydrogen atom of the other water molecule, respectively, which was reported by the previous first-principles MD simulation. This indicates that the dipole moments of water and TiO2 induced by the water-TiO2 interactions have significant impact on molecular conformations of the water/TiO2 interface.

  9. Adsorption of formic acid on rutile TiO2 (110) revisited: An infrared reflection-absorption spectroscopy and density functional theory study

    NASA Astrophysics Data System (ADS)

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

    2014-01-01

    Formic acid (HCOOH) adsorption on rutile TiO2 (110) has been studied by s- and p-polarized infrared reflection-absorption spectroscopy (IRRAS) and spin-polarized density functional theory together with Hubbard U contributions (DFT+U) calculations. To compare with IRRAS spectra, the results from the DFT+U calculations were used to simulate IR spectra by employing a three-layer model, where the adsorbate layer was modelled using Lorentz oscillators with calculated dielectric constants. To account for the experimental observations, four possible formate adsorption geometries were calculated, describing both the perfect (110) surface, and surfaces with defects; either O vacancies or hydroxyls. The majority species seen in IRRAS was confirmed to be the bridging bidentate formate species with associated symmetric and asymmetric frequencies of the ν(OCO) modes measured to be at 1359 cm-1 and 1534 cm-1, respectively. The in-plane δ(C-H) wagging mode of this species couples to both the tangential and the normal component of the incident p-polarized light, which results in absorption and emission bands at 1374 cm-1 and 1388 cm-1. IRRAS spectra measured on surfaces prepared to be either reduced, stoichiometric, or to contain surplus O adatoms, were found to be very similar. By comparisons with computed spectra, it is proposed that in our experiments, formate binds as a minority species to an in-plane Ti5c atom and a hydroxyl, rather than to O vacancy sites, the latter to a large extent being healed even at our UHV conditions. Excellent agreement between calculated and experimental IRRAS spectra is obtained. The results emphasize the importance of protonation and reactive surface hydroxyls - even under UHV conditions - as reactive sites in e.g., catalytic applications.

  10. Balsam-pear-like rutile/anatase core/shell titania nanorod arrays for photoelectrochemical water splitting.

    PubMed

    Wen, Wei; Yao, Jin-Cheng; Gu, Yi-Jie; Sun, Tulai; Tian, He; Zhou, Qi-Lai; Wu, Jin-Ming

    2017-09-08

    In this work, a solution combustion followed by dissolution in hydrogen peroxide is adopted to achieve a precursor for decorating anatase TiO2 nanosheets along single-crystalline rutile TiO2 nanorods, which achieves balsam-pear-like core/shell nanorod arrays with enhanced photoelectrochemical water splitting. The photocurrent of the rutile/anatase nanorods is about 1.4 times and 20.7 times that of the rutile nanorods and the anatase nanosheets at 0.8 V vs SCE, respectively. The enhanced photoelectrochemical performance is attributed to the novel nanoarchitecture, which can simultaneously offer high surface area, enhanced light-harvesting, rutile/anatase junction for charge carrier separation and conductive pathway for charge carrier collection. The photoanode design can also give hints to other functional materials. © 2017 IOP Publishing Ltd.

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

    PubMed

    Wu, Jyh Ming

    2012-02-01

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

  12. Physical Mechanism Behind Enhanced Photoelectrochemical and Photocatalytic Properties of Superhydrophilic Assemblies of 3D-TiO2 Microspheres with Arrays of Oriented, Single-Crystalline TiO2 Nanowires as Building Blocks Deposited on Fluorine-Doped Tin Oxide.

    PubMed

    Sadhu, Subha; Gupta, Preeti; Poddar, Pankaj

    2017-03-29

    In comparison to the one-dimensional (1D) semiconductor nanostructures, the hierarchical, three-dimensional (3D) microstructures, composed of the arrays of 1D nanostructures as building blocks, show quite unique physicochemical properties due to efficient photon capture and enhanced surface to volume ratio, which aid in advancing the performance of various optoelectronic devices. In this contribution, we report the fabrication of surfactant-free, radially assembled, 3D titania (rutile-phase) microsphere arrays (3D-TMSAs) composed of bundles of single-crystalline titania nanowires (NWs) directly on fluorine-doped conducting oxide (FTO) substrates with tunable architecture. The effects of growth parameters on the morphology of the 3D-TMSAs have been studied thoroughly. The 3D-TMSAs grown on the FTO-substrate showed superior photon-harvesting owing to the increase in light-scattering. The photocatalytic and photon to electron conversion efficiency of dye-sensitized solar cells (DSSC), where the optimized 3D-TMSAs were used as an anode, showed around 44% increase in the photoconversion efficiency compared to that of Degussa P-25 as a result of the synergistic effect of higher surface area and enhanced photon scattering probability. The TMSA film showed superhydrophilicity without any prior UV irradiation. In addition, the presence of bundles of almost parallel NWs led to the formation of arrays of microcapacitors, which showed stable dielectric performance. The fabrication of single-crystalline, oriented, self-assembled TMSAs with bundles of titania nanowires as their building blocks deposited on transparent conducting oxide (TCO) substrates has vast potential in the area of photoelectrochemical research.

  13. Electrodeposited Ag nanoparticles on TiO2 nanorods for enhanced UV visible light photoreduction CO2 to CH4

    NASA Astrophysics Data System (ADS)

    Kong, Dan; Tan, Jeannie Ziang Yie; Yang, Fei; Zeng, Jieliang; Zhang, Xiwen

    2013-07-01

    We employed the double-potentiostatic methodology to electrodeposit Ag nanoparticles on oriented single-crystalline rutile TiO2 nanorods synthesized by hydrothermal method. The synthesized composites were used as the photocatalyst to reduce CO2 to CH4 under UV irradiation, and tested by SEM, XRD, TEM, XPS, UV-vis and photoluminescence. Deposition with Ag nanoparticles was observed to enhance the photocatalytic activity (≈1.5-2.64 μmol (gcatal h)-1) up to 5 times with respect to undecorated TiO2 nanorods (≈0.5 μmol (gcatal h)-1). The increase in the CH4 yield was correlated with the surface morphology and structure of TiO2 nanorods.

  14. 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

  15. Quasi-intrinsic colossal permittivity in Nb and In co-doped rutile TiO2 nanoceramics synthesized through a oxalate chemical-solution route combined with spark plasma sintering.

    PubMed

    Han, HyukSu; Dufour, Pascal; Mhin, Sungwook; Ryu, Jeong Ho; Tenailleau, Christophe; Guillemet-Fritsch, Sophie

    2015-07-14

    Nb and In co-doped rutile TiO2 nanoceramics (n-NITO) were successfully synthesized through a chemical-solution route combined with a low temperature spark plasma sintering (SPS) technique. The particle morphology and the microstructure of n-NITO compounds were nanometric in size. Various techniques such as X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), thermogravimetric (TG)/differential thermal analysis (DTA), Fourier transform infrared (FTIR), and Raman spectroscopy were used for the structural and compositional characterization of the synthesized compound. The results indicated that the as-synthesized n-NITO oxalate as well as sintered ceramic have a co-doped single phase of titanyl oxalate and rutile TiO2, respectively. Broadband impedance spectroscopy revealed that novel colossal permittivity (CP) was achieved in n-NITO ceramics exhibiting excellent temperature-frequency stable CP (up to 10(4)) as well as low dielectric loss (∼5%). Most importantly, detailed impedance data analyses of n-NITO compared to microcrystalline NITO (μ-NITO) demonstrated that the origin of CP in NITO bulk nanoceramics might be related with the pinned electrons in defect clusters and not to extrinsic interfacial effects.

  16. A simple self-assembly route to single crystalline SnO2 nanorod growth by oriented attachment for dye sensitized solar cells.

    PubMed

    Song, Hui; Lee, Kwang-Ho; Jeong, Huisu; Um, Soong Ho; Han, Gil-Sang; Jung, Hyun Suk; Jung, Gun Young

    2013-02-07

    One-dimensional (1-D) SnO(2) nanorods (NRs) with a rutile structure are grown on various substrates regardless of the lattice-mismatch by using a new nutrient solution based on tin oxalate, which generated supersaturated Sn(2+) sources. These affluent sources are appropriate for producing a large number of SnO(2) nanoparticles, sufficient for stacking on a substrate surface by gravity, which then acts as a seed layer for subsequent nanorod growth. Single crystalline nanorods are grown along the [001] direction by the oriented attachment phenomenon in which the attached nanoparticles were rearranged to reduce the overall surface energy through sharing thermodynamically unstable crystal (001) planes. Furthermore, the grown SnO(2) NRs are covered with a TiO(2) particulate film and utilized as a photoanode in DSSCs. The power conversion efficiency is 8.61%, enhanced by 14.2% compared to the photoanode with only a TiO(2) particulate film.

  17. Single crystalline magnetite nanotubes.

    PubMed

    Liu, Zuqin; Zhang, Daihua; Han, Song; Li, Chao; Lei, Bo; Lu, Weigang; Fang, Jiye; Zhou, Chongwu

    2005-01-12

    We descried a method to synthesize single crystalline Fe3O4 nanotubes by wet-etching the MgO inner cores of MgO/Fe3O4 core-shell nanowires. Homogeneous Fe3O4 nanotubes with controllable length, diameter, and wall thickness have been obtained. Resistivity of the Fe3O4 nanotubes was estimated to be approximately 4 x 10-2 Omega cm at room temperature. Magnetoresistance of approximately 1% was observed at T = 77 K when a magnetic field of B = 0.7 T was applied. The synthetic strategy presented here may be extended to a variety of materials such as YBCO, PZT, and LCMO which should provide ideal candidates for fundamental studies of superconductivity, piezoelectricity, and ferromagnetism in nanoscale structures.

  18. 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.

  19. A DFT+U study of acetylene selective hydrogenation on oxygen defective anatase (101) and rutile (110) TiO2 supported Pd4 cluster

    NASA Astrophysics Data System (ADS)

    Yang, Jie; Lv, Cun-Qin; Guo, Yong; Wang, Gui-Chang

    2012-03-01

    The reaction mechanisms for selective acetylene hydrogenation on three different supports, Pd4 cluster, oxygen defective anatase (101), and rutile (110) titania supported Pd4, cluster are studied using the density functional theory calculations with a Hubbard U correction (DFT+U). The present calculations show that the defect anatase support binds Pd4 cluster more strongly than that of rutile titania due to the existence of Ti3+ in anatase titania. Consequently, the binding energies of adsorbed species such as acetylene and ethylene on Pd4 cluster become weaker on anatase supported catalysts compared to the rutile supported Pd4 cluster. Anatase catalyst has higher selectivity of acetylene hydrogenation than rutile catalyst. On the one hand, the activation energies of ethylene formation are similar on the two catalysts, while they vary a lot on ethyl formation. The rutile supported Pd catalyst with lower activation energy is preferable for further hydrogenation. On the other hand, the relatively weak adsorption energy of ethylene is gained on anatase surface, which means it is easier for ethylene desorption, hence getting higher selectivity. For further understanding, the energy decomposition method and micro-kinetic analysis are also introduced.

  20. 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.

  1. Electron transport and recombination in dye-sensitized solar cells made from single-crystal rutile TiO2 nanowires.

    PubMed

    Enache-Pommer, Emil; Liu, Bin; Aydil, Eray S

    2009-11-14

    Contrary to expectations, the electron transport rate in dye-sensitized solar cells made from single-crystal rutile titanium dioxide nanowires is found to be similar to that measured in dye-sensitized solar cells made from titanium dioxide nanoparticles.

  2. Preparation of Highly Crystalline TiO(2) Nanostructures by Acid-assisted Hydrothermal Treatment of Hexagonal-structured Nanocrystalline Titania/Cetyltrimethyammonium Bromide Nanoskeleton.

    PubMed

    Dai, Shuxi; Wu, Yanqiang; Sakai, Toshio; Du, Zuliang; Sakai, Hideki; Abe, Masahiko

    2010-08-11

    Highly crystalline TiO(2) nanostructures were prepared through a facile inorganic acid-assisted hydrothermal treatment of hexagonal-structured assemblies of nanocrystalline titiania templated by cetyltrimethylammonium bromide (Hex-ncTiO(2)/CTAB Nanoskeleton) as starting materials. All samples were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The influence of hydrochloric acid concentration on the morphology, crystalline and the formation of the nanostructures were investigated. We found that the morphology and crystalline phase strongly depended on the hydrochloric acid concentrations. More importantly, crystalline phase was closely related to the morphology of TiO(2) nanostructure. Nanoparticles were polycrystalline anatase phase, and aligned nanorods were single crystalline rutile phase. Possible formation mechanisms of TiO(2) nanostructures with various crystalline phases and morphologies were proposed.

  3. Preparation of Highly Crystalline TiO2 Nanostructures by Acid-assisted Hydrothermal Treatment of Hexagonal-structured Nanocrystalline Titania/Cetyltrimethyammonium Bromide Nanoskeleton

    PubMed Central

    2010-01-01

    Highly crystalline TiO2 nanostructures were prepared through a facile inorganic acid-assisted hydrothermal treatment of hexagonal-structured assemblies of nanocrystalline titiania templated by cetyltrimethylammonium bromide (Hex-ncTiO2/CTAB Nanoskeleton) as starting materials. All samples were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The influence of hydrochloric acid concentration on the morphology, crystalline and the formation of the nanostructures were investigated. We found that the morphology and crystalline phase strongly depended on the hydrochloric acid concentrations. More importantly, crystalline phase was closely related to the morphology of TiO2 nanostructure. Nanoparticles were polycrystalline anatase phase, and aligned nanorods were single crystalline rutile phase. Possible formation mechanisms of TiO2 nanostructures with various crystalline phases and morphologies were proposed. PMID:21124640

  4. Synergistic manipulation of micro-nanostructures and composition: anatase/rutile mixed-phase TiO2 hollow micro-nanospheres with hierarchical mesopores for photovoltaic and photocatalytic applications.

    PubMed

    Zhu, Qing; Qian, Jieshu; Pan, Hao; Tu, Luo; Zhou, Xingfu

    2011-09-30

    The construction of nanocrystals with controllable composition and desirable micro-nanostructures is a well-known challenge. A combination of favorable composition and optimized micro-nanostructures can enhance the performance of a material significantly. Using TiO(2) as an example, we demonstrate here a facile approach to prepare anatase/rutile mixed-phase TiO(2) hollow micro-nanospheres with hierarchical mesopores. Our strategy relies on polymer-assisted assembly of ∼ 5 nm nano-building blocks into three-dimensional hierarchical hollow micro-nanospheres in a mixed alcohol-water solution. This superior micro-nanostructure endows the sample with hierarchical mesopores and a high surface area of 106 m(2) g(-1). We also show that, due to the synergetic effects of the mixed-phase composition and the micro-nanostructures, the sample exhibited significantly improved photovoltaic performance and similar photocatalytic performance compared with the commercial Degussa P25. These results suggested that our sample has great potential for future photovoltaic and photocatalytic applications.

  5. High efficiency solid-state sensitized solar cell-based on submicrometer rutile TiO2 nanorod and CH3NH3PbI3 perovskite sensitizer.

    PubMed

    Kim, Hui-Seon; Lee, Jin-Wook; Yantara, Natalia; Boix, Pablo P; Kulkarni, Sneha A; Mhaisalkar, Subodh; Grätzel, Michael; Park, Nam-Gyu

    2013-06-12

    We report a highly efficient solar cell based on a submicrometer (~0.6 μm) rutile TiO2 nanorod sensitized with CH3NH3PbI3 perovskite nanodots. Rutile nanorods were grown hydrothermally and their lengths were varied through the control of the reaction time. Infiltration of spiro-MeOTAD hole transport material into the perovskite-sensitized nanorod films demonstrated photocurrent density of 15.6 mA/cm(2), voltage of 955 mV, and fill factor of 0.63, leading to a power conversion efficiency (PCE) of 9.4% under the simulated AM 1.5G one sun illumination. Photovoltaic performance was significantly dependent on the length of the nanorods, where both photocurrent and voltage decreased with increasing nanorod lengths. A continuous drop of voltage with increasing nanorod length correlated with charge generation efficiency rather than recombination kinetics with impedance spectroscopic characterization displaying similar recombination regardless of the nanorod length.

  6. 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.

  7. 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.

  8. Solid state perovskite solar modules by vacuum-vapor assisted sequential deposition on Nd:YVO4 laser patterned rutile TiO2 nanorods

    NASA Astrophysics Data System (ADS)

    Fakharuddin, Azhar; Palma, Alessandro L.; Di Giacomo, Francesco; Casaluci, Simone; Matteocci, Fabio; Wali, Qamar; Rauf, Muhammad; Di Carlo, Aldo; Brown, Thomas M.; Jose, Rajan

    2015-12-01

    The past few years have witnessed remarkable progress in solution-processed methylammonium lead halide (CH3NH3PbX3, X = halide) perovskite solar cells (PSCs) with reported photoconversion efficiency (η) exceeding 20% in laboratory-scale devices and reaching up to 13% in their large area perovskite solar modules (PSMs). These devices mostly employ mesoporous TiO2 nanoparticles (NPs) as an electron transport layer (ETL) which provides a scaffold on which the perovskite semiconductor can grow. However, limitations exist which are due to trap-limited electron transport and non-complete pore filling. Herein, we have employed TiO2 nanorods (NRs), a material offering a two-fold higher electronic mobility and higher pore-filing compared to their particle analogues, as an ETL. A crucial issue in NRs’ patterning over substrates is resolved by using precise Nd:YVO4 laser ablation, and a champion device with η ∼ 8.1% is reported via a simple and low cost vacuum-vapor assisted sequential processing (V-VASP) of a CH3NH3PbI3 film. Our experiments showed a successful demonstration of NRs-based PSMs via the V-VASP technique which can be applied to fabricate large area modules with a pin-hole free, smooth and dense perovskite layer which is required to build high efficiency devices.

  9. Hydrogen-Treated Rutile TiO2 Shell in Graphite-Core Structure as a Negative Electrode for High-Performance Vanadium Redox Flow Batteries.

    PubMed

    Vázquez-Galván, Javier; Flox, Cristina; Fàbrega, Cristian; Ventosa, Edgar; Parra, Andres; Andreu, Teresa; Morante, Joan Ramón

    2017-05-09

    Hydrogen-treated TiO2 as an electrocatalyst has shown to boost the capacity of high-performance all-vanadium redox flow batteries (VRFBs) as a simple and eco-friendly strategy. The graphite felt-based GF@TiO2 :H electrode is able to inhibit the hydrogen evolution reaction (HER), which is a critical barrier for operating at high rate for long-term cycling in VRFBs. Significant improvements in charge/discharge and electron-transfer processes for the V(3+) /V(2+) reaction on the surface of reduced TiO2 were achieved as a consequence of the formation of oxygen functional groups and oxygen vacancies in the lattice structure. Key performance indicators of VRFB have been improved, such as high capability rates and electrolyte-utilization ratios (82 % at 200 mA cm(-2) ). Additionally, high coulombic efficiencies (ca. 100 % up to the 96th cycle, afterwards >97 %) were obtained, demonstrating the feasibility of achieving long-term stability. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. In situ study of photo- and thermo-induced color centers in photochromic rutile TiO2 in the temperature range 90-720 K.

    PubMed

    Kuznetsov, V N; Glazkova, N I; Mikhaylov, R V; Serpone, N

    2016-10-05

    This article reports an in situ UV-Vis-NIR diffuse reflectance (DR) spectroscopic and kinetic study of the photoformation and thermal annealing of light absorbing electronic point defects (color centers) in photochromic TiO2 in the temperature range 90-720 K using a simple laboratory-made cryostat-type accessory (for a Cary 5000 spectrophotometer equipped with an integrating sphere). The accessory also allowed for UV-Vis-NIR DR studies to be undertaken either in vacuum or in an oxygen atmosphere at significantly high temperatures (to 720 K) to assess dark chemical events occurring in photochromic titania with the participation of color centers. The DR spectral and kinetic measurements provided the opportunity to examine the separation of photoinduced charge carriers at traps and thermally stimulated carrier detrapping and recombination, as well as the response of color centers to oxidative/reductive treatments of photochromic TiO2. Kinetic results also demonstrate the applicability of the fabricated DR accessory as a high-temperature reaction cell in the systematic study of the principal regularities in the formation and destruction of color centers in titania at various temperatures and gaseous atmospheres.

  11. 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.

  12. 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

    2016-05-05

    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.

  13. 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.

  14. Single crystalline mesoporous silicon nanowires.

    PubMed

    Hochbaum, Allon I; Gargas, Daniel; Hwang, Yun Jeong; Yang, Peidong

    2009-10-01

    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.

  15. A Strategy for Synthesis of Nanosheets Consisting of Alternating Spinel Li4Ti5O12 and Rutile TiO2 Lamellas for High-Rate Anodes of Lithium-Ion Batteries.

    PubMed

    Wu, Libo; Leng, Xuning; Liu, Yan; Wei, Sufeng; Li, Chunlin; Wang, Guoyong; Lian, Jianshe; Jiang, Qing; Nie, Anmin; Zhang, Tong-Yi

    2017-02-08

    Ultrathin dual phase nanosheets consisting of alternating spinel Li4Ti5O12 (LTO) and rutile TiO2 (RT) lamellas are synthesized through a facile and scalable hydrothermal method, and the formation mechanism is explored. The thickness of constituent lamellas can be controlled exactly by adjusting the mole ratio of Li:Ti in the original reactants. Alternating insertion of the RT lamellas significantly improves the electrochemical performance of LTO nanosheets, especially at high charge/discharge rates. As anodes in lithium-ion batteries (LIBs), the dual phase nanosheet electrode with the optimized phase ratio can deliver stable discharge capacities of 178.5, 154.9, 148.4, 142.3, 138.2, and 131.4 mA h g(-1) at current densities of 1, 10, 20, 30, 40, and 50 C, respectively. Meanwhile, they inherit the excellent cyclic stability of pure spinel LTO and exhibit a capacity retention of 93.1% even after 500 cycles at 50 C. Our results indicate that the alternating nanoscaled lamella structure is a good alternative to facilitate the transfer of both the Li ions and electrons into the spinel LTO, giving rise to an excellent cyclability and fast rate performance. Therefore, the newly prepared carbon-free LTO-RT nanosheets with high safety provide a new opportunity to develop high-power anodes for LIBs.

  16. 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.

  17. 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.

  18. Charge separation in branched TiO2 nanorod array homojunction aroused by quantum effect for enhanced photocatalytic decomposition of gaseous benzene

    NASA Astrophysics Data System (ADS)

    Wang, Xiaoxia; Ni, Qian; Zeng, Dawen; Liao, Guanglan; Xie, Changsheng

    2016-12-01

    As known, the electron transfer behavior in photocatalysis is short-distance transportation, which leads the photo-induced electrons and holes to be localized. The temporarily separated electrons and holes will recombine with each other in the localized region. In this paper, we successfully achieved electron transfer in a homojunction of branched rutile TiO2 nanorod @nanoparticle core-shell architecture by quantum confinement effect aroused by the nanoparticle, which is proved by the blue-shifting in UV-vis absorption spectrum of the homojunction. Meanwhile, an absolute charge separation is also achieved by the long-distance electron transfer along the single-crystalline rutile TiO2 nanorod as uninterrupted high-speed electron transfer channel to FTO substrates. Based on the effective charge separation, the photocatalytic decomposition of gaseous benzene by the homojunction is significantly enhanced, yielding 10 times CO2 than that of the nanorod array. This homojunction interfacial charge separation, aroused by quantum effect, through long-distance transfer along the single-crystalline nanorod gives us inspiration to achieve efficient charge separation with defect-less interfaces, which might can be utilized for real-time environmental abatement and energy generation simultaneously.

  19. 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.

  20. Single-crystalline self-branched anatase titania nanowires for dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Li, Zhenquan; Yang, Huang; Wu, Fei; Fu, Jianxun; Wang, Linjun; Yang, Weiguang

    2017-03-01

    The morphology of the anatase titania plays an important role in improving the photovoltaic performance in dye-sensitized solar cells. In this work, single-crystalline self-branched anatase TiO2 nanowires have been synthesized by hydrothermal method using TBAH and CTAB as morphology controlling agents. The obtained self-branched TiO2 nanowires dominated by a large percentage of (010) facets. The photovoltaic conversion efficiency (6.37%) of dye-sensitized solar cell (DSSC) based on the self-branched TiO2 nanowires shows a significant improvement (26.6%) compared to that of P25 TiO2 (5.03%). The enhanced performance of the self-branched TiO2 nanowires-based DSSC is due to heir large percent of exposed (010) facets which have strong dye adsorption capacity and effective charge transport of the self-branched 1D nanostructures.

  1. Single-crystalline self-branched anatase titania nanowires for dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Li, Zhenquan; Yang, Huang; Wu, Fei; Fu, Jianxun; Wang, Linjun; Yang, Weiguang

    2016-12-01

    The morphology of the anatase titania plays an important role in improving the photovoltaic performance in dye-sensitized solar cells. In this work, single-crystalline self-branched anatase TiO2 nanowires have been synthesized by hydrothermal method using TBAH and CTAB as morphology controlling agents. The obtained self-branched TiO2 nanowires dominated by a large percentage of (010) facets. The photovoltaic conversion efficiency (6.37%) of dye-sensitized solar cell (DSSC) based on the self-branched TiO2 nanowires shows a significant improvement (26.6%) compared to that of P25 TiO2 (5.03%). The enhanced performance of the self-branched TiO2 nanowires-based DSSC is due to heir large percent of exposed (010) facets which have strong dye adsorption capacity and effective charge transport of the self-branched 1D nanostructures.

  2. Anatase TiO2 sheet-assisted synthesis of Ti(3+) self-doped mixed phase TiO2 sheet with superior visible-light photocatalytic performance: Roles of anatase TiO2 sheet.

    PubMed

    Zhang, Xiaojie; Zuo, Guoqing; Lu, Xin; Tang, Changqing; Cao, Shuo; Yu, Miao

    2017-03-15

    On the basis of measurements, such as field emission scanning electron microscope, UV-Vis diffuse reflectance spectra, X-ray diffraction, electron paramagnetic resonance, photoluminescence spectra, and photocurrent measurements, the roles of anatase TiO2 sheet on synthesizing Ti(3+) self-doped mixed phase TiO2 nanosheets (doped TiO2 (A/R, TiO2 (A))) and on improving the performance for photocatalytic CO2 reduction were explored systematically. High surface area anatase TiO2 nanosheets (TiO2 (A)) as a substrate, structure directing agent, and inhibitor, mediated the synthesis of Ti(3+) self-doped mixed phase TiO2 nanosheets. Addition of TiO2 (A) significantly improved not only visible light absorption of doped TiO2 (A/R, TiO2 (A)), but also the efficiency of photo-excited charges separations due to the existence of interfacial regions of anatase-rutile TiO2 junctions. Finally, a possible mechanism for interfacial charge transfer at the anatase-rutile TiO2 interface and for photocatalytic CO2 reduction over Pt loaded doped TiO2 (A/R, TiO2 (A)) were proposed.

  3. Synthesis and Characterization of Bowl-Like Single-Crystalline BaTiO3 Nanoparticles

    PubMed Central

    2010-01-01

    Novel bowl-like single-crystalline BaTiO3 nanoparticles were synthesized by a simple hydrothermal method using Ba(OH)2·8H2O and TiO2 as precursors. The as-prepared products were characterized by XRD, Raman spectroscopy, SEM and TEM. The results show that the bowl-like BaTiO3 nanoparticles are single-crystalline and have a size about 100–200 nm in diameter. Local piezoresponse force measurements indicate that the BaTiO3 nanoparticles have switchable polarization at room temperature. The local effective piezoelectric coefficient is approximately 28 pm/V. PMID:20596350

  4. Energetics of nanocrystalline TiO2

    PubMed Central

    Ranade, M. R.; Navrotsky, A.; Zhang, H. Z.; Banfield, J. F.; Elder, S. H.; Zaban, A.; Borse, P. H.; Kulkarni, S. K.; Doran, G. S.; Whitfield, H. J.

    2002-01-01

    The energetics of the TiO2 polymorphs (rutile, anatase, and brookite) were studied by high temperature oxide melt drop solution calorimetry. Relative to bulk rutile, bulk brookite is 0.71 ± 0.38 kJ/mol (6) and bulk anatase is 2.61 ± 0.41 kJ/mol higher in enthalpy. The surface enthalpies of rutile, brookite, and anatase are 2.2 ± 0.2 J/m2, 1.0 ± 0.2 J/m2, and 0.4 ± 0.1 J/m2, respectively. The closely balanced energetics directly confirm the crossover in stability of nanophase polymorphs inferred by Zhang and Banfield (7). An amorphous sample with surface area of 34,600 m2/mol is 24.25 ± 0.88 kJ/mol higher in enthalpy than bulk rutile. PMID:11880610

  5. Thermo-selective Tm(x)Ti(1-x)O(2-x/2) nanoparticles: from Tm-doped anatase TiO2 to a rutile/pyrochlore Tm2Ti2O7 mixture. An experimental and theoretical study with a photocatalytic application.

    PubMed

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

    2014-11-07

    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 Tm(3+) replaces Ti(4+) 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 Tm(3+) in the samples synthesized, which produces oxygen vacancies to maintain the local neutrality in the lattice. The presence of Tm(3+) 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.

  6. 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

  7. 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.

  8. 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

  9. 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.

  10. 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

    2016-03-07

    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.

  11. Ideal, defective, and gold-promoted rutile TiO2(110) surfaces interacting with CO, H2, and H2O: Structures, energies, thermodynamics, and dynamics from PBE+U

    NASA Astrophysics Data System (ADS)

    Farnesi Camellone, Matteo; Kowalski, Piotr M.; Marx, Dominik

    2011-07-01

    Extensive first-principles calculations are carried out to investigate gold-promoted TiO2(110) surfaces in terms of structure optimizations, electronic structure analyses, ab initio thermodynamics calculations of surface phase diagrams, and ab initio molecular dynamics simulations. All computations rely on density functional theory in the generalized gradient approximation (PBE) and account for on-site Coulomb interactions via inclusion of a Hubbard correction PBE+U, where U is computed from linear response theory. This approach is validated by investigating the interaction between TiO2(110) surfaces and typical probe species (H, H2O, and CO). Relaxed structures and binding energies are compared to both data from the literature and plain PBE results, thus allowing the performance of the PBE+U approach for the specific purpose to be verified. The main focus of the study is on the properties of gold-promoted titania surfaces and their interactions with CO. Both PBE+U and PBE optimized structures of Au adatoms adsorbed on stoichiometric and reduced TiO2 surfaces are computed, along with their electronic structure. The charge rearrangement induced by the adsorbates at the metal (oxide) contact are also analyzed in detail and discussed. By performing PBE+U ab initio molecular dynamics simulations, it is demonstrated that the diffusion of Au adatoms on the stoichiometric surface is highly anisotropic. The metal atoms migrate either along the top of the bridging oxygen rows or around the area between these rows, from one bridging position to the next along the [001] direction. No translational motion perpendicular to this direction is observed. Approximate ab initio thermodynamics predicts that under O-rich conditions, structures obtained by substituting a Ti5c atom with an Au atom are thermodynamically stable over a wide range of temperatures and pressures that are relevant to applications in the realm of catalysis. Finally, it is shown that TiO2(110) surfaces containing positively charged Au ions activate molecular CO, whereas a single negatively charged Au-δ species bound to an O vacancy only weakly interacts with CO. Despite this, the calculations predict that the reactivity of gold nanoparticles nucleated at O vacancies can be recovered for cluster sizes as small as Au2.

  12. Influence of annealing on optical and photovoltaic properties of nanostructured TiO2 films

    NASA Astrophysics Data System (ADS)

    Serikov, T. M.; Ibrayev, N. Kh; Smagulov, Zh Kh; Kuterbekov, К. А.

    2017-01-01

    Spectral and kinetic characteristics of the photoluminescence of TiO2 films obtained from TiO2 nanoparticles and nanotubes were studied. Luminescence spectra typical for the TiO2 with anatase structure were observed under UV excitation of the films. Heat treatment of the films at T=1273 K leads to a long-wavelength shift of the photoluminescence band with maximum at 850 nm, which corresponds to the rutile structure. The luminescence duration of rutile films is longer than the luminescence duration of the anatase films as for nanoparticles and for nanotubes. The photovoltaic properties of TiO2 films with different structures were investigated. It was established that anatase structured films have a higher photocurrent than the rutile structured film. By impedance spectroscopy method it was found that the electron transport resistance in the nanotube films is higher but the recombination rate is lower than in the TiO2 nanoparticle films.

  13. 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.

  14. Optimized nanostructured TiO2 photocatalysts

    NASA Astrophysics Data System (ADS)

    Topcu, Selda; Jodhani, Gagan; Gouma, Pelagia

    2016-07-01

    Titania is the most widely studied photocatalyst. In it’s mixed-phase configuration (anatase-rutile form) -as manifested in the commercially available P25 Degussa material- titania was previously found to exhibit the best photocatalytic properties reported for the pure system. A great deal of published research by various workers in the field have not fully explained the underlying mechanism for the observed behavior of mixed-phase titania photocatalysts. One of the prevalent hypothesis in the literature that is tested in this work involves the presence of small, active clusters of interwoven anatase and rutile crystallites or “catalytic “hot-spots””. Therefore, non-woven nanofibrous mats of titania were produced and upon calcination the mats consisted of nanostructured fibers with different anatase-rutile ratios. By assessing the photocatalytic and photoelectrochemical properties of these samples the optimized photocatalyst was determined. This consisted of TiO2 nanostructures annealed at 500˚C with an anatase /rutile content of 90/10. Since the performance of this material exceeded that of P25 complete structural characterization was employed to understand the catalytic mechanism involved. It was determined that the dominant factors controlling the photocatalytic behavior of the titania system are the relative particle size of the different phases of titania and the growth of rutile laths on anatase grains which allow for rapid electron transfer between the two phases. This explains how to optimize the response of the pure system.

  15. Surface photovoltage studies of nonstoichiometric rutile titanium dioxide

    NASA Astrophysics Data System (ADS)

    Sheppard, L. R.; Dittrich, T.; Nowotny, J.; Bak, T.

    2010-02-01

    The aim of the present investigation was to assess how processing at elevated temperatures impacts upon the room temperature electronic structure of rutile TiO2. Consequently, strongly reduced and oxidized rutile TiO2 pellets were processed under controlled conditions and studied using surface photovoltage spectroscopy. Under illumination with photon energies above the band gap energy, reduced and oxidized rutile, respectively, displayed positive and negative surface photovoltages. This result indicates that undoped TiO2 may be tailored to promote either photoreduction or photo-oxidation reactions. Several transitions involving surface and bulk electronic states within the band gap were observed in oxidized rutile, but in contrast, similar states could not be readily distinguished in reduced rutile. A band diagram of oxidized rutile is proposed.

  16. 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

  17. Shock induced phase transition of different TiO2 precursors

    NASA Astrophysics Data System (ADS)

    Chen, Pengwan; Gao, Xiang; Liu, Jianjun; Zhou, Qiang

    2011-06-01

    To investigate the effects of phase composition and particle size on shock-induced phase transition of TiO2, different TiO2 precursors including MC-150 TiO2(pure anatase,5nm), P25 TiO2(85% anatase/15% rutile,15nm), T2 TiO2(pure anatase,35nm) and T1 TiO2(pure rutile, 24nm) were impacted by detonation-driven high velocity flyers. Powder X-ray diffraction(XRD) was used to characterize the phase composition of recovered samples. Two types of phase transition were observed, including anatase to rutile transition and anatase to high pressure phase of srilankite transition. The phase transition mechanisms and effects of shock conditions, initial phase composition and particle size were analyzed. Complete transition from anatase to srilankite can be obtained by adjusting the shock conditions. In the case of impacting pure P25 TiO2, anatase to srilankite transition was hardly observed, which may be due to the restraint of initial phase of thermodynamically stable rutile. However, in the case of impacting a mixture of P25 TiO2 and dicyandiamide(C2N4H4) , it is interesting to observe anatase to srilankite transition and the mechanisms was analyzed. National Natural Science Foundation of China

  18. Optimized method for preparation of TiO2 nanoparticles dispersion for biological study.

    PubMed

    Zhang, Xiaoqiang; Yin, Lihong; Tang, Meng; Pu, Yuepu

    2010-08-01

    The objective of the present study was to develop a practical method to prepare a stable dispersion of TiO2 nanoparticles for biological studies. To address this matter a variety of different approaches for suspension of nanoparticles were conducted. TiO2 (rutile/anatase) dispersions were prepared in distilled water following by treated with different ultrasound energies and various dispersion stabilizers (1.0% carboxymethyl cellulose, 0.5% hydroxypropyl methyl cellulose K4M, 100% fetal bovine serum, and 2.5% bovine serum albumin). The average size of dispersed TiO2 (rutile/anatase) nanoparticles was measured by dynamic light scattering device. Agglomerate sizes of TiO2 in distilled water and 100% FBS were estimated using TEM analysis. Sedimentation rate of TiO2 (rutile/anatase) nanoparticles in dispersion was monitored by optical absorbance detection. In vitro cytotoxicity of various stabilizers in 16-HBE cells was measured using MTT assay. The optimized process for preparation of TiO2 (rutile/anatase) nanoparticles dispersion was first to vibrate the nanoparticles by vortex and disperse particles by ultrasonic vibration in distilled water, then to add dispersion stabilizers to the dispersion, and finally to sonicate the nanoparticles in dispersion. TiO2 (rutile/anatase) nanoparticles were disaggregated sufficiently with an ultrasound energy of 33 W for 10 min. The formation of TiO2 (rutile/anatase) agglomerates in distilled water was decreased obviously by addition of 1.0% CMC, 0.5% HPMC K4M, 100% FBS and 2.5% BSA. For the benefit of cell growth, FBS is the most suitable stabilizer for preparation of TiO2 (rutile/anatase) particle dispersions and subsequent investigation of the in vivo and in vitro behavior of TiO2 (rutile/anatase) nanoparticles. This method is practicable to prepare a stable dispersion of TiO2 (rutile/anatase) nanoparticles for at least 120 h.

  19. Single-crystalline titanium dioxide hollow tetragonal nanocones with large exposed (101) facets for excellent photocatalysis.

    PubMed

    Wu, Zhengcui; Xue, Yejing; Zou, Zexian; Wang, Xia; Gao, Feng

    2017-03-15

    Crystal facet engineering and surface modification of semiconductor have become important strategies to improve photocatalytic activity by optimizing surface charge carrier separation/transfer and extending solar spectrum utilization. In this work, we report anatase single-crystalline TiO2 hollow tetragonal nanocones with large exposed (101) facets by a facile liquid-phase interfacial synthetic strategy, using the hydrolysis of tetrabutyltitanate with adscititious water in the organic solvent of cyclohexane and a capping agent of 1, 6-hexanediamine. The specific surface area of these TiO2 hollow tetragonal nanocones is as high as 331.3m(2)/g. Thanks to large exposed (101) facets and high surface area, these TiO2 hollow tetragonal nanocones exhibited excellent full-arc photocatalytic activities for the degradation of organic pollutants. Remarkably, the butoxy group could be modified onto TiO2 hollow tetragonal nanocones through post-synthesis treatment in tetrabutyltitanate glycol solution, which brought about eximious visible light photocatalytic activities for the degradation of colored dyes of RhB and MO, especially for RhB, by virtue of much improved electron trapping ability of the Ti-O group from the excited dye due to the strong electronegativity of the oxygen atom in the butoxy group. This work advances us to rationally tailor the atomic and electronic structure of the photocatalyst for outstanding photocatalytic properties in various environmental and energy-related applications. Copyright © 2016 Elsevier Inc. All rights reserved.

  20. 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.

  1. Experimental Studies on Rutile Solubility

    NASA Astrophysics Data System (ADS)

    Rapp, J. F.; Klemme, S.; Butler, I. B.; Harley, S. L.

    2007-12-01

    Rutile (TiO2) is an important high field strength element (HFSE) sequestering mineral, and has been implicated in the observed depletion of HFSE in arc magmas. It is thought that rutile is insoluble in slab-derived fluids, and remains residual in the subducted slab. Indeed, experimental data indicates a very low solubility of rutile in pure H2O (Tropper and Manning, 2005), and this low solubility may result in HFSE depleted fluids imparting a depleted signature to arc magmas. However, there is scant experimental data available on rutile solubility in fluids of more complex compositions (Ayers and Watson, 1993). We are carrying out a systematic experimental study into the effect of specific chemical components on rutile solubility in fluids and also silicate melts. This should further our understanding of HFSE mobility in metamorphic rocks within subduction zones. References: J. C. Ayers and E. B. Watson (1993) Rutile solubility in supercritical aqueous fluids and the high P-T mobility of elements it concentrates. Contrib. Mineral. Petrol. 114, 321-330. P. Tropper and C. E. Manning (2005) Very low solubility of rutile in H2O at high pressure and temperature, and its implications for Ti mobility in subduction zones. American Mineralogist 90(2-3), 502-505.

  2. Oriented epitaxial TiO2 nanowires for water splitting

    NASA Astrophysics Data System (ADS)

    Hou, Wenting; Cortez, Pablo; Wuhrer, Richard; Macartney, Sam; Bozhilov, Krassimir N.; Liu, Rong; Sheppard, Leigh R.; Kisailus, David

    2017-06-01

    Highly oriented epitaxial rutile titanium dioxide (TiO2) nanowire arrays have been hydrothermally grown on polycrystalline TiO2 templates with their orientation dependent on the underlying TiO2 grain. Both the diameter and areal density of the nanowires were tuned by controlling the precursor concentration, and the template surface energy and roughness. Nanowire tip sharpness was influenced by precursor solubility and diffusivity. A new secondary ion mass spectrometer technique has been developed to install additional nucleation sites in single crystal TiO2 templates and the effect on nanowire growth was probed. Using the acquired TiO2 nanowire synthesis knowhow, an assortment of nanowire arrays were installed upon the surface of undoped TiO2 photo-electrodes and assessed for their photo-electrochemical water splitting performance. The key result obtained was that the presence of short and dispersed nanowire arrays significantly improved the photocurrent when the illumination intensity was increased from 100 to 200 mW cm-2. This is attributed to the alignment of the homoepitaxially grown nanowires to the [001] direction, which provides the fastest charge transport in TiO2 and an improved pathway for photo-holes to find water molecules and undertake oxidation. This result lays a foundation for achieving efficient water splitting under conditions of concentrated solar illumination.

  3. AC conductivity studies of Fe doped TiO2 nanotubes

    NASA Astrophysics Data System (ADS)

    Vijayan, P. P.; Thomas, M.; George, K. C.

    2015-02-01

    Fe-doped TiO2 nanotubes are prepared by the combination of sol-gel process with hydrothermal treatment. The morphology and crystalline structure of TiO2 nanotubes are characterized by transmission electron microscopy (TEM), X-ray diffraction respectively (XRD). Fe doping induces a structural transformation from anatase to rutile. The temperature dependence of the ac electrical conductivity is investigated in the temperature range 303-413 K. Positive temperature coefficient of resistance is observed in the Fe doped TiO2 nanotubes. PL spectrum shows the presence of oxygen vacancies and self trapped excitons in Fe doped TiO2 nanotubes and undoped samples.

  4. Unusual microstructures in TiO2 ceramic pellets with asymmetrical electrical conductivity

    NASA Astrophysics Data System (ADS)

    Shinozaki, S. S.; Donlon, W. T.; Meitzler, A. H.

    1982-11-01

    Ceramic pellets of TiO2 (rutile), with embedded Pt wire electrodes, have been heat treated in a manner that changed the normal electrical properties of rutile at room temperature from those of an insulator to those of a semiconductor with rectifying characteristics. This change in electrical properties was accompanied by the development of unusual microstructures in the rutile grains which were analyzed by a combination of techniques including transmission electron microscopy and scanning transmission electron microscopy. These analyses indicated that, under the applied conditions of heat treatment, Pt diffused into the rutile and reacted initially with the TiO2 at oxygen vacancy sites to form point-defect agglomerates and that these point defects blocked the normal formation of crystallographic shear planes. As the process proceeded by continued Pt diffusion, thin planar precipitates of PtTi3 were formed in epitaxial relation to the surrounding rutile matrix.

  5. 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.

  6. 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.

  7. Multiphoton Effects in Rutile.

    NASA Astrophysics Data System (ADS)

    Royce, Gerald A.

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

  8. 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

  9. 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.

  10. Ab initio modeling of TiO2 nanotubes

    NASA Astrophysics Data System (ADS)

    Szieberth, Dénes; Ferrari, Anna Maria; Noel, Yves; Ferrabone, Matteo

    2010-01-01

    TiO2 nanotubes constructed from a lepidocrocite-like TiO2 layer were investigated with ab initio methods employing the periodic CRYSTAL code. The dependence of strain energies, structural and electronic properties on the tube diameter was investigated in the 18-57 Å range. Nanotubes constructed by a (0,n) rollup proved to be the most stable at all diameters. All three types of rollup undergo significant reconstruction at diameters <25 Å. All investigated structures possess a high (~5.4 eV) band gap compared to bulk TiO2 phases (3.96 and 4.63 eV for rutile and anatase calculated with the same functional and basis set).

  11. Microscale material testing of single crystalline silicon

    NASA Astrophysics Data System (ADS)

    Yi, Taechung

    The mechanical properties of single crystalline silicon (SCS) in microscale are characterized using a uniaxial tension test. The samples are prepared using, various micromachining techniques. The dimensions of the tension specimen at the maximum stress region are 5 to 10 mum in thickness and 20 to 100 mum in width. The sample has two illumination marks on the top surface for strain measurement. The uniaxial tension test setup has been built to accommodate requirements such as sample handling, sample alignment, and friction elimination. Stress is measured using a commercial load cell. Strain is measured by laser interferometry. All the components are connected to a data acquisition board and controlled by a personal computer. Measured Young's moduli in three directions agree well with the reference values and verify the reliability of the setup and measurement procedure. The measured fracture strength is 0.6 GPa to 1.2 GPa, depending on sample preparation methods and loading directions. Preliminary work for fracture toughness measurements using a sharp initial crack is also presented. Future works include further investigation of fracture surfaces, fracture toughness measurement using crack opening criteria, and improvement of the testing apparatus.

  12. Gel-sol synthesis of rutile nanoparticles.

    PubMed

    Verhovšek, Dejan; Lešnik, Maja; Veronovski, Nika; Samardžija, Zoran; Žagar, Kristina; Čeh, Miran

    2014-01-01

    Titanium dioxide (TiO(2)) rutile nanoparticles were synthesized at temperatures below 100 °C using a gel-sol process that provides control of the final particles' characteristics, such as the nanoparticle size, morphology, crystal structure and crystallinity. The synthesized rutile nanoparticles were analyzed using X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results show that the gel-sol process allows control over the final nanoparticle characteristics with the proper choice of reaction parameters. The most profound influence on the nanoparticles' properties is achieved by the type and concentration of the acid used in the reaction mixture. The gel-sol synthesis resulted in anisotropic rutile nanoparticles that are 60-160 nm long, depending on the reaction parameters, and have an aspect ratio of about 5. A reaction mechanism is presented, explaining the influence of various reaction parameters on the characteristics of the TiO(2) nanoparticles.

  13. Study of concentration-dependent cobalt ion doping of TiO2 and TiO(2-x)Nx at the nanoscale.

    PubMed

    Gole, James L; Prokes, Sharka M; Glembocki, O J; Wang, Junwei; Qiu, Xiaofeng; Burda, Clemens

    2010-07-01

    Experiments with a porous sol-gel generated TiO(2) nanocolloid and its corresponding oxynitride TiO(2-x)N(x) are carried out to evaluate those transformations which accompany additional doping with transition metals. In this study, doping with cobalt (Co(ii)) ions is evaluated using a combination of core level and VB-photoelectron and optical spectroscopy, complementing data obtained from Raman spectroscopy. Raman spectroscopy suggests that cobalt doping of porous sol-gel generated anatase TiO(2) and nitridated TiO(2-x)N(x) introduces a spinel-like structure into the TiO(2) and TiO(2-x)N(x) lattices. TEM and XPS data complemented by valence band-photoelectron spectra demonstrate that metallic cobalt clusters are not formed even at high doping levels. As evidenced by Raman spectroscopy, the creation of a spinel-like structure is commensurate with the room temperature conversion of the oxide and its oxynitride from the anatase to the rutile form. The onset of this kinetically driven process correlates with the formation of spinel sites within the TiO(2) and TiO(2-x)N(x) particles. Despite their visible light absorption, the photocatalytic activity of these cobalt seeded systems is diminished relative to the oxynitride TiO(2-x)N(x).

  14. 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

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

    NASA Astrophysics Data System (ADS)

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

    2013-05-01

    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.

  16. Structural analysis of TiO2 and TiO2-Ag thin films and their antibacterial behaviors

    NASA Astrophysics Data System (ADS)

    Hsieh, J. H.; Yu, R. B.; Chang, Y. K.; Li, C.

    2012-01-01

    TiO2 (rutile and anatase) thin films was first prepared using reactive sputtering, in an Ar+O2 plasma. In the 2nd stage of the experiment, various amounts (3, 7, and 10 at. %) of Ag was doped into the rutile film in order to form TiO2-Ag thin films. These films were annealed for one hour in Ar atmosphere, at 300, 400, and 500 °C. The films' structures were then examined using X-ray diffractometry. FESEM (field-emission scaning electron microscopy) was used to investigate the surface emergence of Ag particles. As for the examination of optical band gaps and absorption of these films, UV-Vis-NIR photometer was used. The results show that, in as-deposited condition, the addition of Ag might disrupt the growth of crystalline structure and cause the formation of amorphous films. After annealing, it is found that the structure tends to become anatase phase which is a metastable phase between amorphous titanium oxide and rutile. More importantly, the absorption of the Ag-doped films would be enhanced in the visible-light range. Some of the enhancement is clearly due to plasmon resonance effect. The Ag-doped samples have shown some antibacterial effect in dark. When irradiated with light, the samples show a synergistic behavior combining the bactericidal effect of Ag ions and photocatalytic effect of TiO2.

  17. Influence of terbium on structure and luminescence of nanocrystalline TiO2 thin films

    NASA Astrophysics Data System (ADS)

    Wojcieszak, Damian; Kaczmarek, Danuta; Domaradzki, Jaroslaw; Lukowiak, Anna; Strek, Wieslaw

    2013-02-01

    In this work analysis of the structural and optical properties of TiO2 thin films doped with terbium has been described. Samples were prepared by a high energy reactive magnetron sputtering process under low pressure of oxygen plasma. X-ray diffraction results have shown that different TiO2 crystal forms have been produced, depending on the amount of Tb dopant. The undoped matrix had rutile structure with crystallites with a size of 8.7 nm, while incorporation of 0.4 at. % of Tb into the film during the sputtering process resulted in anatase structure with bigger crystallites (11.7 nm). Increasing the amount of terbium up to 2 at. % and 2.6 at. % gave rutile structure with crystallites with a size of 6.6 nm for both films. However, Raman spectroscopy has revealed that in the case of TiO2:(2 at. % Tb), except for the rutile form, the presence of fine-crystalline anatase was observed. Moreover, the lack of Raman peaks shift attests to the lack of stress in the titania lattice of all of the TiO2:Tb films. This fact indicates localization of Tb3+ ions on the surface of TiO2 nanocrystals. In the case of optical investigation, results have shown that doping with terbium has a significant influence on the properties of TiO2, but it does not decrease the high transparency of the matrix. The observed changes of the transmission characteristics were produced only due to modification of the TiO2:Tb structure. Photoluminescence measurements have shown that emission of light from TiO2:Tb films occurs when the amount of terbium is 2.6 at. %. Based on the obtained results a scheme of direct energy transfer from titanium dioxide matrix (with rutile structure) to Tb3+ ions has been proposed.

  18. Comparison study on photocatalytic oxidation of pharmaceuticals by TiO2-Fe and TiO2-reduced graphene oxide nanocomposites immobilized on optical fibers.

    PubMed

    Lin, Lu; Wang, Huiyao; Jiang, Wenbin; Mkaouar, Ahmed Radhi; Xu, Pei

    2017-03-08

    Incorporating reduced graphene oxide (rGO) or Fe(3+) ions in TiO2 photocatalyst could enhance photocatalytic degradation of organic contaminants in aqueous solutions. This study characterized the photocatalytic activities of TiO2-Fe and TiO2-rGO nanocomposites immobilized on optical fibers synthesized by polymer assisted hydrothermal deposition method. The photocatalysts presented a mixture phase of anatase and rutile in the TiO2-rGO and TiO2-Fe nanocomposites. Doping Fe into TiO2 particles (2.40eV) could reduce more band gap energy than incorporating rGO (2.85eV), thereby enhancing utilization efficiency of visible light. Incorporating Fe and rGO in TiO2 decreased significantly the intensity of TiO2 photoluminescence signals and enhanced the separation rate of photo-induced charge carriers. Photocatalytic performance of the synthesized nanocomposites was measured by the degradation of three pharmaceuticals under UV and visible light irradiation, including carbamazepine, ibuprofen, and sulfamethoxazole. TiO2-rGO exhibited higher photocatalytic activity for the degradation of pharmaceuticals under UV irradiation, while TiO2-Fe demonstrated more suitable for visible light oxidation. The results suggested that the enhanced photocatalytic performance of TiO2-rGO could be attributed to reduced recombination rate of photoexcited electrons-hole pairs, but for TiO2-Fe nanocomposite, narrower band gap would contribute to increased photocatalytic activity.

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

    PubMed Central

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

    2013-01-01

    Summary 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. PMID:23844339

  20. 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.

  1. 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

  2. Impact of bimetal electrodes on dielectric properties of TiO2 and Al-doped TiO2 films.

    PubMed

    Kim, Seong Keun; Han, Sora; Jeon, Woojin; Yoon, Jung Ho; Han, Jeong Hwan; Lee, Woongkyu; Hwang, Cheol Seong

    2012-09-26

    Rutile structured Al-doped TiO(2) (ATO) and TiO(2) films were grown on bimetal electrodes (thin Ru/thick TiN, Pt, and Ir) for high-performance capacitors. The work function of the top Ru layer decreased on TiN and increased on Pt and Ir when it was thinner than ~2 nm, suggesting that the lower metal within the electrodes influences the work function of the very thin Ru layer. The use of the lower electrode with a high work function for bottom electrode eventually improves the leakage current properties of the capacitor at a very thin Ru top layer (≤2 nm) because of the increased Schottky barrier height at the interface between the dielectric and the bottom electrode. The thin Ru layer was necessary to achieve the rutile structured ATO and TiO(2) dielectric films.

  3. Effects of TiO2 structures in dye-sensitized solar cell.

    PubMed

    Kim, Bok-Min; Rho, Seon-Gyun; Kang, Choon-Hyoung

    2011-02-01

    In this work, the effects of crystalline structure of the TiO2, which is incorporated in fabrication of the n-type electrode, on the DSSC performance were investigated in terms of the energy conversion efficiency. In this effort, TiO2 nanoparticle pastes with varying contents of rutile and anatase structures were prepared by using the ethanol mixing method. The most efficient photo-electro-chemical performance was achieved for the DSSC fabricated with the TiO2 paste in which the anatase form of the nanocrystal extends to 90%.

  4. Local Bonding Analysis of the Valence and Conduction Band Features of TiO2

    DTIC Science & Technology

    2007-01-01

    nanocrystalline samples tenuous at best. Hence, the phase of the unannealed TiO2 films cannot conclusively be identified as either anatase or rutile...reveals the local physical origin of the electronic structure in nanocrystalline films . TiO2 has further been chosen as a natural starting point to...thickness ratio is 2:1 for TiO2 . This assump- tion has been verified by XPS studies of the substrate Si 2p core-level spectra with film thickness. The

  5. Raman study of TiO2 coatings modified by UV pulsed laser

    NASA Astrophysics Data System (ADS)

    Belka, Radosław; Keczkowska, Justyna; Sek, Piotr

    2016-12-01

    The TiO2 coatings were prepared by simple sol-gel method and modified by UV pulsed laser. TiO2, also know as titania, is a ceramic compound, existing in numerous polymorphic forms, mainly as tetragonal rutile and anatase, and rhomboidal brookite. Rutile is the most stable form of titanium dioxide, whereas anatase is a metastable form, created in lower temperatures than rutile. Anatase is marked with higher specific surface area, porosity and a higher number of surface hydroxyl groups as compared to rutile. The unique optical and electronic properties of TiO2 results in its use as semiconductors dielectric mirrors, sunscreen and UV-blocking pigments and especially as photocatalyst. In this paper, the tetraisopropoxide was used as Ti precursor according to sol-gel method. An organic base was applied during sol preparation. Prepared gel was coated on glass substrates and calcined in low temperature to obtain amorphous phase of titania. Prepared coatings were modified by UV picosecond pulse laser with different pulse repetition rate and pulse power. Physical modification of the coatings using laser pulses was intended in order change the phase content of the produced material. Raman spectroscopy (RS) method was applied to studies of modified coatings as it is one of the basic analytical techniques, supporting the identification of compounds and obtaining information about the structure. Especially, RS is a useful method for distinguishing the anatase and rutile phases. In these studies, anatase to rutile transformation was observed, depending on laser parameters.

  6. Novel (1 × 1)-reconstructions and native defects of TiO2 anatase (101) surface

    NASA Astrophysics Data System (ADS)

    Wang, Qinggao; Ren, Fengzhu; Dong, Huafeng; Wang, Yuanxu

    2017-05-01

    In this paper, reconstructions and native defects of TiO2 anatase (101) surface are studied using the state-of-the-art theoretical method. We find that O interstitials are dominated defects at an oxidization environment. These O interstitials induce acceptor energy levels, corresponding to an indirect-direct band transition and a bandgap narrowing. And thus, the experimental result that an O-rich anatase TiO2 has the higher photocatalytic activity can be understood. The formation of O vacancies and Ti interstitials becomes feasible at a reduced condition, and reconstructed TiO2 anatase (101)-(1 × 1) structures present with increasing reduction degree. Furthermore, the Fermi levels of defected and reconstructed TiO2 anatse (101) can be modulated in a wide range (i.e., nearly the whole band gap), which are different from those of TiO2 rutile (110).

  7. Effects of annealed temperature on the properties of TiO2 thin films

    NASA Astrophysics Data System (ADS)

    Kumar, Avesh

    2016-05-01

    In this work, the structural, morphological and electrical properties of TiO2 thin films are studied. The phase transformation of TiO2 from anatase to rutile is occurred at a certain temperature. This transformation increases defects concentration onthe surface of the film which acts as trapping sites for carriers, thereby affecting the Fermi level of TiO2 film.Quantitative estimation of Fermi level shifting is measured in terms of work function measurement using scanning Kelvin probe measurement. Work function of TiO2 was found to decrease with increasing annealed temperature indicating shifting of Fermi level towards conduction band. Position of Fermi level plays an important role in phase transformation and electronic properties of TiO2.

  8. Photoconductivity studies on amorphous and crystalline TiO2 films doped with gold nanoparticles

    NASA Astrophysics Data System (ADS)

    Valverde-Aguilar, G.; García-Macedo, J. A.; Rentería-Tapia, V.; Aguilar-Franco, M.

    2011-06-01

    In this work, amorphous and crystalline TiO2 films were synthesized by the sol-gel process at room temperature. The TiO2 films were doped with gold nanoparticles. The films were spin-coated on glass wafers. The crystalline samples were annealed at 100°C for 30 minutes and sintered at 520°C for 2 h. All films were characterized using X-ray diffraction, transmission electronic microscopy and UV-Vis absorption spectroscopy. Two crystalline phases, anatase and rutile, were formed in the matrix TiO2 and TiO2/Au. An absorption peak was located at 570 nm (amorphous) and 645 nm (anatase). Photoconductivity studies were performed on these films. The experimental data were fitted with straight lines at darkness and under illumination at 515 nm and 645 nm. This indicates an ohmic behavior. Crystalline TiO2/Au films are more photoconductive than the amorphous ones.

  9. One-Step Solvothermal Synthesis of Black TiO2 Films for Enhanced Visible Absorption.

    PubMed

    Chen, Shanlong; Tao, Jie; Tao, Haijun; Wang, Chen; Shen, Yizhou; Jiang, Jiajia; Zhu, Lumin; Zeng, Xiaofei; Wang, Tao

    2016-03-01

    An economic and facile solvothermal method was reported to prepare black TiO2 films on Ti foils that possessed the property of optical absorption in the visible region. The UV-vis spectra showed that the black TiO2 samples exhibited highly enhanced visible-light absorption from 400-600 nm. The black TiO2 films were compact and uniform, composed of nanoparticles and nanosheets. Moreover, a mixed structure of anatase and rutile was present in black TiO2 films. The electron paramagnetic resonance (EPR) spectra confirmed the presence of Ti3+ in samples, which accounted for longer wavelength optical absorption. The results showed that the TiO2 films had retained their black color upon storage in ambient atmosphere for more than one month. Therefore, it was supposed that the ethylene glycol in solvothermal reaction was the key factor for the extension of the absorption spectrum.

  10. Natural dye sensitized TiO2 nanorods assembly of broccoli shape based solar cells.

    PubMed

    Yuvapragasam, Akila; Muthukumarasamy, N; Agilan, S; Velauthapillai, Dhayalan; Senthil, T S; Sundaram, Senthilarasu

    2015-07-01

    TiO2 nanorods based thin films with rutile phase have been synthesized using template free low temperature hydrothermal method. The scanning electron microscope images showed that the prepared TiO2 samples were made of TiO2 nanorods and the nanorods had arranged by itself to form a broccoli like shape. The X-ray diffraction studies revealed that the prepared TiO2 samples exhibit rutile phase. The grown TiO2 nanorods had been sensitized using the flowers of Sesbania (S) grandiflora, leaves of Camellia (C) sinensis and roots of Rubia (R) tinctorum. Dye sensitized solar cells had been fabricated using the natural dye sensitized TiO2 nanorods based thin film photoelectrode and the open circuit voltage and short circuit current density were found to lie in the range of 0.45-0.6 V and 5.6-6.4 mA/cm(2) respectively. The photovoltaic performance of all the fabricated natural dye sensitized TiO2 solar cells indicate that natural dyes have the potential to be used as effective sensitizer in dye sensitized solar cells.

  11. 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.

  12. 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

    2012-12-07

    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.

  13. 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.

  14. 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.

  15. 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

  16. 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.

  17. High efficiency dye-sensitized solar cell based on novel TiO2 nanorod/nanoparticle bilayer electrode.

    PubMed

    Hafez, Hoda; Lan, Zhang; Li, Qinghua; Wu, Jihuai

    2010-08-26

    High light-to-energy conversion efficiency was achieved by applying novel TiO2 nanorod/nanoparticle (NR/NP) bilayer electrode in the N719 dye-sensitized solar cells. The short-circuit current density (J SC), the open-circuit voltage (V OC), the fill factor (FF), and the overall efficiency (η) were 14.45 mA/cm(2), 0.756 V, 0.65, and 7.1%, respectively. The single-crystalline TiO2 NRs with length 200-500 nm and diameter 30-50 nm were prepared by simple hydrothermal methods. The dye-sensitized solar cells with pure TiO2 NR and pure TiO2 NP electrodes showed only a lower light-to-electricity conversion efficiency of 4.4% and 5.8%, respectively, compared with single-crystalline TiO2 NRs. This can be attributed to the new NR/NP bilayer design that can possess the advantages of both building blocks, ie, the high surface area of NP aggregates and rapid electron transport rate and the light scattering effect of single-crystalline NRs.

  18. Optical properties of hierarchical-nanostructured TiO2 and its time-dependent photo-degradation of gaseous acetaldehyde

    NASA Astrophysics Data System (ADS)

    Ahn, Kyun; Kim, Min-Sun; Kim, Soon-Hyun; Hyun Kim, Jae; Jeong, Se-Young; Kim, Jong-Pil; Sung Jin, Jong; Cho, Chae-Ryong

    2013-12-01

    The TiO2 hierarchical nanostructures (HNs) composed of rutile TiO2 nanowires on anatase TiO2 nanofibers had higher photocatalytic activities of 62% and 48% than the commercial TiO2 nanoparticles (˜21 nm diameter) in the continuous flow mode and closed-circulation mode, respectively, leading to an efficient degradation of gaseous acetaldehyde under UV-light irradiation. This behavior may be attributed to the effective TiO2 HNs with specific surface area of 85.1 m2/g and lower radiative recombination of self-trapped excitons, enabling an effective electron-hole separation.

  19. Absence of ferromagnetism in Fe-doped TiO2 nanoparticles

    NASA Astrophysics Data System (ADS)

    Balcells, Ll.; Frontera, C.; Sandiumenge, F.; Roig, A.; Martínez, B.; Kouam, J.; Monty, C.

    2006-09-01

    The structural and magnetic properties of Ti1-xFexO2-ɛ (x≈0.13) nanoparticles prepared by vaporization-condensation method are analyzed. Samples, mainly of rutile phase, exhibit a pronounced mosaic structure and are free of secondary phases or impurities. Mössbauer spectroscopy evidences the absence of magnetic ordering and shows features indicative of the existence of two doublets assigned to two different structural arrangements of Fe3+ ions substituting for Ti4+ ions in the rutile structure. The application of the Goodenough-Kanamori rules clearly indicates that conventional FM ordering should not be expected in Fe-doped TiO2 with rutile structure.

  20. 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.

  1. 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

  2. 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.

  3. Unprecedented coloration of rutile titanium dioxide nanocrystalline thin films.

    PubMed

    Mane, Rajaram S; Joo, Oh-Shim; Lee, Won Joo; Han, Sung-Hwan

    2007-01-01

    In this communication, TiO2 nanocrystalline thin films synthesized by a room temperature (27 degrees C) chemical dip process. To our knowledge, this is first report of the preparation of nanoscale rutile TiO2 particles from common inorganic salt at such low temperature. Interestingly, unprecedented dynamic color change accompanies with titanium dioxide grain size, which can be seen with the naked eye that generated curiosity in our mind to check UV-vis absorption, where significant changes were observed. The room temperature synthesized thin films of rutile titanium dioxide make it a potential candidate for high-compatibility material, which can be used in artificial heart valves.

  4. Preparation of anatase/rutile mixed-phase titania nanoparticles for dye-sensitized solar cells.

    PubMed

    Hwang, Yong-Kyung; Park, Sung Soo; Lim, Jun-Heok; Won, Yong Sun; Huh, Seong

    2013-03-01

    Acid-labile high surface mesoporous ZnO/Zn(OH)2 composite material is used as a novel hard template for the preparation of mesoporous amorphous TiO2. The template-free amorphous TiO2 material is then thermally crystallized at suitable temperature to control the relative ratio of anatase and rutile phases in a particle. Four different anatase/rutile (AR) mixed-phase TiO2 nanoparticles (AR-3, AR-15, AR-20, and AR-23 denoted for the samples of 3%, 15%, 20%, and 23% rutile phase, respectively) are prepared and characterized by powder X-ray diffraction (PXRD) and transmission electron microscopy (TEM). The coexistence of anatase and rutile phases in a TiO2 nanoparticle is visually confirmed by HRTEM analysis. These mixed-phase TiO2 nanoparticles are examined as candidates for photoelectrodes of dye-sensitized solar cells (DSSCs). The J-V curves and IPCE spectra for the DSSCs prepared from the mixed-phase TiO2 nanoparticles are obtained, and their photovoltaic properties are investigated. The photo-conversion efficiency (eta) indicates the highest value of 5.07% for AR-20. The synergistic effect of coexisting anatase and rutile phases with an optimal ratio in a TiO2 nanoparticle of AR-20 for an efficient interfacial transfer of photo-generated electrons is likely to lead to the highest efficiency among the AR-n samples.

  5. 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.

  6. Temperature dependent tuning of the flat band voltages of TiO2/Si interfaces

    NASA Astrophysics Data System (ADS)

    Nasim, F.; Ali, A.; Bhatti, A. S.; Naseem, S.

    2011-12-01

    In this work, we present study of charge accumulation at the TiO2/Si interfaces and its variation in the TiO2 thin films sputter-deposited on n-Si, p-Si, and B-implanted Si substrates at various growth temperatures. TiO2 films, deposited in an oxygen deficient environment, showed significant growth of rutile phase and absence of anatase phase in the as-grown films. Annealing in air resulted in emergence of anatase phase, thus improving the ratio of anatase to rutile phase in TiO2 films. The flatband voltages determined from capacitance-voltage measurements were observed to be high in the rutile phase TiO2 and dropped considerably on annealing, due to formation of the anatase phase. The drop in the flatband voltages on annealing was also observed to depend strongly on the initial growth temperature. Films grown at high temperatures showed relatively low flatband voltages as compared to the films grown at room temperature. It is demonstrated that VFB strongly depends on the interface traps, and oxide-related defects were two orders of magnitude smaller than interface traps. The amount of depletion of the interface charge was found to depend on annealing. In the end, we also demonstrate that interface traps and oxide defects are not the only factors affecting the band bending, but the underlying substrate also plays an important role.

  7. 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.

  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

    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.

  10. 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.

  11. 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

  12. Synthesis and characterization of structural and optical properties of single crystalline a-TiO2 films on MgAl2O4(111) substrate

    NASA Astrophysics Data System (ADS)

    Xu, Haisheng; Feng, Xianjin; Luan, Caina; Ma, Jin

    2017-01-01

    Anatase phase TiO2 (a-TiO2) films have been deposited on MgAl2O4(111) substrates by the metal organic chemical vapor deposition (MOCVD) method at the substrate temperatures of 500-650°C. The structural analyses showed that the films were highly (004) oriented with tetragonal anatase structure and the epitaxial relationship was given as a-TiO2(004)||MgAl2O4 (111). The sample prepared at 600°C exhibited the best crystallization with a single-crystalline epitaxial film. The average transmittance of every TiO2 film in the visible range exceeded 90% excluding the influence of the substrate. The morphology and composition of the TiO2 films have also been studied in detail.

  13. Size effect on thermal stability of nanocrystalline anatase TiO2

    NASA Astrophysics Data System (ADS)

    Wang, Junwei; Mishra, Ashish Kumar; Zhao, Qing; Huang, Liping

    2013-06-01

    Thermal stability of nanocrystalline anatase TiO2 against coarsening and anatase-rutile phase transformation was studied using both a pyroprobe heater and a conventional furnace. The pyroprobe heater, because of the programmable control and the ultra-fast heating rate (up to 20 000 °C s-1), for the first time, allows us to access the very early stage of the sintering and phase-transformation processes. Our short time (0-30 s) heat treatments reveal that rapid grain growth takes place first in anatase nanoparticles (NPs) upon the initial heating due to the lower activation energy compared with that for the anatase-rutile phase transformation. Meanwhile, rutile-like structural elements develop at the interface between anatase NPs during the fast grain growth period, which evolve into rutile nuclei with time, followed by nuclei growth, to convert nanocrystalline anatase into rutile rapidly in the temperature range where the phase transformation does not occur in coarse anatase TiO2. Overall, both grain growth and phase transformation in smaller anatase NPs happen at lower temperatures and faster than in bigger ones. The coupled sintering-phase-transformation mechanism can be exploited to design thermally stable nanocrystalline anatase TiO2 by reducing the sintering kinetics, for example, via minority additives.

  14. Hydroxyapatite growth on anodic TiO2 nanotubes.

    PubMed

    Tsuchiya, Hiroaki; Macak, Jan M; Müller, Lenka; Kunze, Julia; Müller, Frank; Greil, Peter; Virtanen, Sannakaisa; Schmuki, Patrik

    2006-06-01

    In the present work, we study the growth of hydroxyapatite formation on different TiO(2) nanotube layers. The nanotube layers were fabricated by electrochemical anodization of titanium in fluoride-containing electrolytes. To study various nanotube lengths, layers with an individual tube diameter of 100 nm were grown to a thickness of approximately 2 mum or 500 nm. The ability to form apatite on the nanotube layers was examined by immersion tests combined with SEM, XRD and FT-IR investigations. For reference, experiments were also carried out on compact anodic TiO(2) layers. The results clearly show that the presence of the nanotubes on a titanium surface enhances the apatite formation and that the 2-mum thick nanotube layer triggers deposition faster than the thinner layers. Tubes annealed to anatase, or a mixture of anatase and rutile are clearly more efficient in promoting apatite formation than the tubes in their "as-formed" amorphous state.

  15. 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.

  16. 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.

  17. Thermally induced superhydrophilicity in TiO2 films prepared by supersonic aerosol deposition.

    PubMed

    Park, Jung-Jae; Kim, Do-Yeon; Latthe, Sanjay S; Lee, Jong-Gun; Swihart, Mark T; Yoon, Sam S

    2013-07-10

    Superhydrophilic and superhydrophobic surfaces enable self-cleaning phenomena, either forming a continuous water film or forming droplets that roll off the surface, respectively. TiO2 films are well-known for their extreme hydrophilicity and photocatalytic characteristics. Here, we describe nanostructured TiO2 thin films prepared by supersonic aerosol deposition, including a thorough study of the effects of the annealing temperature on the crystal structure, surface morphology, surface roughness, and wetting properties. Powder X-ray diffraction showed that supersonic deposition resulted in fragmentation and amorphization of the micrometer-size anatase (60%)-rutile (40%) precursor powder and that, upon annealing, a substantial fraction of the film (~30%) crystallized in the highly hydrophilic but metastable brookite phase. The film morphology was also somewhat modified after annealing. Scanning electron microscopy and atomic force microscopy revealed rough granular films with high surface roughness. The as-deposited TiO2 films were moderately hydrophilic with a water contact angle (θ) of ~45°, whereas TiO2 films annealed at 500 °C became superhydrophilic (θ ~ 0°) without UV illumination. This thermally induced superhydrophilicity of the TiO2 films can be explained on the basis of the combined effects of the change in the crystal structure, surface microstructure, and surface roughness. Supersonic aerosol deposition followed by annealing is uniquely able to produce these nanostructured films containing a mixture of all three TiO2 phases (anatase, rutile, and brookite) and exhibiting superhydrophilicity without UV illumination.

  18. Photocatalytic degradation of Rhodamine B by C-N-S tridoped TiO2 nanoparticles

    NASA Astrophysics Data System (ADS)

    Amreetha, S.; Dhanuskodi, S.; Nithya, A.; Jothivenkatachalam, K.

    2014-03-01

    C-N-S tridoped TiO2 nanoparticles were synthesized by sol-gel method using thiourea as a source compound for carbon (C), nitrogen (N) and sulphur (S). The crystalline phase and morphology of the doped and undoped TiO2 nanoparticles are analyzed by XRD and FESEM. FTIR confirms the bonding interaction of C, N and S in TiO2 lattice. Compared to the doped samples undoped sample annealed at 600°C shows more absorbance in the visible region due to the existence of rutile phase. Presence of oxygen vacancy is confirmed from the photoluminescence spectra. XPS indicates the existence of the carbon atom in the form of carbonaceous species on the surface of the TiO2 and absorbs the visible light to enhance the photocatalytic activity. The photocatalytic activity of C-N-S tridoped TiO2 nanoparticles were evaluated for the degradation of Rhodamine B organic dye under the visible light irradiation. Maximum of ~ 100% degradation exhibits for the C-N-S tridoped sample (D4) calcined at 600°C. This highly active photocatalytic performance is associated with the existence of oxygen vacancies, the acidic sites on the surface (SO4 2-) and the mixed phases of anatase and rutile in TiO2 lattices.

  19. From titanium oxydifluoride (TiOF2) to titania (TiO2): phase transition and non-metal doping with enhanced photocatalytic hydrogen (H2) evolution properties.

    PubMed

    Wen, Ci Zhang; Hu, Qiu Hong; Guo, Ya Nan; Gong, Xue Qing; Qiao, Shi Zhang; Yang, Hua Gui

    2011-06-07

    Single-crystalline TiOF(2) crystals with cubical morphology were prepared via a facile solvothermal method and their transformation to anatase TiO(2) under different calcination conditions such as pure argon, moist argon and pure hydrogen sulfide (H(2)S) was explored by using XRD/Raman/UV-Vis/SEM/TEM/SAED. The non-metal sulfur doping was successfully fulfilled and the doped TiO(2) microcubes showed the best photocatalytic H(2) evolution property.

  20. 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.

  1. Oxygen release and structural changes in TiO2 films during photocatalytic oxidation

    NASA Astrophysics Data System (ADS)

    Yoshida, Kenta; Nanbara, Takahiro; Yamasaki, Jun; Tanaka, Nobuo

    2006-04-01

    Changes in the crystal structure and grain modifications in titanium oxide (TiO2) thin films were observed during the photocatalytic oxidation of hydrocarbons. When the hydrocarbon and collodion films were irradiated, single crystalline titanium oxide transformed into polycrystals. The titanium oxide films gradually became network aggregates. These changes were analyzed with a dedicated in situ transmission electron microscope and observed three dimensionally by electron tomography. A detailed analysis of electron energy loss spectra of the samples also revealed that the changes were associated with the loss of oxygen atoms in the TiO2 crystal lattice. Correlations between the polycrystalline grain size of TiO2 and its catalyst activity were discussed based on the measured data.

  2. Phase-dependant photochemistry of TiO2 nanoparticles in the degradation of organic dye methylene blue under solar light irradiation

    NASA Astrophysics Data System (ADS)

    Prasannalakshmi, P.; Shanmugam, N.

    2017-09-01

    This paper describes the photochemistry of nanoparticles of TiO2 in anatase, anatase/rutile, and rutile phases for the degradation of methylene blue (MB) under solar light irradiation. For this process, TiO2 nanoparticles were synthesized by a sol-gel method, and different phases were achieved by annealing the prepared particles at various temperatures. Further, the annealed products were subjected to structural, optical, and morphological characterizations. The photocatalytic measurements show that TiO2 in the anatase phase possesses superior activity towards the degradation of MB due to its smaller crystallite size, enhanced BET surface area, higher pore size, and low charge transfer resistance.

  3. 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.

  4. Synthesis of single-crystalline -Ga2O3 nanoribbons

    NASA Astrophysics Data System (ADS)

    Yang, Z. X.; Wu, Y. J.; Zhu, F.; Zhang, Y. F.

    2004-11-01

    Quasi-one-dimensional thin single-crystalline -Ga2O3 nanoribbons have been successfully synthesized via thermal evaporation of a Ga droplet at temperatures as low as 900 °C without the presence of a catalyst. Unlike the commonly used thermal evaporation method, the liquid phase was employed to synthesize the nanoribbons. The as-synthesized -Ga2O3 nanoribbons are pure, structurally uniform, single crystalline, and most of them are free from defects. Other interesting -Ga2O3 microstructures have also been found and can be helpful in understanding the growth mechanisms of β-Ga2O3 nanoribbons.

  5. 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.

  6. 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

  7. Controlled crystal phase of TiO2 by spray pyrolysis method

    NASA Astrophysics Data System (ADS)

    Aji, B. B.; Shih, S. J.; Pradita, T.

    2017-04-01

    TiO2 in powder form was preferred due to its flexibility and easy handling. TiO2 powders with controlled crystal phase were successfully synthesised by ultrasonic spray pyrolysis from titanium tetraisopropoxide (TTIP) precursor. The effect of various acid solvents (nitric acid, acetic acid and citric acid) in relationship with crystal compositions have been well-studied. This experimental study suggested that the ratio of anatase phase achieved from TiO2 prepared by nitric, acid acetic acid and citric acid solvent are 85%, 39% and 27% respectively. Spurs-Myers equation used to determine the anatase-rutile phase. Crystal sizes were calculated using Scherer equation. Both of ratio and crystal size were estimated from corresponding X-ray diffraction pattern. Precipitation and chelating process were the keys to determine the last composition of TiO2.

  8. Phase stability frustration on ultra-nanosized anatase TiO2.

    PubMed

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

    2015-06-04

    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.

  9. Self-assembled TiO2-Graphene Hybrid Nanostructures for Enhanced Li-ion Insertion

    SciTech Connect

    Wang, Donghai; Choi, Daiwon; Li, Juan; Yang, Zhenguo; Nie, Zimin; Kou, Rong; Hu, Dehong; Wang, Chong M.; Saraf, Laxmikant V.; Zhang, Jiguang; Aksay, Ilhan A.; Liu, Jun

    2009-04-01

    We used anionic sulfate surfactants to assist the stabilization of graphene in aqueous solutions and facilitate the self-assembly of in-situ grown nanocrystalline TiO2, rutile and anatase, with graphene. These nanostructured TiO2-graphene hybrid materials were used for investigation of Li-ion insertion properties. The hybrid materials showed significantly enhanced Li-ion insertion/extraction in TiO2. The specific capacity was more than doubled at high charge rates, as compared with the pure TiO2 phase. The improved capacity at high charge-discharge rate may be attributed to increased electrode conductivity in presence of a percolated graphene network embedded into the metal oxide electrodes.

  10. 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

  11. Photoresponse and Donor Concentration of Plasma-Sprayed TiO2 and TiO2-ZnO Electrodes

    NASA Astrophysics Data System (ADS)

    Ye, F.-X.; Ohmori, A.; Li, C.-J.

    2005-12-01

    The photoelectrochemical characteristics of plasma-sprayed porous TiO2, TiO2-5%ZnO, and TiO2-10%ZnO electrodes in 0.1 N NaOH solution were studied through a three-electrode cell system. The microstructure, morphology, and composition of the electrodes were analyzed using an electron probe surface roughness analyzer (ERA-8800FE), scanning electron microscopy, and x-ray diffraction. The results indicate that the sprayed electrodes have a porous microstructure, which is affected by the plasma spray parameters and composition of the powders. The TiO2-ZnO electrodes consist of anatase TiO2, rutile TiO2, and Zn2Ti3O8 phase. The photoresponse characteristics of the plasma-sprayed electrodes are comparable to those of single-crystal TiO2, but the breakdown voltage is close to 0.5 V (versus that of a saturated calomel electrode). The short-circuit photocurrent density ( J SC) increases with a decrease of donor concentration, which was calculated according to the Gartner-Butler model. For the lowest donor concentration of a TiO2-5%ZnO electrode sprayed under an arc current of 600 A, the short-circuit J SC is approximately 0.4 mA/cm2 higher than that of the TiO2 electrodes under 30 mW/cm2 xenon light irradiation. The J SC increases linearly with light intensity.

  12. Synthesis of 1-D porous TiO2 on fly ash carriers through surface modification method

    NASA Astrophysics Data System (ADS)

    Wang, Jingang; Wang, Haiying; Yu, Jiemei

    2017-08-01

    By modification of silane coupling agent, the TiO2 nanocrystal seeds layer was loaded on the surface of fly ash carriers. Based on that, the hydrothermal method was adopted to synthetize the one-dimensional (1-D) TiO2 which were loaded on the carriers densely under the condition of a low concentration TiO2 precursor. Because of the calcination residual of modifier, the transmission and diffusion of ions on the surface of TiO2 would be hindered, and the 1-D TiO2 with porous surface can be obtained. The specific surface area of porous TiO2/fly-ash composite particles reaches 174.8 m2/g. HRTEM and XRD results suggested that the TiO2 prepared was a single-crystalline structure featuring the (110) plane, but the plane had some structural defects for being bended and interrupted. Results of photocatalytic degradation of Rhodamine B showed that the catalytic activity of 1-D porous TiO2 was higher than that without a porous structure.

  13. Photoelectrochemical study on charge transfer properties of TiO2-B nanowires with an application as humidity sensors.

    PubMed

    Wang, Geng; Wang, Qiang; Lu, Wu; Li, Jinghong

    2006-11-02

    One-dimensional (1-D) TiO2-B nanowires have been synthesized via a facile solvothermal route. The morphology and crystalline structures of the nanowires were characterized by using powder X-ray diffraction, low/high-resolution transmission electron microscopy, and Brunauer-Emmett-Teller methods. It is important with the calcination treatment at 350 degrees C to maintain 1-D morphologies of the material in the form of single-crystalline TiO2-B nanowires. In addition, a simple method was used to study the photogenerated charge transfer and photoelectrochemical properties of the TiO2-B nanowires in comparison with commercial TiO2 P25 nanoparticles based on the experimental data from the electric field-effected photocurrent action spectrum and Mott-Schottky measurements. It was revealed that TiO2-B nanostructures played an important role in the photoelectrochemical processes. The synthetic TiO2-B nanowire electrode exhibited unique electronic properties, e.g., favorable charge-transfer ability, negative-shifted appearing flat-band potential, existence of abundant surface states or oxygen vacancies, and high-level dopant density. Moreover, the obtained TiO2-B nanowires were found to display excellent humidity sensing abilities as functional materials in the humidity sensor application. With relative humidity increased from 5% to 95%, about one and half orders of magnitude change in resistance was observed in the TiO2-B nanowire-based surface-type humidity sensors.

  14. Synthesis of TiO2/WO3 nanoparticles via sonochemical approach for the photocatalytic degradation of methylene blue under visible light illumination.

    PubMed

    Anandan, Sambandam; Sivasankar, Thirugnanasambandam; Lana-Villarreal, Teresa

    2014-11-01

    Through an ultrasound assisted method, TiO2/WO3 nanoparticles were synthesized at room temperature. The XRD pattern of as-prepared TiO2/WO3 nanoparticles matches well with that of pure monoclinic WO3 and rutile TiO2 nanoparticles. TEM images show that the prepared TiO2/WO3 nanoparticles consist of mixed square and hexagonal shape particles about 8-12nm in diameter. The photocatalytic activity of TiO2/WO3 nanoparticles was tested for the degradation of a wastewater containing methylene blue (MB) under visible light illumination. The TiO2/WO3 nanoparticles exhibits a higher degradation rate constant (6.72×10(-4)s(-1)) than bare TiO2 nanoparticles (1.72×10(-4)s(-1)) under similar experimental conditions. Copyright © 2014 Elsevier B.V. All rights reserved.

  15. 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.

  16. Electrochemical degradation of refractory pollutants using TiO2 single crystals exposed by high-energy {001} facets.

    PubMed

    Zhang, Ai-Yong; Long, Lu-Lu; Liu, Chang; Li, Wen-Wei; Yu, Han-Qing

    2014-12-01

    Anodic material plays a vital role in electrochemical water treatment. Titanium dioxide (TiO2) has been widely recognized as an excellent semiconductor photocatalyst, rather than an efficient electrocatalyst, due to its relatively low electric conductivity and poor electrochemical activity. In this work, it is found that TiO2 can actually become a superior electrocatalyst when its crystal shape and exposed facet are finely tuned. The shape-engineered TiO2 single crystals with {001} facets exhibit an excellent electro-catalytic activity and stability for degrading typical organic pollutants such as rhodamine B and bisphenol A, and treating complex landfill leachate. Its electro-catalytic superiority is mainly attributed to the single-crystalline structure and exposed polar {001} facet. Our findings could provide new possibility of utilizing TiO2 for efficient electrochemical water treatment because of its high activity, great stability, low cost and no toxicity. Copyright © 2014 Elsevier Ltd. All rights reserved.

  17. Growth of single-crystalline particles of metallic copper

    NASA Astrophysics Data System (ADS)

    Guo, Jinlei; Shen, Shaobo; Zhao, Yingshi; Wang, Fuming

    2016-10-01

    Most of ultrafine particles of metallic copper reported so far were of polycrystalline structures. Here, some ultrafine particles of metallic copper of single-crystalline structure were synthesized in gas phase. Some mixtures of a raw copper powder (about 79 μm) and sodium chloride powder were used as the precursor materials. The materials were chlorinated by dry chlorine at 400 °C. Some anhydrous eutectics composed of copper chlorides and sodium chloride were thus obtained. The eutectics were first heated in situ up to 900 °C and then carried to a gas space by evaporation using a flowing Argon, where they met H2 and were reduced to metallic copper particles. It was found that all these copper particles prepared were of single-crystalline structure irrespective of the molar ratio of raw copper and sodium chloride. When the molar ratio of NaCl to Cu in the precursor materials was 1 to 3, some dispersed octahedral particles of single-crystalline copper with an average size of 776 nm were prepared. However, when the ratio was increased to 4 to 1, some dispersed spherical particles of single-crystalline copper with a size of 92 nm were obtained. No impurities from the two shapes of copper particles were detected. The mechanisms involved in controlling the shape and size of copper particles were proposed.

  18. Nonequilibrium synthesis of highly porous single-crystalline oxide nanostructures

    DOE PAGES

    Lee, Dongkyu; Gao, Xiang; Fan, Lisha; ...

    2017-01-20

    A novel synthesis route to the formation of vertically aligned single-crystalline oxide nanostructures is found by precisely controlling the nonequilibrium pulsed laser deposition process. Here, the columnar nanostructures with deep crevices offering a large surface area are generated owing to the diffusion limited geometric shadowing effect.

  19. Synthesis of single crystalline layered lithium manganese oxide nanorods

    NASA Astrophysics Data System (ADS)

    Wang, Xiong; Song, Jimei; Gao, Lisheng; Zheng, Huagui; Ji, Mingrong; Zhang, Zude

    2004-12-01

    Single-crystalline layered lithium manganese oxide nanorods were prepared via a low-temperature molten salt synthesis method. The material was investigated by a variety of techniques, including X-ray powder diffraction (XRD), transmission electron microscopy (TEM), and X-ray photoelectron spectrum (XPS).

  20. 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

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

    NASA Astrophysics Data System (ADS)

    Wang, Jingang; Yu, Jiemei; Zhu, Xiaoli; Kong, Xiang Zheng

    2012-11-01

    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.

  2. A novel 3D structure composed of strings of hierarchical TiO2 spheres formed on TiO2 nanobelts with high photocatalytic properties

    NASA Astrophysics Data System (ADS)

    Jiang, Yongjian; Li, Meicheng; Song, Dandan; Li, Xiaodan; Yu, Yue

    2014-03-01

    A novel hierarchical titanium dioxide (TiO2) composite nanostructure with strings of anatase TiO2 hierarchical micro-spheres and rutile nanobelts framework (TiO2 HSN) is successfully synthesized via a one-step hydrothermal method. Particularly, the strings of hierarchical spheres are assembled by very thin TiO2 nanosheets, which are composed of highly crystallized anatase nanocrystals. Meanwhile, the HSN has a large surface area of 191 m2/g, which is about 3 times larger than Degussa P25. More importantly, the photocatalytic activity of HSN and P25 were evaluated by the photocatalytic oxidation decomposition of methyl orange (MO) under UV light illumination, and the TiO2 HSN shows enhanced photocatalytic activity compared with Degussa P25, as result of its continuous hierarchical structures, special conductive channel and large specific surface area. With these features, the hierarchical TiO2 may have more potential applications in the fields of dye-sensitized solar cells and lithium ion batteries.

  3. Density functional theory study of dopants in polycrystalline TiO2

    NASA Astrophysics Data System (ADS)

    Körner, Wolfgang; Elsässer, Christian

    2011-05-01

    We present a density functional theory (DFT) study of doped rutile and anatase TiO2 in which we investigate the impact of grain boundaries on the physics of atomic defects. The main goal is to obtain information about the positions of the defect levels generated by an oxygen vacancy, a titanium interstitial, cation dopants Nb, Al, and Ga, and an anion dopant N in the electronic band gap having in mind the application of TiO2 as a transparent conducting oxide (TCO) or its use in heterogeneous catalysis. Due to the known deficiency of the local density approximation (LDA) of DFT to yield accurate values for band gap energies for insulators such as TiO2, a self-interaction correction (SIC) to the LDA is employed. The main result of our study is that grain boundaries do affect the defect formation energies as well as the position and shape of the dopant-induced electronic energy levels significantly with respect to the single crystal. According to our study Nb doping may lead to n-conducting TiO2 whereas doping with N, Al, or Ga is not promising in order to achieve p-conducting TiO2. Furthermore an increase in the photoconductivity of TiO2:N and the colorlessness of TiO2:Al may be explained by our results.

  4. Light-induced antifungal activity of TiO 2 nanoparticles/ZnO nanowires

    NASA Astrophysics Data System (ADS)

    Haghighi, N.; Abdi, Y.; Haghighi, F.

    2011-09-01

    Antifungal activity of TiO2/ZnO nanostructures under visible light irradiation was investigated. A simple chemical method was used to synthesize ZnO nanowires. Zinc acetate dihydrate, Polyvinyl Pyrrolidone and deionized water were used as precursor, capping and solvent, respectively. TiO2 nanoparticles were deposited on ZnO nanowires using an atmospheric pressure chemical vapor deposition system. X-ray diffraction pattern of TiO2/ZnO nano-composite has represented the diffraction peaks relating to the crystal planes of the TiO2 (anatase and rutile) and ZnO. TiO2/ZnO nanostructure antifungal effect on Candida albicans biofilms was studied and compared with the activity of TiO2 nanoparticles and ZnO nanowires. The high efficiency photocatalytic activity of TiO2 nanoparticles leads to increased antifungal activity of ZnO nanowires. Scanning electron microscope was utilized to study the morphology of the as prepared nanostructures and the degradation of the yeast.

  5. Fabrication and characterization of abrupt TiO2-SiOx core-shell nanowires by a simple heat treatment

    NASA Astrophysics Data System (ADS)

    Folger, Alena; Kalb, Julian; Schmidt-Mende, Lukas; Scheu, Christina

    2017-08-01

    Three dimensional hierarchical metal oxide nanostructures, like TiO2 nanowire arrays, have attracted great attention for electrochemical energy conversion and storage applications. The functionality of such devices can be further enhanced by adding a nanowire shell with a different stoichiometry or composition compared to the core. Here, we report an approach with a facile heat treatment at 1050 °C, which allows the fabrication of rutile TiO2-SiOx core-shell nanowire arrays on silicon substrates. Our detailed electron microscopic investigation shows that this method is able to cover hydrothermally grown rutile TiO2 nanowires with a uniform shell of several nanometers in thickness. Moreover, the treatment improves the quality of the rutile TiO2 core by removing lattice defects, introduced from the hydrothermal growth. Electron energy loss spectroscopy reveals that the homogeneous shell around the TiO2 core consists of amorphous SiOx and does not form any intermediate phase with TiO2 at the interface. Thus, the properties of the TiO2 core are not affected by the shell, while the shell suppresses undesired electron back transfer. Latter leads to performance losses in many applications, e.g., dye sensitized solar cells, and is the main reason for a fast degradation of devices incorporating organic materials and TiO2.

  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. Optimization of charge transfer and transport processes at the CdSe quantum dots/TiO2 nanorod interface by TiO2 interlayer passivation

    NASA Astrophysics Data System (ADS)

    Jaramillo-Quintero, O. A.; Triana, M. A.; Rincon, M. E.

    2017-06-01

    Surface trap states hinder charge transfer and transport properties in TiO2 nanorods (NRs), limiting its application on optoelectronic devices. Here, we study the interfacial processes between rutile TiO2 NR and CdSe quantum dots (QDs) using TiO2 interlayer passivation treatments. Anatase or rutile TiO2 thin layers were deposited on an NR surface by two wet-chemical deposition treatments. Reduced interfacial charge recombination between NRs and CdSe QDs was observed by electrochemical impedance spectroscopy with the introduction of TiO2 thin film interlayers compared to bare TiO2 NRs. These results can be ascribed to in-gap trap state passivation of the TiO2 NR surface, which led to an increase in open circuit voltage. Moreover, the rutile thin layer was more efficient than anatase to promote a higher photo-excited electron transfer from CdSe QDs to TiO2 NRs due to a large driving force for charge injection, as confirmed by surface photovoltage spectroscopy.

  8. 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.

  9. The effect of silica thickness on nano TiO2 particles for functional polyurethane nanocomposites.

    PubMed

    Chen, Chao; Wu, Wei; Xu, William Z; Charpentier, Paul A

    2017-03-17

    In order to help reduce the agglomeration of TiO2 nanoparticles in polyurethane coatings while enhancing their photoactivity and mechanical/physical properties, this work examined encapsulating TiO2 nanoparticles in a thin layer of SiO2, prior to their nanocomposite polymerization. By applying a Stöber process, varying thicknesses of SiO2 were successfully coated onto the surface of anatase and rutile TiO2 nanoparticles. The methylene blue results showed that different loadings of SiO2 onto the TiO2 surface significantly influenced their photocatalytic activity. When the loading weight of SiO2 was lower than 3.25 wt%, the photocatalytic activity was enhanced, while with higher loadings, it gave lower photocatalytic activity. When the rutile phase TiO2 surface was fully covered with SiO2, an enhanced photocatalytic activity was observed. When these silica coated nanoparticles were applied in polyurethane coatings, increasing the amount of SiO2 on the titania surface increased the coatings contact angle from 75° to 87° for anatase phase and 70°-78° for rutile phase. The Young's modulus was also increased from 1.06 GPa to 2.77 GMPa for anatase phase and 1.06-2.17 GPa for rutile phase, attributed to the silica layer giving better integration. The thermal conductivity of the polyurethane coatings was also successfully decreased by encapsulating SiO2 on the titania surface for next generation high performance coatings.

  10. The effect of silica thickness on nano TiO2 particles for functional polyurethane nanocomposites

    NASA Astrophysics Data System (ADS)

    Chen, Chao; Wu, Wei; Xu, William Z.; Charpentier, Paul A.

    2017-03-01

    In order to help reduce the agglomeration of TiO2 nanoparticles in polyurethane coatings while enhancing their photoactivity and mechanical/physical properties, this work examined encapsulating TiO2 nanoparticles in a thin layer of SiO2, prior to their nanocomposite polymerization. By applying a Stöber process, varying thicknesses of SiO2 were successfully coated onto the surface of anatase and rutile TiO2 nanoparticles. The methylene blue results showed that different loadings of SiO2 onto the TiO2 surface significantly influenced their photocatalytic activity. When the loading weight of SiO2 was lower than 3.25 wt%, the photocatalytic activity was enhanced, while with higher loadings, it gave lower photocatalytic activity. When the rutile phase TiO2 surface was fully covered with SiO2, an enhanced photocatalytic activity was observed. When these silica coated nanoparticles were applied in polyurethane coatings, increasing the amount of SiO2 on the titania surface increased the coatings contact angle from 75° to 87° for anatase phase and 70°-78° for rutile phase. The Young’s modulus was also increased from 1.06 GPa to 2.77 GMPa for anatase phase and 1.06-2.17 GPa for rutile phase, attributed to the silica layer giving better integration. The thermal conductivity of the polyurethane coatings was also successfully decreased by encapsulating SiO2 on the titania surface for next generation high performance coatings.

  11. A one-step process for the antimicrobial finishing of textiles with crystalline TiO2 nanoparticles.

    PubMed

    Perelshtein, Ilana; Applerot, Guy; Perkas, Nina; Grinblat, Judith; Gedanken, Aharon

    2012-04-10

    Titanium oxide (TiO(2)) nanoparticles (NPs) in their two forms, anatase and rutile, were synthesized and deposited onto the surface of cotton fabrics by using ultrasonic irradiation. The structure and morphology of the nanoparticles were analyzed by using characterization methods such as XRD, TEM, STEM, and EDS. The antimicrobial activities of the TiO(2)-cotton composites were tested against Escherichia coli (gram-negative) and Staphylococcus aureus (gram-positive) strains, as well as against Candida albicans. Significant antimicrobial effect was observed, mainly against Staphylococcus aureus. In addition, the combination of visible light and TiO(2) NPs showed enhanced antimicrobial activity.

  12. A metal matrix composite prepared from electrospun TiO2 nanofibers and an Al 1100 alloy via friction stir processing.

    PubMed

    Zhang, Lifeng; Chandrasekar, Ramya; Howe, Jane Y; West, Michael K; Hedin, Nyle E; Arbegast, William J; Fong, Hao

    2009-05-01

    Electrospun TiO2 nanofibers, consisting of anatase phase TiO2 single-crystalline crystallites with sizes of approximately 10 nm, were impregnated into an Al 1100 alloy by the technique of friction stir processing (FSP). The studies of the resulting TiO2-Al composite revealed that the electrospun TiO2 nanofibers with diameters of approximately 200 nm were broken into nanoparticles during FSP; the in situ generated pristine surfaces led to the interfacial reaction between TiO2 and Al and resulted in the formation of strong interfaces between the electrospun TiO2 nanoparticles and the Al 1100 matrix. This was evidenced by the fact that the filler-matrix fracture always occurred on the Al matrix side in the interfacial region. Consequently, the TiO2-Al composite made from the electrospun TiO2 nanofibers possessed a significantly higher Vickers hardness than that made from a commercially available anatase phase TiO2 nanopowder, of which the organic and/or carbonaceous contaminants on the surface impeded the interfacial reaction between TiO2 and Al during FSP.

  13. Mn-doped TiO2 thin films with significantly improved optical and electrical properties

    NASA Astrophysics Data System (ADS)

    Lu, Liu; Xia, Xiaohong; Luo, J. K.; Shao, G.

    2012-12-01

    TiO2 thin films with various Mn doping contents were fabricated by reactive magnetron sputtering deposition at 550 °C and their structural, optical and electrical properties were characterized. All films were made of densely packed columnar grains with a fibrous texture along the normal direction of the substrate. The as-deposited structure in the pure TiO2 film consisted of anatase grains with the [1 0 1] texture. Mn incorporation stabilized the rutile phase and induced lattice contraction in the [1 0 0] direction. The texture in the Mn-doped films changed from [1 1 0] to [2 0 0] with increasing Mn content. The incorporation of Mn in the TiO2 lattice introduced intermediate bands into its narrowed forbidden gap, leading to remarkable red-shifts in the optical absorption edges, together with significantly improved electrical conductivity of the thin films. Hall measurement showed that the incorporation of Mn-induced p-type conductivity, with hole mobility in heavily doped TiO2 (˜40% Mn) being about an order higher than electron mobility in single-crystal rutile TiO2. Oxygen vacancies, on the other hand, interacted with substitutional Mn atoms to reduce its effect on optical and electrical properties.

  14. Immobilized TiO2 nanoparticles produced by flame spray for photocatalytic water remediation

    NASA Astrophysics Data System (ADS)

    Bettini, Luca Giacomo; Diamanti, Maria Vittoria; Sansotera, Maurizio; Pedeferri, Maria Pia; Navarrini, Walter; Milani, Paolo

    2016-08-01

    Anatase/rutile mixed-phase titanium dioxide (TiO2) photocatalysts in the form of nanostructured powders with different primary particle size, specific surface area, and rutile content were produced from the gas-phase by flame spray pyrolysis (FSP) starting from an organic solution containing titanium (IV) isopropoxide as Ti precursor. Flame spray-produced TiO2 powders were characterized by means of X-ray diffraction, Raman spectroscopy, and BET measurements. As-prepared powders were mainly composed of anatase crystallites with size ranging from 7 to 15 nm according to the synthesis conditions. TiO2 powders were embedded in a multilayered fluoropolymeric matrix to immobilize the nanoparticles into freestanding photocatalytic membranes. The photocatalytic activity of the TiO2-embedded membranes toward the abatement of hydrosoluble organic pollutants was evaluated employing the photodegradation of rhodamine B in aqueous solution as test reaction. The photoabatement rate of best performing membranes significantly overcomes that of membranes produced by the same method and incorporating commercial P25-TiO2.

  15. Structure and Formation Mechanism of Black TiO2 Nanoparticles

    DOE PAGES

    Tian, Mengkun; Mahjouri-Samani, Masoud; Eres, Gyula; ...

    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

  16. 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

  17. 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).

  18. 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.

  19. 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.

  20. Enhanced photocatalytic activity of TiO2 nanobarbed fibers treated with atmospheric pressure plasma using O2 gas

    NASA Astrophysics Data System (ADS)

    Lee, Hyun-Uk; Ahn, Kyun; Jeong, Se-Young; Cho, Chae-Ryong; Kim, Jong-Pil; Bae, Jong-Seong; Kim, Hyun-Gyu; Kwon, Se-Hun; Lee, Hyung Woo

    2010-11-01

    TiO2 nanobarbed fibers (NBFs) were prepared by growing rutile TiO2 nanorods on anatase TiO2 nanofibers via electrospinning and hydrothermal reaction processes. There was a large increase in the photocatalytic activity of O2-plasma-treated (OP)-TiO2 NBFs relative to that of the TiO2 NBFs; this is due to the hydroxylation of the surface of the TiO2 NBFs by OP treatment. The repeatability of the photocatalytic activity of the OP-TiO2 NBFs was found to be high and the decolorization rate after ten cycles was 88.3% of the initial value. These results indicate that OP-TiO2 NBFs have great potential for use as a photocatalyst.

  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.

  2. 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

  3. Simultaneous phase- and size-controlled synthesis of TiO(2) nanorods via non-hydrolytic sol-gel reaction of syringe pump delivered precursors.

    PubMed

    Koo, Bonil; Park, Jongnam; Kim, Yukyeong; Choi, Sang-Hyun; Sung, Yung-Eun; Hyeon, Taeghwan

    2006-12-07

    The simultaneous phase- and size-controlled synthesis of TiO(2) nanorods was achieved via the non-hydrolytic sol-gel reaction of continuously delivered two titanium precursors using two separate syringe pumps. As the injection rate was decreased, the length of the TiO(2) nanorods was increased and their crystalline phase was simultaneously transformed from anatase to rutile. When the reaction was performed by injecting titanium precursors contained in two separate syringes into a hot oleylamine surfactant solution with an injection rate of 30 mL/h, anatase TiO(2) nanorods with dimensions of 6 nm (thickness) x 50 nm (length) were produced. When the injection rate was decreased to 2.5 mL/h, star-shaped rutile TiO(2) nanorods with dimensions of 25 nm x 200 nm and a small fraction of rod-shaped anatase TiO(2) nanorods with dimensions of 9 nm x 100 nm were synthesized. Pure star-shaped rutile TiO(2) nanorods with dimensions of 25 nm x 450 nm were synthesized when the injection rate was further decreased to 1.25 mL/h. The simultaneous phase transformation and length elongation of the TiO(2) nanorods were achieved. Under optimized reaction conditions, as much as 3.5 g of TiO(2) nanorods were produced. The TiO(2) nanorods were used to produce dye-sensitized solar cells, and the photoconversion efficiency of the mixture composed of star-shaped rutile TiO(2) nanorods and a small fraction of anatase nanorods were comparable to that of Degussa P-25.

  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. Synthesis and characterization of LaFeO3/TiO2 nanocomposites for visible light photocatalytic activity

    NASA Astrophysics Data System (ADS)

    Dhinesh Kumar, R.; Thangappan, R.; Jayavel, R.

    2017-02-01

    LaFeO3/TiO2 nanocomposites were successfully synthesized by hydrothermal method. The as-prepared nanoparticles were characterized by TGA, XRD, HRSEM, EDS, TEM, VSM and UV-Vis techniques. Thermal stability of the material was studied by thermal analysis. XRD studies confirm the orthorhombic and rutile phase for pure LaFeO3 and TiO2 nanoparticles. The LaFeO3/TiO2 composite shows the coexistence of LaFeO3 and TiO2 phases with no extra peaks. Morphological analysis shows the spherical nanoparticles and the average particle size of LaFeO3, TiO2 and LaFeO3/TiO2 was around 60 nm. The LaFeO3/TiO2 nanocomposites show a significant shift in the UV-vis absorption spectra in comparison with both TiO2 and LaFeO3 nanoparticles. The photocatalytic activity of the samples were tested for the degradation of methyl orange (MO) in aqueous solutions under visible light irradiations for 180 min. The LaFeO3/TiO2 composite exhibits enhanced visible light photocatalytic properties in comparison with that of LaFeO3 nanoparticles.

  6. 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.

  7. Photocatalytic activity and characterization of sol-gel-derived Ni-doped TiO2-coated active carbon composites

    NASA Astrophysics Data System (ADS)

    Bhosale, R. R.; Pujari, S. R.; Lande, M. K.; Arbad, B. R.; Pawar, S. B.; Gambhire, A. B.

    2012-11-01

    Ni-doped, TiO2-coated active carbon (Ni-TiO2/AC) were prepared by a sol-gel method. The effect of supports, including TiO2 and active carbon (AC), on the molecular structure and photocatalytic activity of nickel oxide for complete decomposition of methylene blue has been examined with respect to the content of Ni on the catalyst surface. The photocatalytic activities of the Ni-TiO2/AC composites were evaluated in the decomposition of methylene blue solution under visible-light irradiation. The results indicate that Ni-TiO2/AC has a higher efficiency in decomposition of methylene blue than TiO2 and TiO2/AC. This was attributed to the different functions of active carbon and nickel species. First, nanosize TiO2 particles on composites were not reunited, possible because active carbon retards transformation of anatase into rutile and decrease the crystallite size. Second, production of high concentrations of organic compound near Ni-TiO2. Third, carbon in active carbon causes some of the TiO2 to reduce to Ti3+ ions, which prevents electron-hole pair recombination. It was found that the addition of Ni to TiO2 sol could suppress the grain growth of TiO2 crystals and increase the hydroxyl content on the surface of TiO2/AC. The photocatalytic efficiency and activity of the composites remained good, even after three cycles.

  8. 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

  9. Imparting amphiphobicity on single-crystalline porous materials.

    PubMed

    Sun, Qi; He, Hongming; Gao, Wen-Yang; Aguila, Briana; Wojtas, Lukasz; Dai, Zhifeng; Li, Jixue; Chen, Yu-Sheng; Xiao, Feng-Shou; Ma, Shengqian

    2016-10-31

    The sophisticated control of surface wettability for target-specific applications has attracted widespread interest for use in a plethora of applications. Despite the recent advances in modification of non-porous materials, surface wettability control of porous materials, particularly single crystalline, remains undeveloped. Here we contribute a general method to impart amphiphobicity on single-crystalline porous materials as demonstrated by chemically coating the exterior of metal-organic framework (MOF) crystals with an amphiphobic surface. As amphiphobic porous materials, the resultant MOF crystals exhibit both superhydrophobicity and oleophobicity in addition to retaining high crystallinity and intact porosity. The chemical shielding effect resulting from the amphiphobicity of the MOFs is illustrated by their performances in water/organic vapour adsorption, as well as long-term ultrastability under highly humidified CO2 environments and exceptional chemical stability in acid/base aqueous solutions. Our work thereby pioneers a perspective to protect crystalline porous materials under various chemical environments for numerous applications.

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

    NASA Astrophysics Data System (ADS)

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

    2015-01-01

    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 Al2O3 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.

  11. 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.

  12. Subsurface damage of single crystalline silicon carbide in nanoindentation tests.

    PubMed

    Yan, Jiwang; Gai, Xiaohui; Harada, Hirofumi

    2010-11-01

    The response of single crystalline silicon carbide (SiC) to a Berkovich nanoindenter was investigated by examining the indents using a transmission electron microscope and the selected area electron diffraction technique. It was found that the depth of indentation-induced subsurface damage was far larger than the indentation depth, and the damaging mechanism of SiC was distinctly different from that of single crystalline silicon. For silicon, a broad amorphous region is formed underneath the indenter after unloading; for SiC, however, no amorphous phase was detected. Instead, a polycrystalline structure with a grain size of ten nanometer level was identified directly under the indenter tip. Micro cracks, basal plane dislocations and possible cross slips were also found around the indent. These finding provide useful information for ultraprecision manufacturing of SiC wafers.

  13. Single-crystalline nanoporous Nb2O5 nanotubes

    PubMed Central

    2011-01-01

    Single-crystalline nanoporous Nb2O5 nanotubes were fabricated by a two-step solution route, the growth of uniform single-crystalline Nb2O5 nanorods and the following ion-assisted selective dissolution along the [001] direction. Nb2O5 tubular structure was created by preferentially etching (001) crystallographic planes, which has a nearly homogeneous diameter and length. Dense nanopores with the diameters of several nanometers were created on the shell of Nb2O5 tubular structures, which can also retain the crystallographic orientation of Nb2O5 precursor nanorods. The present chemical etching strategy is versatile and can be extended to different-sized nanorod precursors. Furthermore, these as-obtained nanorod precursors and nanotube products can also be used as template for the fabrication of 1 D nanostructured niobates, such as LiNbO3, NaNbO3, and KNbO3. PMID:21711650

  14. Imparting amphiphobicity on single-crystalline porous materials

    NASA Astrophysics Data System (ADS)

    Sun, Qi; He, Hongming; Gao, Wen-Yang; Aguila, Briana; Wojtas, Lukasz; Dai, Zhifeng; Li, Jixue; Chen, Yu-Sheng; Xiao, Feng-Shou; Ma, Shengqian

    2016-10-01

    The sophisticated control of surface wettability for target-specific applications has attracted widespread interest for use in a plethora of applications. Despite the recent advances in modification of non-porous materials, surface wettability control of porous materials, particularly single crystalline, remains undeveloped. Here we contribute a general method to impart amphiphobicity on single-crystalline porous materials as demonstrated by chemically coating the exterior of metal-organic framework (MOF) crystals with an amphiphobic surface. As amphiphobic porous materials, the resultant MOF crystals exhibit both superhydrophobicity and oleophobicity in addition to retaining high crystallinity and intact porosity. The chemical shielding effect resulting from the amphiphobicity of the MOFs is illustrated by their performances in water/organic vapour adsorption, as well as long-term ultrastability under highly humidified CO2 environments and exceptional chemical stability in acid/base aqueous solutions. Our work thereby pioneers a perspective to protect crystalline porous materials under various chemical environments for numerous applications.

  15. 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.

  16. Synthesis and characterization of single crystalline selenium nanowire arrays

    SciTech Connect

    Zhang, X.Y. . E-mail: apzhxy@polyu.edu.hk; Xu, L.H.; Dai, J.Y.; Cai, Y.; Wang, N.

    2006-09-14

    Ordered selenium nanowire arrays with diameters about 40 nm have been fabricated by electrodeposition using anodic porous alumina templates. As determined by X-ray diffraction, Raman spectra, electron diffraction and high-resolution transmission electron microscopy, selenium nanowires have uniform diameters, which are fully controllable. Single crystalline trigonal selenium nanowires have been obtained after postannealing at 180 deg. C. These nanowires are perfect with a c-axis growth orientation. The optical absorption spectra reveal two types of electron transition activity.

  17. Beneficial surface passivation of hydrothermally grown TiO2 nanowires for solar water oxidation

    NASA Astrophysics Data System (ADS)

    Yun, Gun; Song, Gwang Yeom; Ahn, Bo-Eun; Lee, Sang-Kwon; Heo, Jaeyeong; Ahn, Kwang-Soon; Kang, Soon Hyung

    2016-03-01

    Rutile TiO2 nanowires (TONWs) with a length of 2.0 μm were synthesized using a facile hydrothermal method in a strong acid solution. To investigate the effect of surface passivation of TONW arrays, a TiO2 layer with a thickness varying from 5 to 20 nm on TONW arrays was applied by atomic layer deposition (ALD). No distinct morphological modification was observed in all prepared TONW arrays in the environment where the diameter of the TONW arrays was systematically increased from 10 to 40 nm. In this study, Mott-Schottky analysis revealed that 10 nm TiO2-coated TONW (denoted as TiO2(10 nm)/TONW) arrays showed the highest electronic conductivity, followed by the 5 nm, 20 nm, and 0 nm TiO2/TONW arrays. The photoelectrochemical (PEC) performance was assessed in 0.1 M KOH, which revealed that TiO2(10 nm)/TONW arrays displayed a photocurrent density (3.92 mA/cm2 at 0.5 VNHE) higher than that (2.72 mA/cm2) of TONW arrays. This may be ascribed to the surface passivation of trap or defect sites by the thin TiO2 surface coating, leading to the increased electron densities and improving the PEC performance. For a more definitive examination, photovoltage decay measurement was performed to calculate the decay lifetime, which is closely correlated to the electron-hole recombination reaction. In this study, TiO2(10 nm)/TONW arrays exhibited a decay lifetime (0.7 s) shorter than that (1.1 s) of TONW arrays, proving the suppressed charge recombination in the thin TiO2/TONW arrays.

  18. 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.

  19. 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.

  20. Synergistic effects of F and Fe in co-doped TiO2 nanoparticles

    NASA Astrophysics Data System (ADS)

    Zhang, Yufei; Shen, Huiyuan; Liu, Yanhua

    2016-03-01

    TiO2 photocatalysts co-doped with F and Fe were synthesized by a sol-gel method. Synergistic effects of F and Fe in the co-doped TiO2 were verified by NH3 decomposition, X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS) and ultraviolet-visible (UV-Vis) absorption spectroscopy, and was analyzed by the simulation based on the density functional theory (DFT). The results from NH3 decomposition confirmed that the cooperation of F and Fe broadened the optical response of TiO2 to visible light region and also enhanced the photocatalytic activity of TiO2 under ultraviolet light. XRD patterns, SEM and HRTEM images showed that the co-doped samples were nanometric anatase with an average particle size of 25 nm. Co-doping with F and Fe inhibited the grain growth of TiO2 from anatase to rutile and resulted in a larger lattice defect. XPS analysis exhibited that the doped F and Fe atoms were into the TiO2 lattice. UV-Vis absorption spectra showed that its optical absorption edge was moved up to approximately 617 nm and its ultraviolet absorption was also enhanced. The DFT results indicated that the cooperation of Fe 3d and O 2p orbits narrowed the band gap of TiO2 and F 2p orbit widened the upper valence bands. The synergistic electron density around F and Fe in co-doped TiO2 was capable to enhance the photo-chemical stability of TiO2.

  1. TiO2 Nanorods Preparation from Titanyl Sulphate Produced by Dissolution of Ilmenite

    NASA Astrophysics Data System (ADS)

    Wahyuningsih, S.; Rinawati, L.; Munifa, R. M. I.; Ramelan, A. H.; Sulistyono, Eko

    2017-02-01

    One-dimensional titanium oxides (TiO2) nanorods have substantial applications in photocatalytic, nanoelectronic, and photoelectrochemical solar cells. These applications require large quantities of materials and a production technique suitable for future industry fabrication. We demonstrate here a new method of TiO2 nanorods production from ilmenite sands (FeTiO3). In this process, the roasted ilmenite sand was separated from the iron content and dissolved in the sulphuric acid solution. Separation process of TiO2 from ilmenite has been carried out by roasting, leaching and precipitation processes. The roasting process was conducted by the addition of Na2S at a temperature of 800°C that had been deomposed ilmenite into hematite (Fe2O3), anatase TiO2, rutile TiO2, Na2SO4, NaFeS2 and NaFeO2. Separation TiO2 from titanyl sulfate (TiOSO4) after leaching in H2SO4 solution was conducted by hydrolysis-condensation step and complexation step of Fe2+ content. KCNS solution was used as a complexing agent. The xerogel synthesized TiO2 then was prepared to 1-D nanostructure of TiO2 nanorods by hydrothermal process under alkaline condition. By the two-step method, we finally gain the 1D nanorods TiO2 extracted from ilmenite sand. The characterization using the Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) obtained the nanorod morphology at a diameter about 9.6 nm.

  2. 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

  3. Single-crystalline germanium nanomembrane photodetectors on foreign nanocavities

    DOE PAGES

    Xia, Zhenyang; Song, Haomin; Kim, Munho; ...

    2017-07-07

    Miniaturization of optoelectronic devices offers tremendous performance gain. As the volume of photoactive material decreases, optoelectronic performance improves, including the operation speed, the signal-to-noise ratio, and the internal quantum efficiency. Over the past decades, researchers have managed to reduce the volume of photoactive materials in solar cells and photodetectors by orders of magnitude. However, two issues arise when one continues to thin down the photoactive layers to the nanometer scale (for example, <50 nm). First, light-matter interaction becomes weak, resulting in incomplete photon absorption and low quantum efficiency. Second, it is difficult to obtain ultrathin materials with single-crystalline quality. Wemore » introduce a method to overcome these two challenges simultaneously. It uses conventional bulk semiconductor wafers, such as Si, Ge, and GaAs, to realize single-crystalline films on foreign substrates that are designed for enhanced light-matter interaction. We use a high-yield and high-throughput method to demonstrate nanometer-thin photodetectors with significantly enhanced light absorption based on nanocavity interference mechanism. As a result, these single-crystalline nanomembrane photodetectors also exhibit unique optoelectronic properties, such as the strong field effect and spectral selectivity.« less

  4. Single-crystalline germanium nanomembrane photodetectors on foreign nanocavities

    PubMed Central

    Xia, Zhenyang; Song, Haomin; Kim, Munho; Zhou, Ming; Chang, Tzu-Hsuan; Liu, Dong; Yin, Xin; Xiong, Kanglin; Mi, Hongyi; Wang, Xudong; Xia, Fengnian; Yu, Zongfu; Ma, Zhenqiang (Jack); Gan, Qiaoqiang

    2017-01-01

    Miniaturization of optoelectronic devices offers tremendous performance gain. As the volume of photoactive material decreases, optoelectronic performance improves, including the operation speed, the signal-to-noise ratio, and the internal quantum efficiency. Over the past decades, researchers have managed to reduce the volume of photoactive materials in solar cells and photodetectors by orders of magnitude. However, two issues arise when one continues to thin down the photoactive layers to the nanometer scale (for example, <50 nm). First, light-matter interaction becomes weak, resulting in incomplete photon absorption and low quantum efficiency. Second, it is difficult to obtain ultrathin materials with single-crystalline quality. We introduce a method to overcome these two challenges simultaneously. It uses conventional bulk semiconductor wafers, such as Si, Ge, and GaAs, to realize single-crystalline films on foreign substrates that are designed for enhanced light-matter interaction. We use a high-yield and high-throughput method to demonstrate nanometer-thin photodetectors with significantly enhanced light absorption based on nanocavity interference mechanism. These single-crystalline nanomembrane photodetectors also exhibit unique optoelectronic properties, such as the strong field effect and spectral selectivity. PMID:28695202

  5. Photoelectrochemical characterization of a robust TiO2/BDD heterojunction electrode for sensing application in aqueous solutions.

    PubMed

    Han, Yanhe; Zhang, Shanqing; Zhao, Huijun; Wen, William; Zhang, Haimin; Wang, Hongjuan; Peng, Feng

    2010-04-20

    Titanium dioxide (TiO(2)) and boron-doped diamond (BDD) are two of the most popular functional materials in recent years. In this work, TiO(2) nanoparticles were immobilized onto the BDD electrodes by a dip-coating technique. Continuous and uniform mixed-phase (anatase and rutile) and pure-anatase TiO(2)/BDD electrodes were obtained after calcination processes at 700 and 450 degrees C, respectively. The particle sizes of both types of TiO(2) film range from 20 to 30 nm. In comparison with a TiO(2)/indium tin oxide (ITO) electrode, the TiO(2)/BDD electrode demonstrates a higher photoelectrocatalytic activity toward the oxidation of organic compounds, such as glucose and potassium hydrogen phthalate. Among all the tested TiO(2) electrodes, the mixed-phase TiO(2)/BDD electrode demonstrated the highest photoelectrocatalytic activity, which can be attributed to the formation of the p-n heterojunction between TiO(2) and BDD. The electrode was subsequently used to detect a wide spectrum of organic compounds in aqueous solution using a steady-state current method. An excellent linear relationship between the steady-state photocurrents and equivalent organic concentrations was attained. The steady-state oxidation photocurrents of the mixed-phase TiO(2)/BDD electrode were insensitive to pH in the range of pH 2-10. Furthermore, the electrodes exhibited excellent robustness under strong acidic conditions that the TiO(2)/ITO electrodes cannot stand. These characteristics bestow the mixed-phase TiO(2)/BDD electrode to be a versatile material for the sensing of organic compounds.

  6. Polymorphic transformations in nanostructured anatase (TiO2) under high-pressure shock compression

    NASA Astrophysics Data System (ADS)

    Molodets, A. M.; Golyshev, A. A.; Shul'ga, Yu. M.

    2013-07-01

    The action of dynamic pressure and temperature on polymorphic transformations in nanostructured (grain size of 8-20 nm) anatase (TiO2) is studied. The dynamic pressure of a loading pulse (10-45 GPa) is measured with a manganin gauge. The temperature of shock-compressed specimens, which is varied by varying the initial temperature and initial porosity, is found to fall into the range 500-2500 K. It is shown that as the temperature and shock compression pressure rise, the nanostructured anatase turns into a nanoanatase-nanocolumbite or columbite-rutile mixture or into almost impurity-free (pure) nanocolumbite or impurity-free microcrystalline rutile.

  7. 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...

  8. 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...

  9. 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.

  10. Degradation of the ammonia wastewater in aqueous medium with ozone in combination with mesoporous TiO2 catalytic

    NASA Astrophysics Data System (ADS)

    Liu, Zhiwu; Qiu, Jianping; Zheng, Chaocan; Li, Liqing

    2017-03-01

    TiO2 mesoporous nanomaterials are now widely used in catalytic ozone technology. In this paper, the market P25 as precursor hydrothermal method to prepare TiO2 mesoporous materials, ozone catalyst material characterization by transmission electron microscopy, surface area analyzers, and X-ray diffraction technique and found that nanotubes, nanosheets, nanorods through characterization results, nano-particles of different morphology and anatase and rutile proportion of the ozone catalytic material can be controlled by the calcination temperature and the temperature of hot water to give, and with the hot water temperature and calcination temperature, the catalyst becomes small aperture size larger catalyst crystalline phase from anatase to rutile gradually shift. Catalytic materials have been prepared by the Joint ozone degradation of ammonia wastewater to evaluate mesoporous TiO2 nanomaterials ozone catalytic performance, the results showed that: ammonia wastewater removal efficiency of various catalytic materials relatively separate ozone and markets P25 effects are significantly improved, and TiO2 nanotubes cooperate with ozone degradation ammonia wastewater highest efficiency, in addition, rutile TiO2 catalysts, the more the better the performance of their ozone catalysis.

  11. 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.

  12. 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.

  13. Applications of TiO2, ZnO and Ag Nanomaterials to Denim Fabric.

    PubMed

    Becenen, Nilgün; Altun, Özlen

    2016-05-01

    In previous studies much research has reported the determination of applications of TiO2 (rutile and anatase), ZnO and Ag nanomaterials onto various textile surfaces, but in this study for the first time application to denim fabric and testing of the finished fabric for antimicrobial activities of these nanomaterials was investigated. The presence of nanoparticles on dyed denim fabric surfaces was confirmed by Scanning Electron Microscope (SEM). The nanomaterial-impregnated denim fabric (100% cotton) showed significant antibacterial activity against Staphylococcus aureus, Escherichia coli and Escherichia coli isolated from pasta. Additionally, the UV tests indicated excellent improvement in the UV absorbing activity of the TiO2 (rutile and anatase), ZnO and Ag nanomaterial-treated fabrics.

  14. Synthesis of TiO2 NRs - ZnO Composite for Dye Sensitized Solar Cell Photoanodes

    NASA Astrophysics Data System (ADS)

    Wahyuningsih, S.; Ramelan, A. H.; Hidayat, R.; Fadillah, G.; Munawaroh, H.; Saputri, L. N. M. Z.

    2017-07-01

    Composite of TiO2 NRs - ZnO were synthesized for DSSCs photoanode materials. TiO2 NRs was synthesized from TiO2 anatase by mechanochemical technique using ball milling process with agitation speed of 1000 rpm. While, the further hydrothermal refluxing process was conducted at 120°C under various concentration of NaOH in aqueous solution. The starting material of ZnO was prepared from ZnSO4.7H2O as a precursor. The hydrothermal treated TiO2 was added to the ZnO powder in a certain composition of 1:1, 1:2 and 2:1 (w/w), and the mixtures were then annealed at 400°C. The resulting material was characterized by X-ray diffraction (XRD), Surface area analyzer (SAA), Transmission electron microscopy (TEM), and Thermogravimetry/Differential thermal analysis (TG/DTA). The TiO2 revolution occurs from anatase phase into brookite phase. Rutile TiO2 phase was increasing when the NaOH was added at about 12 M. Nanograf of TEM showed the optimum condition for the formation of TiO2 NRs was obtained when 12 M NaOH was used. Structural transformation to 1D nanorods of TiO2 capable increase surface area up to 79 m2/g. TiO2 NRs-ZnO composite was prepared from TiO2 NRs and ZnO using comparation of TiO2 NRs: ZnO = 1:1, 1:2, dan 2:1. Anatase phase TiO2 as a single phase TiO2 was obtained in the TiO2-ZnO composite (1:1 w/w) upon heating the sample until 400°C. Difference TiO2 NRs-ZnO composite materials were investigated as good photovoltaic materials. Evaluation of the performance of DSSCs was conducted by I-V Keithley 2602A measurement indicate that photoanode built of TiO2 NRs - ZnO thin film has a higher solar cell efficiency than that of TiO2 thin film photoanode.

  15. 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.

  16. Multi-Layered TiO2 Films towards Enhancement of Escherichia coli Inactivation

    PubMed Central

    Yoriya, Sorachon; Chumphu, Angkana; Pookmanee, Pusit; Laithong, Wreerat; Thepa, Sirichai; Songprakorp, Roongrojana

    2016-01-01

    Crystalline TiO2 has shown its great photocatalytic properties in bacterial inactivation. This work presents a design fabrication of low-cost, layered TiO2 films assembled reactors and a study of their performance for a better understanding to elucidate the photocatalytic effect on inactivation of E. coli in water. The ability to reduce the number of bacteria in water samples for the layered TiO2 composing reactors has been investigated as a function of time, while varying the parameters of light sources, initial concentration of bacteria, and ratios of TiO2 film area and volume of water. Herein, the layered TiO2 films have been fabricated on the glass plates by thermal spray coating prior to screen printing, allowing a good adhesion of the films. Surface topology and crystallographic phase of TiO2 for the screen-printed active layer have been characterized, resulting in the ratio of anatase:rutile being 80:20. Under exposure to sunlight and a given condition employed in this study, the optimized film area:water volume of 1:2.62 has shown a significant ability to reduce the E. coli cells in water samples. The ratio of surface area of photocatalytic active base to volume of water medium is believed to play a predominant role facilitating the cells inactivation. The kinetic rate of inactivation and its behavior are also described in terms of adsorption of reaction species at different contact times. PMID:28773930

  17. Enhanced bolometric properties of TiO2-x thin films by thermal annealing

    NASA Astrophysics Data System (ADS)

    Ashok Kumar Reddy, Y.; Shin, Young Bong; Kang, In-Ku; Lee, Hee Chul; Sreedhara Reddy, P.

    2015-07-01

    The effect of thermal annealing on the bolometric properties of TiO2-x films was investigated. The test-patterned TiO2-x samples were annealed at 300 °C temperature in order to enhance their structural and electrical properties for effective infrared image sensor device applications. The crystallinity was changed from amorphous to rutile/anatase in annealed TiO2-x films. Compared to the as-deposited samples, a decrement of the band gap and a decrease of the electrical resistivity were perceived in annealed samples. We found that the annealed samples show linear current-voltage (I-V) characteristic performance, which implies that ohmic contact was well formed at the interface between the TiO2-x and the Ti electrode. Moreover, the annealed TiO2-x sample had a significantly low 1/f noise parameter (1.21 × 10-13) with a high bolometric parameter (β) value compared to those of the as-deposited samples. As a result, the thermal annealing process can be used to prepare TiO2-x film for a high-performance bolometric device.

  18. High photoactive TiO2/SnO2 nanocomposites prepared by laser pyrolysis

    NASA Astrophysics Data System (ADS)

    Scarisoreanu, Monica; Fleaca, Claudiu; Morjan, Ion; Niculescu, Ana-Maria; Luculescu, Catalin; Dutu, Elena; Ilie, Alina; Morjan, Iuliana; Florescu, Lavinia Gavrila; Vasile, Eugeniu; Fort, Carmen Ioana

    2017-10-01

    TiO2/SnO2 nanocomposites have been prepared by laser pyrolysis of volatile TiCl4 and SnCl4 precursors introduced together or separately in the reaction zone in the presence of air as oxidant and ethylene as sensitizer. Prior to the obtaining of TiO2/SnO2 nanocomposites with the different Sn concentrations (1.1-4.8 at.%), the best experimental conditions were identified for preparing pure anatase phase TiO2 samples considered as photoactive reference sample. The TiO2/SnO2 composites were characterized using X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), and UV-vis diffuse reflectance spectroscopy (DRS) techniques. The structural results show the presence of both TiO2 main phases: anatase (65-82% - the majority one) and rutile, as well as of small amounts of SnO2 tetragonal phase, all those with mean crystallite dimensions in the 8-22 nm range. Laser synthesized TiO2/SnO2 samples have a lower band gap energy and some of them (containing 1.8 or 4.8 at.% Sn) show higher photoactivity in the process of Methyl Orange solutions UV discoloration when compared with the P25 Degussa commercial sample.

  19. 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

  20. Biocompatibility and Surface Properties of TiO2 Thin Films Deposited by DC Magnetron Sputtering

    PubMed Central

    López-Huerta, Francisco; Cervantes, Blanca; González, Octavio; Hernández-Torres, Julián; García-González, Leandro; Vega, Rosario; Herrera-May, Agustín L.; Soto, Enrique

    2014-01-01

    We present the study of the biocompatibility and surface properties of titanium dioxide (TiO2) thin films deposited by direct current magnetron sputtering. These films are deposited on a quartz substrate at room temperature and annealed with different temperatures (100, 300, 500, 800 and 1100 °C). The biocompatibility of the TiO2 thin films is analyzed using primary cultures of dorsal root ganglion (DRG) of Wistar rats, whose neurons are incubated on the TiO2 thin films and on a control substrate during 18 to 24 h. These neurons are activated by electrical stimuli and its ionic currents and action potential activity recorded. Through X-ray diffraction (XRD), the surface of TiO2 thin films showed a good quality, homogeneity and roughness. The XRD results showed the anatase to rutile phase transition in TiO2 thin films at temperatures between 500 and 1100 °C. This phase had a grain size from 15 to 38 nm, which allowed a suitable structural and crystal phase stability of the TiO2 thin films for low and high temperature. The biocompatibility experiments of these films indicated that they were appropriated for culture of living neurons which displayed normal electrical behavior. PMID:28788667

  1. A hybrid ultrovilet detector based on polystyrene sulfate modified TiO2 nanocrystalline film

    NASA Astrophysics Data System (ADS)

    Zheng, Wenji; Dong, Yanan; Yan, Xiaoming; Ding, Rui; He, Gaohong

    2017-08-01

    A hybrid polystyrene sulfate (PSS) modified TiO2 nanocrystalline (NC) composite film based ultrovilet (UV) photodetector (PD) was proposed in this study. TiO2 NC film with uniform size distribution was deposited on FTO glass by doctor blading P25 TiO2 nanoparticles. Through layer-by-layer self-assembly, PSS/TiO2 composite film was prepared and it exhibits a high responsivity of 602 AW-1, a large photo-to-dark current ratio of 193200% and a low dark current of 7 nA at only 0.1 V bias. The obtained high responsivity is almost 1-2 orders of magnitude higher than that of mostly reported TiO2 NC film based UV PDs. The reason is attributed to the injection of electrons from PSS into conduction band of TiO2 and the separation improvement of photogenerated electrons and holes by the rutile/anatase junction in the TiO2 NC film. Considering the high responsive performances and facile low-cost fabrication, the proposed PSS/TiO2 composite film based UV PD shows a bright prospect in large-area UV detection application.

  2. TiO2 embedded in carbon submicron-tablets: synthesis from a metal-organic framework precursor and application as a superior anode in lithium-ion batteries.

    PubMed

    Wang, Peiyu; Lang, Junwei; Liu, Dongxia; Yan, Xingbin

    2015-07-21

    Rutile TiO2 embedded in carbon submicron-tablets (TiO2/C) with a "blueberry muffin" morphology was fabricated via a two-step pyrolysis from a metal-organic framework precursor. Such a unique structure of the TiO2/C submicron-tablets provides the ideal anode characteristics (high reversible capacity, superior rate capability and excellent long-term cycling stability) for fast rechargeable lithium ion batteries.

  3. Hydrogen Photo-production from Ethanol and Water over Au/TiO2 Rutile Single Crystal

    DTIC Science & Technology

    2014-03-26

    Approved for Public Release; Distribution Unlimited Hydrogen Photo-production from Ethanol and Water over Au/ TiO2 Rutile Single Crystal The views...production from Ethanol and Water over Au/ TiO2 Rutile Single Crystal Report Title This project in its final form has focused on hydrogen production from...Hydrogen Production from Ethanol over Au/ TiO2 Nanoparticles”, Nature Chemistry, 3 (6) 489-492 ( 2011.) [2] I.R.Macdonald, R.F.Howe, X.Yang, W.Zhou, “In

  4. 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.

  5. A Study on Structure/Phase Transformation of TiO2 nanorods at Various Annealing Temperatures

    NASA Astrophysics Data System (ADS)

    Wahyuningsih, S.; Ramelan, A. H.; Saputri, L. N. M. Z.

    2017-07-01

    Synthesis of TiO2 nanorods was conducted through mechanochemical of ball milling at speed of 175 rpm for 5 hours and strong base 12 M NaOH reaction by hydrothermal at 150°C overnight on variation annealing at 400, 500, and 600°C. Material characterization were performed by X-Ray Diffraction (XRD), Transmission Electron Microscoe (SEM), and Surface Area Analyzer (SAA). Strong base reaction by hydrothermal showed the presence of anatase, brookite, and rutile phase for annealing up to 400°C. The diffraction pattern of annealing at 500 and 600°C contain peaks of both brookite and rutile phase. Morphology transformation of TiO2 to form nanorods TiO2 was showed by rod-shape from TEM micrographs and increase surface area into 111.9 m2/g.

  6. The nanocrystalline structure of TiO2 film deposited by DC magnetron sputtering at room temperature

    NASA Astrophysics Data System (ADS)

    Liu, Jindong; Ding, Wanyu; Wang, Hualin; Liu, Shimin; Jiang, Weiwei; Liu, Chaoqian; Wang, Nan; Chai, Weiping

    2014-10-01

    At room temperature, titanium dioxide (TiO2) films were deposited by the direct current pulse magnetron sputtering technique. Varying O2/Ar flow ratio, TiO2 films with different nanocrystalline structures were obtained. The high resolution transmission electron microscopy results show that with O2/Ar = 6/14, the nanocrystalline in rutile phase appears in as-deposited film. Then X-ray diffraction patterns of annealed films revealed that with O2/Ar = 6/14, the higher weight fractions of rutile TiO2 appear in films. The optical emission spectroscopy results show that with O2/Ar < 6/14, O element was mainly existed as O-/O+ ions, instead of excited state of O atoms.

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

    PubMed

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

    2016-02-24

    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.

  8. 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.

  9. Facile synthesis of hierarchical porous TiO(2) ceramics with enhanced photocatalytic performance for micropolluted pesticide degradation.

    PubMed

    Xing, Zipeng; Zhou, Wei; Du, Fan; Zhang, Linlin; Li, Zhenzi; Zhang, Hang; Li, Wei

    2014-10-08

    In this research, hierarchical porous TiO2 ceramics were successfully synthesized through a camphene-based freeze-drying route. The well-dispersed TiO2 slurries were first frozen and dried at room temperature, followed by high-temperature sintering. The ceramics were analyzed by X-ray diffraction, Raman spectroscopy, scanning electron microscopy, and transmission electron microscopy. Results indicated that the obtained TiO2 ceramics could inhibit undesirable anatase-to-rutile phase transformation and grain growth even at temperatures as high as 800 °C. In this experiment, optimal compressive strength and porosity of the TiO2 ceramics were produced with the initial TiO2 slurry content of ∼15 wt %. The resultant TiO2 ceramics performed excellently in the photodegradation of atrazine and thiobencarb, and the total organic carbon removal efficiency was up to 95.7% and 96.7%, respectively. More importantly, the TiO2 ceramics were easily recyclable. No obvious changes of the photocatalytic performance were observed after six cycles. Furthermore, the ceramics also effectively degraded other pesticides such as dimethoate, lindane, dipterex, malathion, and bentazone. These hierarchical porous TiO2 ceramics have potential applications in environmental cleanup.

  10. Plasmonic Ag deposited TiO2 nano-sheet film for enhanced photocatalytic hydrogen production by water splitting

    NASA Astrophysics Data System (ADS)

    Liu, Enzhou; Kang, Limin; Yang, Yuhao; Sun, Tao; Hu, Xiaoyun; Zhu, Changjun; Liu, Hanchen; Wang, Qiuping; Li, Xinghua; Fan, Jun

    2014-04-01

    TiO2 nano-sheet film (TiO2 NSF) was prepared by a hydrothermal method. Ag nanoparticles (NPs) were then deposited on the surface of TiO2 NSF (Ag/TiO2 NSF) under microwave-assisted chemical reduction. The prepared samples were characterized by x-ray diffraction (XRD), scanning electron microscopy (SEM), UV-visible (UV-vis) absorption spectroscopy, x-ray photoelectron spectroscopy (XPS), photoluminescence (PL) spectroscopy, and Raman scattering spectroscopy. The results revealed that the Ag NPs were well dispersed on the anatase/rutile mixed-phase TiO2 nano-sheet surface with a metallic state. The visible light absorption and Raman scattering of TiO2 were enhanced by Ag NPs based on its surface plasmon resonance effect. Besides, Ag NPs could also effectively restrain the recombination of photogenerated electrons and holes. Photocatalytic water splitting was conducted on the films to obtain hydrogen, and the experimental results indicated that plasmonic Ag NPs could greatly enhance the photocatalytic activity of TiO2 due to the synergistic effect between electron transfer and surface plasmon resonance enhanced absorption. The hydrogen yield obtained from the optimal sample reached 8.1 μmol cm-2 and the corresponding energy efficiency was about 0.47%, which was 8.5 times higher than that of pure TiO2 film. Additionally, the formation mechanism of TiO2 nano-sheet film is preliminarily discussed.

  11. 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.

  12. Osteoconductivity and Hydrophilicity of TiO2 Coatings on Ti Substrates Prepared by Different Oxidizing Processes

    PubMed Central

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

    2012-01-01

    Various techniques for forming TiO2 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, TiO2 coatings were prepared using the following three processes: anodizing in 0.1 M H3PO4 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 TiO2 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 RB-I value) after 14 d implantation in rats' tibias. Anatase was formed by anodizing and rutile by thermal oxidation, but the difference in the TiO2 crystal structure did not influence the osteoconductivity. Anodized TiO2 coatings were hydrophilic, but thermally oxidized TiO2 coatings were less hydrophilic than anodized TiO2 coatings because they lacked in surface OH groups. The TiO2 coating process using anodizing without thermal oxidation gave effective improvement of the osteoconductivity of Ti samples. PMID:23316128

  13. 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.

  14. 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

  15. Plasmonic Ag deposited TiO2 nano-sheet film for enhanced photocatalytic hydrogen production by water splitting.

    PubMed

    Liu, Enzhou; Kang, Limin; Yang, Yuhao; Sun, Tao; Hu, Xiaoyun; Zhu, Changjun; Liu, Hanchen; Wang, Qiuping; Li, Xinghua; Fan, Jun

    2014-04-25

    TiO2 nano-sheet film (TiO2 NSF) was prepared by a hydrothermal method. Ag nanoparticles (NPs) were then deposited on the surface of TiO2 NSF (Ag/TiO2 NSF) under microwave-assisted chemical reduction. The prepared samples were characterized by x-ray diffraction (XRD), scanning electron microscopy (SEM), UV-visible (UV-vis) absorption spectroscopy, x-ray photoelectron spectroscopy (XPS), photoluminescence (PL) spectroscopy, and Raman scattering spectroscopy. The results revealed that the Ag NPs were well dispersed on the anatase/rutile mixed-phase TiO2 nano-sheet surface with a metallic state. The visible light absorption and Raman scattering of TiO2 were enhanced by Ag NPs based on its surface plasmon resonance effect. Besides, Ag NPs could also effectively restrain the recombination of photogenerated electrons and holes. Photocatalytic water splitting was conducted on the films to obtain hydrogen, and the experimental results indicated that plasmonic Ag NPs could greatly enhance the photocatalytic activity of TiO2 due to the synergistic effect between electron transfer and surface plasmon resonance enhanced absorption. The hydrogen yield obtained from the optimal sample reached 8.1 μmol cm(-2) and the corresponding energy efficiency was about 0.47%, which was 8.5 times higher than that of pure TiO2 film. Additionally, the formation mechanism of TiO2 nano-sheet film is preliminarily discussed.

  16. Fungus-mediated biosynthesis and characterization of TiO2 nanoparticles and their activity against pathogenic bacteria

    NASA Astrophysics Data System (ADS)

    Rajakumar, G.; Rahuman, A. Abdul; Roopan, S. Mohana; Khanna, V. Gopiesh; Elango, G.; Kamaraj, C.; Zahir, A. Abduz; Velayutham, K.

    2012-06-01

    In the present study, the biosynthesis of TiO2 nanoparticles (TiO2 NPs) was achieved by a novel, biodegradable and convenient procedure using Aspergillus flavus as a reducing and capping agent. Research on new, simple, rapid, eco-friendly and cheaper methods has been initiated. TiO2 NPs were characterized by FTIR, XRD, AFM, SEM and TEM studies. The X-ray diffraction showed the presence of increased amount of TiO2 NPs which can state by the presence of peaks at rutile peaks at 1 0 0, 0 0 2, 1 0 0 and anatase forms at 1 0 1 respectively. SEM observations revealed that synthesized TiO2 NPs were spherical, oval in shape; individual nanoparticles as well as a few aggregate having the size of 62-74 nm. AFM shows crystallization temperature was seen on the roughness of the surface of TiO2. The Minimum inhibitory concentration value for the synthesized TiO2 NPs was found to be 40 μg ml-1 for Escherichia coli, which was corresponding to the value of well diffusion test. This is the first report on antimicrobial activity of fungus-mediated synthesized TiO2 NPs, which was proved to be a good novel antibacterial material.

  17. Interface actions between TiO2 and porous diatomite on the structure and photocatalytic activity of TiO2-diatomite

    NASA Astrophysics Data System (ADS)

    Xia, Yue; Li, Fangfei; Jiang, Yinshan; Xia, Maosheng; Xue, Bing; Li, Yanjuan

    2014-06-01

    TiO2-diatomite photocatalysts were prepared by sol-gel process with various pre-modified diatomite. In order to obtain diatomite with different surface characteristics, two modification approaches including calcination and phosphoric acid treatment on the micro-structure of diatomite are introduced. The photocatalysts were characterized by XRD, XPS, nitrogen adsorption-desorption isotherms and micromorphology analysis. The results indicate that, compared with pure TiO2, the anatase-to-rutile phase transition temperature of TiO2 loaded on diatomite carrier is significantly increased to nearly 900 °C, depending on the different pretreatment method of diatomite. The photocatalytic activities of different samples were evaluated by their degradation rate of methyl orange (MO) dye under UV and visible-light irradiation. The samples prepared by phosphoric acid pretreatment method exhibit the highest photocatalytic activity. After 90 min of UV irradiation, about 90% of MO is decomposed by the best effective photocatalyst. And after 8 h visible-light irradiation, nearly 60% of MO is decomposed by the same sample. Further mechanism investigation reveals that the H3PO4 pretreatment process can obviously change the surface features of diatomite carrier, cause the formation of Si-O-Ti bond, increase the binding strength between TiO2 and diatomite, restrain crystal growth of loaded TiO2, and thus form thermal-stable mesoporous structure at the granular spaces. It helps to build micro-, meso- and macro-porous hierarchical porous structure in TiO2-diatomite, and improves the charge and mass transfer efficiency during catalyzing process, resulting in the significantly increased photocatalytic activity of TiO2-diatomite pretreated by phosphoric acid.

  18. The influence of temperature, pressure and Ag doping on the physical properties of TiO2 nanoceramics.

    PubMed

    Tran, V H; Głuchowski, P; Łukowiak, A; Stre Combining Cedilla K, W

    2016-12-01

    Undoped and Ag-doped TiO2 ceramics have been prepared at temperatures between 500-1000 °C and under pressures up to 8 GPa. Their crystal structures and physical properties were investigated by means of EDX, SEM, TEM, X-ray powder diffraction, and magnetization M, specific heat Cp and electrical resistance ρ measurements. It is found that the anatase-structured As-cast powder transforms into rutile and columbite-type at 500 °C and 5.5 GPa. The stabilization of the latter phase is fulfilled under a pressure of 8 GPa and at temperatures above 800 °C. On the basis of experimental results, we conclude that the physical properties of TiO2 can be tailored along with its crystal structure. In particular, magnetic properties change from paramagnetic in anatase and rutile to magnetic correlations and in all likelihood magnetic-field-induced antiferromagnetic short-range order in columbite-structured TiO2. Contrasting behaviour in the temperature dependences of specific heat between anatase/rutile and columbite-type TiO2 is obvious. Differently from anatase/rutile, the Cp of columbite-type TiO2 exhibits a low-temperature excess, being interpreted as due to magnetic correlations, or else the prevalence of soft modes. An analysis of ρ(T) for columbite-type TiO2 in the temperature range of 280-400 K reveals the presence of a new trapping state at an energy level of ∼28 meV within the originally forbidden gap. Furthermore, thermal fluctuation-induced tunnelling and hopping conductivities are suggested to govern in a lower temperature range. We recognize that the Ag-doped contents do not alter the crystal structure but considerably enhance magnetic correlations, compared to undoped samples.

  19. Antibacterial activity of TiO2 nanotubes: Influence of crystal phase, morphology and Ag deposition

    NASA Astrophysics Data System (ADS)

    Li, Huirong; Cui, Qiang; Feng, Bo; Wang, Jianxin; Lu, Xiong; Weng, Jie

    2013-11-01

    TiO2 nanotubes on Ti substrate were fabricated by electrochemical anodization. Ag nanoparticles were deposited on the TiO2 nanotubes by a silver mirror reaction. Antibacterial activity of the nanotubes with different structural features was evaluated by a culture test with Escherichia coli bacteria. The anatase nanotubes showed the highest antibacterial activity among three crystal phases including anatase, rutile and amorphous titania. The diameters of the nanotubes affected the antibacterial activity. The two nanotubes with 200 nm and 50 nm diameters had higher antibacterial rate than those with other diameters. The antibacterial activity of the nanotubes was independent on their lengths. Ag-deposited nanotubes exhibited excellent antibacterial activity and its antibacterial rate was up to approximately 100%. TiO2 nanotubes and Ag-deposited nanotubes on titanium should be potential for antibacterial applications in clinics and industry, especially regarding with their reusability.

  20. Hydrogen donors in ZnO and TiO2

    NASA Astrophysics Data System (ADS)

    Lavrov, Eduard V.

    2016-02-01

    The results of combined IR absorption and photoconductivity studies on hydrogen donors in ZnO and TiO2 are presented. It is shown that hydrogen donors in ZnO and rutile TiO2 can be detected as Fano resonances in the photoconductivity spectra at the frequencies corresponding to the vibrational modes of these defects. In the case of anatase TiO2 IR absorption lines at 3412 and 3417 cm-1 are assigned to the stretching local vibrational modes of a donor in the neutral and the positive charge states, respectively. Interstitial hydrogen is suggested as a tentative model for the defect giving rise to these vibrational modes.

  1. A novel method to synthesize molybdenum doped TiO2 films with enhanced photocatalytic activity

    NASA Astrophysics Data System (ADS)

    Luo, Qiang; Cai, Qizhou

    2017-06-01

    Micro arc oxidation method was utilized to prepare molybdenum doped TiO2 films through adding sodium molybdate into the electrolyte for the first time. The effect of sodium molybdate concentration on the morphology, crystal structure and photophysical properties of the films was investigated by field emission scanning electron microscopy, X-ray diffraction and UV-vis spectrophotometry. The results showed that with increasing of sodium molybdate concentration, the pores of films decreased in size and increased in number, more anatase phase transformed to rutile phase in the films and inter-plane spacing of the films increased. Furthermore, the absorption edges of the films shifted towards longer wavelength and the band gap energies of the films decreased with increasing the concentration of sodium molybdate. In addition, the photocatalytic degradation of methylene blue showed that the photocatalytic activity of the molybdenum doped TiO2 film was about 2.3 times that of pure TiO2 film.

  2. Synthesis, characterization and photocatalytic behavior of Ag doped TiO2 thin film

    NASA Astrophysics Data System (ADS)

    Bensouici, F.; Souier, T.; Dakhel, A. A.; Iratni, A.; Tala-Ighil, R.; Bououdina, M.

    2015-09-01

    In this study, structure, microstructure, optical properties and photocatalytic degradation of Rhodamine B (RhB) have been investigated in an aqueous heterogeneous media containing pure and Ag doped TiO2 nanostructures thin films which were prepared by a simple sol-gel route. Thermal analysis demonstrated that Ag content decreased the temperature of anatase-to-rutile phase transformation. X-ray diffraction analysis confirmed that the prepared nanostructures crystallize within anatase-type structure and that the dopant Ag ions were not fully incorporated within TiO2 host lattice, meanwhile both the refractive index and optical band gap were affected by Ag concentration. The photodegradation of Rhodamine B under UV-C radiation by using pure and Ag-doped TiO2 nanostructures showed that Ag played an important role in a significant improvement of the photodegradation efficiency and that the optimum content of Ag ions was found to be 0.5% molar ratio.

  3. A novel sol-gel method for preparing favorable TiO2 thin film

    NASA Astrophysics Data System (ADS)

    Wang, Xiaoyi; Zhang, Dainan; Li, Jie; Zhong, Zhiyong; Jia, Lijun; Wen, Tianlong; Zhang, Huaiwu; Liao, Yulong

    2016-01-01

    Nanocrystalline TiO2 thin films were synthesized by the sol-gel spin-coating method with different variables. Tetrabutyl titanate (TBOT) proportion and C5H8O2: TBOT molar ratio were confirmed to be influential on the gelation time. X-ray diffraction analysis indicated that the samples presented rutile TiO2 phases, which is a basis for subsequent experiments. Scanning electron microscope results revealed that TiO2 thin films with homogeneous and compact surfaces were synthesized successfully when adding moderate TBOT. It was found the thickness of films could reach about 60 nm when sintered at 750 °C, and the influence of sintering temperature was also investigated.

  4. 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.

  5. Non-Band-Gap Photoexcitation of Hydroxylated TiO2.

    PubMed

    Zhang, Yu; Payne, Daniel T; Pang, Chi L; Fielding, Helen H; Thornton, Geoff

    2015-09-03

    The photochemistry of TiO2 has been studied intensively since it was discovered that TiO2 can act as a photocatalyst. Nevertheless, it has proven difficult to establish the detailed charge-transfer processes involved, partly because the excited states involved are difficult to study. Here we present evidence of the existence of hydroxyl-induced excited states in the conduction band region. Using two-photon photoemission, we show that stepwise photoexcitation from filled band gap states lying 0.8 eV below the Fermi level of rutile TiO2(110) excites hydroxyl-induced states 2.73 eV above the Fermi level that has an onset energy of ∼3.1 eV. The onset is shifted to lower energy by the coadsorption of molecular water, which suggests a means of tuning the energy of the excited state.

  6. Synthesis of TiO2 nanoparticles by hydrolysis and peptization of titanium isopropoxide solution

    NASA Astrophysics Data System (ADS)

    Mahata, S.; Mahato, S. S.; Nandi, M. M.; Mondal, B.

    2012-07-01

    Here we report the synthesis and characterization of a stable suspension of modified titania nanoparticles. Phase-pure TiO2 nanocrystallites with narrow particle-size distributions were selectively prepared by hydrolysis-peptization of modified alkoxide followed by hydrothermal treatment. Autoclaving modified TiO2 in the presence of HNO3 as cooperative catalysts led to the formation of crystalline TiO2 with narrow-sized distribution. Following the hydrothermal treatment at 150°C, X-ray diffraction shows the particles to be exclusively anatase. Synthesized powder is characterized by FT-IR, scanning electron microscopy (FESEM) and transmission electron microscopy (HRTEM). The photocatalytic activity in the degradation of orange-II is quite comparable to good anatase and rutile nanocrystallites.

  7. Effect of oxygen nonstoichiometry on photo-electrochemical properties of TiO 2- x

    NASA Astrophysics Data System (ADS)

    Radecka, M.; Trenczek-Zajac, A.; Zakrzewska, K.; Rekas, M.

    Polycrystalline TiO 2- x pellets were equilibrated at 1220-1420 K in a flow of Ar + 7 vol.% H 2 gas mixture. The resulting deviation x from stoichiometric composition of titanium dioxide was determined gravimetrically. X-ray diffractometry revealed coexistence of rutile with Ti nO 2 n-1 Magnéli phases. Optical reflectance and photocurrent spectroscopies served as experimental methods of the band gap determination. Polycrystalline TiO 2- x were used as photoanodes in a photoelectrochemical cell. The photocurrent response to the applied voltage was studied. It was found that TiO 2- x with x ca. 0.006 exhibited the best photoelectrochemical performance.

  8. 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.

  9. 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.

  10. The preparation of nitrogen-doped TiO 2- xN x photocatalyst coated on hollow glass microbeads

    NASA Astrophysics Data System (ADS)

    Shifu, Chen; Xuqiang, Liu; Yunzhang, Liu; Gengyu, Cao

    2007-01-01

    In this paper, the effective method for nitrogen-doped TiO 2- xN x photocatalyst coated on hollow glass microbeads is described, which uses titanium tetraisopropoxide [Ti( iso-OC 3H 7) 4] as the raw materials and gaseous ammonia as a heat treatment atmosphere. The effects of heat treatment temperature and time on the photocatalytic activity of TiO 2- xN x/beads are studied. The photocatalyst is characterized by the UV-vis diffuse reflection spectroscopy, X-ray photoelectron spectroscopy (XPS), X-ray powder diffraction (XRD), Brunauer-Emmett-Teller (BET) analysis and scanning electron microscopy (SEM). The results show that when the TiO 2- xN x/beads is heated at 650 °C for 5 h, the photocatalytic activity of the TiO 2- xN x/beads is the best. Compared with TiO 2, the photoabsorption wavelength range of nitrogen-doped TiO 2- xN x red shifts of about 60 nm, and the photoabsorption intensity increases as well. The photocatalytic activity of the TiO 2- xN x/beads is higher than that of the TiO 2/beads under visible light irradiation. The presence of nitrogen neither influences on the transformation of anatase to rutile, nor creates new crystal phases. When the TiO 2- xN x/beads is heated at 650 °C for 5 h, the amount of nitrogen-doped is 0.53 wt.% in the TiO 2- xN x. As the density of TiO 2- xN x/beads prepared is lower than 1.0 g/cm 3, it may float on water surface and use broader sunlight spectrum directly.

  11. Crystallization kinetics and phase transformations in aluminum ion-implanted electrospun TiO2 nanofibers

    NASA Astrophysics Data System (ADS)

    Albetran, H.; Low, I. M.

    2016-12-01

    Electrospun TiO2 nanofibers were implanted with aluminum ions, and their crystallization kinetics, phase transformations, and activation energies were investigated from 25 to 900 °C by in situ high-temperature synchrotron radiation diffraction. The amorphous non-implanted and Al ion-implanted TiO2 nanofibers transformed to crystalline anatase at 600 °C and to rutile at 700 °C. The TiO2 phase transformation of the Al ion-implanted material was accelerated relative to non-implanted sample. Compared with non-implanted nanofibers, the Al-implanted materials yielded a decreased activation energies from 69(17) to 29(2) kJ/mol for amorphous-to-anatase transformation and from 112(15) to 129(5) kJ/mol for anatase-to-rutile transformation. A substitution of smaller Al ions for Ti in the TiO2 crystal structure results in accelerated titania phase transformation and a concomitant reduction in the activation energies.

  12. 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-

  13. Photocatalysis of Thin Films of TiO2 on Al2O3 Substrates

    NASA Astrophysics Data System (ADS)

    Turbay, David; Luttrell, Timothy; Batzill, Matthias

    2013-03-01

    Titanium dioxide (TiO2) has grown to be one of the most promising photocatalysts in recent years because of extensive applications in renewable and clean energy. The rise in demand for these new energies has driven an increase in research on metal oxides and their properties. Our interest in growing the rutile structure of TiO2 stems from its lower excitation energy (3.0 eV) when compared to anatase (3.2 eV), which indicates it has better activity in the visible portion of the spectrum. It has been shown that sapphire (Al2O3) substrates are conducive to epitaxial rutile growth. In this study, we measured the photocatalytic activity of thin films of TiO2 on r-Al2O3 (1 -1 0 2) substrates. We used PLD and MBE to grow the films, which were characterized using XPS and AFM. Photoactivity was measured via the decomposition of methyl orange on the film's surface using a UV/VIS spectrophotometer. The decomposition of this organic compound is driven by oxidation-reduction reactions on the surface of the TiO2 film. From this, we calculated the charge carrier diffusion length and compared it to that of anatase. Funding provided by NSF Grant DMR-1004873

  14. 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.

  15. 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.

  16. Thin films of TiO2:N for photo-electrochemical applications.

    PubMed

    Trenczek-Zajac, A; Pamula, E; Radecka, M; Kowalski, K; Reszka, A; Brudnik, A; Kusior, E; Zakrzewska, K

    2012-06-01

    Dc-pulsed magnetron sputtering from Ti target in reactive Ar+O2+N2 atmosphere was used to grow stoichiometric TiO2:N and non-stoichiometric TiO2-x:N thin films. X-ray diffraction at glancing incidence, atomic force microscopy AFM, scanning electron microscopy SEM, X-ray photoelectron spectroscopy XPS, and optical spectrophotometry were applied for sample characterization. Measurements of photocurrent versus voltage and wavelength over the ultraviolet uv and visible vis ranges of the light spectrum were performed in order to assess the performance of nitrogen-doped titanium dioxide thin films as photoanodes for hydrogen generation in photoelectrochemical cells, PEC. Undoped TiO2 and TiO2-x films were found to be composed of anatase and rutile mixture with larger anatase crystallites (25-35 nm) while the growth of smaller rutile crystallites (6-10 nm) predominated at higher nitrogen flow rates etaN2 as measured in standard cubic centimeters, sccm. Nitrogen-to-titanium ratio increased from N/Ti = 0.05 at etaN2 = 0.8 sccm for stoichiometric TiO2:N to N/Ti = 0.11 at etaN2 = 0.8 sccm for nonstoichiometric TiO2-x:N thin films. A red-shift in the optical absorbance was observed with an increase in etaN2. Doping with nitrogen improved photoelectrochemical properties over the visible range of the light spectrum in the case of nonstoichiometric samples.

  17. Formation of titanium monoxide (001) single-crystalline thin film induced by ion bombardment of titanium dioxide (110)

    NASA Astrophysics Data System (ADS)

    Pabón, B. M.; Beltrán, J. I.; Sánchez-Santolino, G.; Palacio, I.; López-Sánchez, J.; Rubio-Zuazo, J.; Rojo, J. M.; Ferrer, P.; Mascaraque, A.; Muñoz, M. C.; Varela, M.; Castro, G. R.; de La Fuente, O. Rodríguez

    2015-02-01

    A plethora of technological applications justify why titanium dioxide is probably the most studied oxide, and an optimal exploitation of its properties quite frequently requires a controlled modification of the surface. Low-energy ion bombardment is one of the most extended techniques for this purpose and has been recently used in titanium oxides, among other applications, to favour resistive switching mechanisms or to form transparent conductive layers. Surfaces modified in this way are frequently described as reduced and defective, with a high density of oxygen vacancies. Here we show, at variance with this view, that high ion doses on rutile titanium dioxide (110) induce its transformation into a nanometric and single-crystalline titanium monoxide (001) thin film with rocksalt structure. The discovery of this ability may pave the way to new technical applications of ion bombardment not previously reported, which can be used to fabricate heterostructures and interfaces.

  18. A novel chemical scheme for flotation of rutile from eclogite tailing

    NASA Astrophysics Data System (ADS)

    Xu, Bo; Liu, Shuang; Li, Hongqiang; Zhao, Yunliang; Li, Hongchao; Song, Shaoxian

    A novel chemical scheme for the flotation of rutile from eclogite tailings has been developed in this work. It consists of lead ion as the activator, sodium fluorosilicate (SF) as the depressant, and styryl phosphonic acid (SPA) and n-octyl alcohol (OCT) as the collector. By using the proposed scheme to treat a feed ore of 4.5% TiO2, a rougher concentrate of grade 84.47% TiO2 was achieved with the recovery of 61.5%. Also, the scheme made a high flotation rate for rutile. The scheme was applied to closed-circuit flotation (one-stage rougher flotation, two-stage scavenger flotation and two-stage cleaner flotation), produced a concentrate of 92% TiO2 with the recovery of 70%. It is shown that the new chemical scheme would be a potential one for the effective separation of rutile from eclogite ores.

  19. 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.

  20. Influence of the oxygen concentration on the formation of crystalline phases of TiO2 during the low-pressure arc-discharge plasma synthesis

    NASA Astrophysics Data System (ADS)

    Ushakov, A. V.; Karpov, I. V.; Lepeshev, A. A.

    2016-02-01

    The synthesis of titanium dioxide (TiO2) nanoparticles with different percentage of anatase and rutile phases is investigated. The synthesis is performed by controlling the oxygen percentage in the gas mixture in the plasmachemical evaporation-condensation process employing a low-pressure arc discharge. In all our experiments, the pressure in the plasmachemical reactor and the average size of particles remain constant and are 60 Pa and 6 nm, respectively. The crystal structure of synthesized TiO2 is studied using X-ray diffraction; the morphology of the particles is analyzed employing transmission electron microscopy. Using X-ray phase analysis, it is established that the concentration of the TiO2 anatase phase decreases upon a decrease in the oxygen concentration in the gas mixture. It is shown that the TiO2 anatase phase is more efficient for photocatalytic decomposition of methylene blue than the rutile phase.