Antibacterial photocatalytic activity of different crystalline TiO2 phases in oral multispecies biofilm.

PubMed

Pantaroto, Heloisa N; Ricomini-Filho, Antonio P; Bertolini, Martinna M; Dias da Silva, José Humberto; Azevedo Neto, Nilton F; Sukotjo, Cortino; Rangel, Elidiane C; Barão, Valentim A R

2018-07-01

Titanium dioxide (TiO 2 ) incorporation in biomaterials is a promising technology due to its photocatalytic and antibacterial activities. However, the antibacterial potential of different TiO 2 crystalline structures on a multispecies oral biofilm remains unknown. We hypothesized that the different crystalline TiO 2 phases present different photocatalytic and antibacterial activities. Three crystalline TiO 2 films were deposited by magnetron sputtering on commercially pure titanium (cpTi), in order to obtain four groups: (1) machined cpTi (control); (2) A-TiO 2 (anatase); (3) M-TiO 2 (mixture of anatase and rutile); (4) R-TiO 2 (rutile). The morphology, crystalline phase, chemical composition, hardness, elastic modulus and surface free energy of the surfaces were evaluated. The photocatalytic potential was assessed by methylene blue degradation assay. The antibacterial activity was evaluated on relevant oral bacteria, by using a multispecies biofilm (Streptococcus sanguinis, Actinomyces naeslundii and Fusobacterium nucleatum) formed on the treated titanium surfaces (16.5h) followed by UV-A light exposure (1h) to generate reactive oxygen species production. All TiO 2 films presented around 300nm thickness and improved the hardness and elastic modulus of cpTi surfaces (p<0.05). A-TiO 2 and M-TiO 2 films presented superior photocatalytic activity than R-TiO 2 (p<0.05). M-TiO 2 revealed the greatest antibacterial activity followed by A-TiO 2 (≈99.9% and 99% of bacterial reduction, respectively) (p<0.001 vs. control). R-TiO 2 had no antibacterial activity (p>0.05 vs. control). This study brings new insights on the development of extra oral protocols for the photocatalytic activity of TiO 2 in oral biofilm-associated disease. Anatase and mixture-TiO 2 showed antibacterial activity on this oral bacterial biofilm, being promising surface coatings for dental implant components. Copyright © 2018 The Academy of Dental Materials. All rights reserved.

Tunable photovoltaic performance of preferentially oriented rutile TiO2 nanorod photoanode based dye sensitized solar cells with quasi-state electrolyte

NASA Astrophysics Data System (ADS)

Sabari Girisun, T. C.; Jeganathan, C.; Pavithra, N.; Anandan, S.

2018-02-01

Photoanodes made of highly oriented TiO2 nanorod (NR) arrays with different aspect ratios were synthesized via a one-step hydrothermal technique. Preferentially oriented single crystalline rutile TiO2 was confirmed by the single peak in an XRD pattern (2θ = 63°, (0 0 2)). FESEM images evidenced the growth of an array of NRss having different geometries with respect to reaction time and solution refreshment rate. The length, diameter and aspect ratio of the NRs increased with reaction time as 4 h (1.98 μm, 121 nm, 15.32), 8 h (4 μm, 185 nm, 22.70), 12 h (5.6 μm, 242 nm, 27.24) and 16 h (8 μm, 254 nm, 38.02), respectively. Unlike a conventional dye-sensitized solar cell (DSSC) with a liquid electrolyte, DSSCs were fabricated here using one-dimensional rutile TiO2 NR based photoanodes, N719 dye and a quasi-state electrolyte. The charge transport properties were investigated using current-voltage curves and fitted using the one-diode model. Interestingly the photovoltaic performance of the DSSCs increased exponentially with the length of the NR and was attributed to a higher surface to volume ratio, more dye anchoring, and channelized electron transport. The higher photovoltaic performance (Jsc = 5.99 mA cm-2, Voc = 750 mV, η = 3.08%) was observed with photoanodes (16 h) made with the longer, densely packed TiO2 NRs (8 μm, 254 nm).

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.

Microscopic origin of lattice contraction and expansion in undoped rutile TiO2 nanostructures

NASA Astrophysics Data System (ADS)

Santara, Batakrushna; Giri, P. K.; Imakita, Kenji; Fujii, Minoru

2014-05-01

We have investigated the microscopic origin of lattice expansion and contraction in undoped rutile TiO2 nanostructures by employing several structural and optical spectroscopic tools. Rutile TiO2 nanostructures with morphologies such as nanorods, nanopillars and nanoflowers, depending upon the growth conditions, are synthesized by an acid-hydrothermal process. Depending on the growth conditions and post-growth annealing, lattice contraction and expansion are observed in the nanostructures and it is found to correlate with the nature and density of intrinsic defects in rutile TiO2. The change in lattice volume correlates well with the optical bandgap energy. Irrespective of growth conditions, theTiO2 nanostructures exhibit strong near infrared (NIR) photoluminescence (PL) at 1.43 eV and a weak visible PL, which are attributed to the Ti interstitials and O vacancies, respectively, in rutile TiO2 nanostructures. Further, ESR study reveals the presence of singly ionized oxygen vacancy defects. It is observed that lattice distortion depends systematically on the relative concentration and type of defects such as oxygen vacancies and Ti interstitials. XPS analyses revealed a downshift in energy for both Ti 2p and O 1s core level spectra for various growth conditions, which is believed to arise from the lattice distortions. It is proposed that the Ti4+ interstitial and F+ oxygen vacancy defects are primarily responsible for lattice expansion, whereas the electrostatic attraction between Ti4+ interstitial and O2- interstitial defects causes the lattice contraction in the undoped TiO2 nanostructures. The control of lattice parameters through the intrinsic defects may provide new routes to achieving novel functionalities in advanced materials that can be tailored for future technological applications.

Tunable photovoltaic performance of preferentially oriented rutile TiO2 nanorod photoanode based dye sensitized solar cells with quasi-state electrolyte.

PubMed

Girisun, T C Sabari; Jeganathan, C; Pavithra, N; Anandan, S

2018-01-23

Photoanodes made of highly oriented TiO 2 nanorod (NR) arrays with different aspect ratios were synthesized via a one-step hydrothermal technique. Preferentially oriented single crystalline rutile TiO 2 was confirmed by the single peak in an XRD pattern (2θ = 63°, (0 0 2)). FESEM images evidenced the growth of an array of NRss having different geometries with respect to reaction time and solution refreshment rate. The length, diameter and aspect ratio of the NRs increased with reaction time as 4 h (1.98 μm, 121 nm, 15.32), 8 h (4 μm, 185 nm, 22.70), 12 h (5.6 μm, 242 nm, 27.24) and 16 h (8 μm, 254 nm, 38.02), respectively. Unlike a conventional dye-sensitized solar cell (DSSC) with a liquid electrolyte, DSSCs were fabricated here using one-dimensional rutile TiO 2 NR based photoanodes, N719 dye and a quasi-state electrolyte. The charge transport properties were investigated using current-voltage curves and fitted using the one-diode model. Interestingly the photovoltaic performance of the DSSCs increased exponentially with the length of the NR and was attributed to a higher surface to volume ratio, more dye anchoring, and channelized electron transport. The higher photovoltaic performance (J sc  = 5.99 mA cm -2 , V oc  = 750 mV, η = 3.08%) was observed with photoanodes (16 h) made with the longer, densely packed TiO 2 NRs (8 μm, 254 nm).

Influence of energy band alignment in mixed crystalline TiO2 nanotube arrays: good for photocatalysis, bad for electron transfer

NASA Astrophysics Data System (ADS)

Mohammadpour, Raheleh

2017-12-01

Despite the wide application ranges of TiO2, the precise explanation of the charge transport dynamic through a mixed crystal phase of this semiconductor has remained elusive. Here, in this research, mixed-phase TiO2 nanotube arrays (TNTAs) consisting of anatase and 0-15% rutile phases has been formed through various annealing processes and employed as a photoelectrode of a photovoltaic cell. Wide ranges of optoelectronic experiments have been employed to explore the band alignment position, as well as the depth and density of trap states in TNTAs. Short circuit potential, as well as open circuit potential measurements specified that the band alignment of more than 0.2 eV exists between the anatase and rutile phase Fermi levels, with a higher electron affinity for anatase; this can result in a potential barrier in crystallite interfaces and the deterioration of electron mobility through mixed phase structures. Moreover, a higher density of shallow localized trap states below the conduction band with more depth (133 meV in anatase to 247 meV in 15% rutile phase) and also deep oxygen vacancy traps have been explored upon introducing the rutile phase. Based on our results, employing TiO2 nanotubes as just the electron transport medium in mixed crystalline phases can deteriorate the charge transport mechanism, however, in photocatalytic applications when both electrons and holes are present, a robust charge separation in crystalline anatase/rutile interphases will result in better performances.

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.

Hydrothermal synthesis and enhanced photocatalytic activity of mixed-phase TiO2 powders with controllable anatase/rutile ratio

NASA Astrophysics Data System (ADS)

Wang, Qi; Qiao, Zhi; Jiang, Peng; Kuang, Jianlei; Liu, Wenxiu; Cao, Wenbin

2018-03-01

In this study, mixed-phase TiO2 powders were novelly synthesized via a facile and mild hydrothermal method without any post-heat treatment. TiOSO4 and peroxide titanic acid (PTA) were used as inorganic titanium sources, while no special solvent or additive were introduced. The XRD and TEM results showed the mixed-phase TiO2 powders were composed of anatase and rutile phases, and the PTA sol played an important role on forming the rutile nucleus. The proportion of rutile in the mixed-phase TiO2 could be easily controlled in the range of 0%-70.5% by changing the amount of PTA sol used in the synthesis process. The UV-Visible absorption spectra indicated the prepared mixed-phase TiO2 showed enhanced visible light absorption with the increase of rutile ratio. The photodegradation experiments revealed the mixed-phase TiO2 exhibited the best photocatalytic activity at the rutile ratio of 41.5%, while a higher or lower rutile ratio both resulted in the decrease of photocatalytic activity.

Defect types and room temperature ferromagnetism in N-doped rutile TiO2 single crystals

NASA Astrophysics Data System (ADS)

Qin, Xiu-Bo; Li, Dong-Xiang; Li, Rui-Qin; Zhang, Peng; Li, Yu-Xiao; Wang, Bao-Yi

2014-06-01

The magnetic properties and defect types of virgin and N-doped TiO2 single crystals are probed by superconducting quantum interference device (SQUID), X-ray photoelectron spectroscopy (XPS), and positron annihilation analysis (PAS). Upon N doping, a twofold enhancement of the saturation magnetization is observed. Apparently, this enhancement is not related to an increase in oxygen vacancy, rather to unpaired 3d electrons in Ti3+, arising from titanium vacancies and the replacement of O with N atoms in the rutile structure. The production of titanium vacancies can enhance the room temperature ferromagnetism (RTFM), and substitution of O with N is the onset of ferromagnetism by inducing relatively strong ferromagnetic ordering.

Electronic properties of Cr-N codoped rutile TiO2(110) thin films

NASA Astrophysics Data System (ADS)

Cheng, Zhengwang; Zhang, Lili; Dong, Shihui; Ma, Xiaochuan; Ju, Huanxin; Zhu, Junfa; Cui, Xuefeng; Zhao, Jin; Wang, Bing

2017-12-01

We report our investigation on the electronic properties of Cr-N codoped rutile TiO2(110) single crystal thin films, homoepitaxially grown by pulsed-laser-deposition method, and characterized using scanning tunneling microscopy and spectroscopy (STM/STS), X-ray/ultraviolet photoemission spectroscopy (XPS/UPS), in combination with first-principles calculations. Our results show that the bandgap reduction of the TiO2(110) surface is mainly contributed by the delocalized states whose position is at 2.0 eV below the Fermi level, introduced by the substitutional codoped Cr-2N pair, which is evidenced by the accordance of the results between the STS spectra and the calculated DOS. The codoped Cr-N pair contributes the gap state at about 0.8 eV below the Fermi level, in consistent with the theoretical calculations. While, the monodoped Cr contributes the states either close to the valence band maximum or the conduction band minimum, which should not contribute to the bandgap reduction too much. Our experimental results joint with theoretical calculations provide an atomic view of the bandgap reduction of the rutile TiO2(110) surface, which indicates that the excess substitutional N atoms should be important to efficiently narrow the bandgap by introducing the Cr-2N pairs.

First-principles investigation of aluminum intercalation and diffusion in TiO2 materials: Anatase versus rutile

NASA Astrophysics Data System (ADS)

Tang, Weiqiang; Xuan, Jin; Wang, Huizhi; Zhao, Shuangliang; Liu, Honglai

2018-04-01

Aluminum-ion batteries, emerging as a promising post-lithium battery solution, have been a subject of increasing research interest. Yet, most existing aluminum-ion research has focused on electrode materials development and synthesis. There has been a lack of fundamental understanding of the electrode processes and thus theoretical guidelines for electrode materials selection and design. In this study, by using density functional theory, we for the first time report a first-principles investigation on the thermodynamic and kinetic properties of aluminum intercalation into two common TiO2 polymorphs, i.e., anatase and rutile. After examining the aluminum intercalation sites, intercalation voltages, storage capacities and aluminum diffusion paths in both cases, we demonstrate that the stable aluminum intercalation site locates at the center of the O6 octahedral for TiO2 rutile and off center for TiO2 anatase. The maximum achievable Al/Ti ratios for rutile and anatase are 0.34375 and 0.36111, respectively. Although rutile is found to have an aluminum storage capacity slightly higher than anatase, the theoretical specific energy of rutile can reach 20.90 Wh kg-1, nearly twice as high as anatase (9.84 Wh kg-1). Moreover, the diffusion coefficient of aluminum ions in rutile is 10-9 cm2 s-1, significantly higher than that in anatase (10-20 cm2 s-1). In this regard, TiO2 rutile appears to be a better candidate than anatase as an electrode material for aluminum-ion batteries.

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.

Acidic Peptizing Agent Effect on Anatase-Rutile Ratio and Photocatalytic Performance of TiO2 Nanoparticles

NASA Astrophysics Data System (ADS)

Mahmoud, Hatem A.; Narasimharao, Katabathini; Ali, Tarek T.; Khalil, Kamal M. S.

2018-02-01

TiO2 nanoparticles were synthesized from titanium isopropoxide by a simple peptization method using sulfuric, nitric, and acetic acids. The effect of peptizing acid on physicochemical and photocatalytic properties of TiO2 powders was studied. The structural properties of synthesized TiO2 powders were analyzed by using XRD, TEM, N2-physisorption, Raman, DR UV- vis, FTIR, and X-ray photoelectron spectroscopy techniques. The characterization results showed that acetic acid peptization facilitated the formation of pure anatase phase after thermal treatment at 500 °C; in contrast, nitric acid peptization led to a major rutile phase formation (67%). Interestingly, the sample peptized using sulfuric acid yielded 95% anatase and 5% rutile phases. The photocatalytic activity of synthesized TiO2 nanoparticles was evaluated for degradation of selected organic dyes (crystal violet, methylene blue, and p-nitrophenol) in aqueous solution. The results confirmed that the TiO2 sample peptized using nitric acid (with rutile and anatase phases in 3:1 ratio) offered the highest activity for degradation of organic dyes, although, TiO2 samples peptized using sulfuric acid and acetic acid possessed smaller particle size, higher band gap energy, and high surface area. Interestingly, TiO2 sample peptized with nitric acid possessed relatively high theoretical photocurrent density (0.545 mAcm-2) and pore diameter (150 Å), which are responsible for high electron-hole separation efficiency and diffusion and mass transportation of organic reactants during the photochemical degradation process. The superior activity of TiO2 sample peptized with nitric acid is due to the effective transfer of photogenerated electrons between rutile and anatase phases.

Thermodynamic investigation of the phase equilibrium boundary between TiO2 rutile and its α-PbO2-type high-pressure polymorph

NASA Astrophysics Data System (ADS)

Kojitani, Hiroshi; Yamazaki, Monami; Kojima, Meiko; Inaguma, Yoshiyuki; Mori, Daisuke; Akaogi, Masaki

2018-06-01

Heat capacity (C P) of rutile and α-PbO2 type TiO2 (TiO2-II) were measured by the differential scanning calorimetry and thermal relaxation method. Using the results, standard entropies at 1 atm and 298.15 K of rutile and TiO2-II were determined to be 50.04(4) and 46.54(2) J/mol K, respectively. Furthermore, thermal expansivity (α) determined by high-temperature X-ray diffraction measurement and mode Grüneisen parameters obtained by high-pressure Raman spectroscopy suggested the thermal Grüneisen parameter (γ th) for TiO2-II of 1.7(1). By applying the obtained low-temperature C P and γ th, the measured C P and α data of TiO2-II were extrapolated to higher temperature region using a lattice vibrational model calculation, as well as rutile. Internally consistent thermodynamic data sets of both rutile and TiO2-II assessed in this study were used to thermodynamically calculate the rutile‒TiO2-II phase equilibrium boundary. The most plausible boundary was obtained to be P (GPa) = 0.0074T (K) - 1.7. Our boundary suggests that the crystal growth of TiO2-II observed below 5.5 GPa and 900 K in previous studies advanced in its stability field. The phase boundary calculation also suggested small, exothermic phase transition enthalpy from rutile to TiO2-II at 1 atm and 298.15 K of - 0.5 to - 1.1 kJ/mol. This implies that the thermodynamic stability of rutile at 1 atm above room temperature is due to larger contribution of entropy term.

Trophic transfer potential of two different crystalline phases of TiO2 NPs from Chlorella sp. to Ceriodaphnia dubia.

PubMed

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

2018-04-01

Owing to the increase in the usage of titanium dioxide nanoparticles (TiO 2 NPs), their release into the aquatic environment is inevitable. In the aquatic ecosystem, TiO 2 NPs can bio-magnify at various trophic levels in the food chain through dietary exposure. In the current study, the trophic transfer potential of two crystalline phases of TiO 2, anatase and rutile nanoparticles (individual as well as a binary mixture) has been evaluated in the lake water matrix using algae-daphnia system. Chlorella sp. and Ceriodaphnia dubia were used as test organisms to represent the algae-daphnia food chain of the freshwater ecosystem. Other than crystallinity, the effect of irradiation (visible and UV-A) was also investigated at the test concentrations, 75, 300, and 1200 μM. TiO 2 NPs treated algal diet produced significant mortality only at the test concentrations, 300 and 1200 μM. The type of irradiation and crystallinity doesn't have any impact on the mortality of daphnids through the dietary exposure of TiO 2 NPs. Comparing the mixture with individual NPs, binary mixture induced less mortality on C. dubia which signifies the antagonistic effect of NPs when they coexist. Statistical modeling confirmed the antagonistic effect of the binary mixture on C. dubia. As individual NPs, anatase and rutile forms showed a maximum Ti accumulation under UV-A and visible irradiation, respectively. BMF of TiO 2 NPs has been in validation with the bioaccumulation noted in C. dubia. Individual NPs (75 μM) showed higher BMF value of ∼23 under both UV-A (anatase) and visible (rutile) irradiation. Individual NPs showing higher BMF confirmed their trophic transfer potential in the aquatic food chain, primarily through the diet. In contrast, the binary mixture obtained a higher BMF of 1.9 and 0.79 at 75 and 300 μM under visible and UV-A irradiation, respectively. The plausible reason behind this decrement was the antagonistic effect of the mixture which significantly reduced

Revelation of rutile phase by Raman scattering for enhanced photoelectrochemical performance of hydrothermally-grown anatase TiO2 film

NASA Astrophysics Data System (ADS)

Cho, Hsun-Wei; Liao, Kuo-Lun; Yang, Jih-Sheng; Wu, Jih-Jen

2018-05-01

Photoelectrochemical (PEC) performances of the anatase TiO2 films hydrothermally grown on the seeded fluorine-doped tin oxide (FTO) substrates are examined in this work. Structural characterizations of the TiO2 films were conducted using Raman scattering spectroscopy. Although there is no obvious rutile peak appearing, an asymmetrical peak centered at ∼399 cm-1 was observed in the Raman spectra of the TiO2 films deposited either on the low-temperature-formed seed layers or with low concentrations of Ti precursor. The asymmetrical Raman shift can be deconvoluted into the B1g mode of anatase and Eg mode of rutile TiO2 peaks centered at ∼399 cm-1 and ∼447 cm-1, respectively. Therefore, a minute quantity of rutile phase was inspected in the anatase film using Raman scattering spectroscopy. With the same light harvesting ability, we found that the PEC performance of the anatase TiO2 film was significantly enhanced as the minute quantity of rutile phase existing in the film. It is ascribed to the formation of the anatase/rutile heterojunction which is beneficial to the charge separation in the photoanode.

Visible Light-Driven H 2 Production over Highly Dispersed Ruthenia on Rutile TiO 2 Nanorods

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

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

2016-01-04

The immobilization of miniscule quantities of RuO 2 (~0.1%) onto one-dimensional (1D) TiO 2 nanorods (NRs) allows H 2 evolution from water under visible light irradiation. Rod-like rutile TiO 2 structures, exposing preferentially (110) surfaces, are shown to be critical for the deposition of RuO 2 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 RuO 2(110) grown as 1D nanowires on rutile TiO 2(110), which occurs only at extremely low loads of RuO 2, leads to the formation of a heterointerface that efficientlymore » adsorbs visible light. The surface defects, band gap narrowing, visible photoresponse, and favorable upward band bending at the heterointerface drastically facilitate the transfer and separation of photogenerated charge carriers« less

Visible Light-Driven H 2 Production over Highly Dispersed Ruthenia on Rutile TiO 2 Nanorods

DOE PAGES

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

2015-12-02

The immobilization of miniscule quantities of RuO 2 (~0.1%) onto one-dimensional (1D) TiO 2 nanorods (NRs) allows H 2 evolution from water under visible light irradiation. In addition, rod-like rutile TiO 2 structures, exposing preferentially (110) surfaces, are shown to be critical for the deposition of RuO 2 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 RuO 2(110) grown as 1D nanowires on rutile TiO 2(110), which occurs only at extremely low loads of RuO 2, leads to the formation of a heterointerfacemore » that efficiently adsorbs visible light. The surface defects, band gap narrowing, visible photoresponse, and favorable upward band bending at the heterointerface drastically facilitate the transfer and separation of photogenerated charge carriers.« less

Rapid synthesis of rutile TiO2 nano-flowers by dealloying Cu60Ti30Y10 metallic glasses

NASA Astrophysics Data System (ADS)

Wang, Ning; Pan, Ye; Wu, Shikai; Zhang, Enming; Dai, Weiji

2018-01-01

The 3D nanostructure rutile TiO2 photocatalyst was rapidly synthesized by dealloying method using Cu60Ti30Y10 amorphous ribbons as precursors. The preparation period was kept down to just 3 h, which is much shorter than those of the samples by dealloying Cu60Ti30Al10, Cu70Ti30 and Cu60Ti30Sn10. The synthesized sample was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). XRD and XPS reveal the successful synthesis of rutile TiO2. The SEM and TEM images show that the synthesized rutile TiO2 nano-material presents homogeneous distributed 3D nanoflowers structure, which is composed of large quantities of fine rice-like nanorods (40-150 nm in diameter and 100-250 nm in length). BET specific surface areas of the samples were investigated by N2 adsorption-desorption isotherms, the fabricated rutile TiO2 exhibits very high specific surface area (194.08 m2/g). The photocatalytic activities of the samples were evaluated by degrading rhodamine B (RhB) dye (10 mg/L) under the irradiation of both simulated visible light (λ > 420 nm) and ultraviolet (UV) light (λ = 365 nm). The results show that the photocatalytic activity of rutile TiO2 prepared by dealloying Cu60Ti30Y10 amorphous ribbons is higher than those of commercial rutile and the sample synthesized by dealloying Cu70Ti30 precursors. The advantages of both short preparation period and superior photocatalytic activity suggest that Cu60Ti30Y10 metallic glasses are really a kind of perfect titanium source for rapidly fabricating high efficient TiO2 nano-materials. In addition, the influence of chemical composition of the amorphous precursors on preparation period of the rutile TiO2 nano-material was investigated from the point of view of standard electrode potentials.

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.

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

NASA Astrophysics Data System (ADS)

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

2014-08-01

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

Kinetically controlled fabrication of single-crystalline TiO 2 nanobrush architectures with high energy {001} facets

DOE PAGES

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

2017-03-01

Here, this study demonstrates that precise control of nonequilibrium growth conditions during pulsed laser deposition (PLD) can be exploited to produce single-crystalline anatase TiO 2 nanobrush architectures with large surface areas terminated with high energy {001} facets. The data indicate that the key to nanobrush formation is controlling the atomic surface transport processes to balance defect aggregation and surface-smoothing processes. High-resolution scanning transmission electron microscopy data reveal that defect-mediated aggregation is the key to TiO 2 nanobrush formation. The large concentration of defects present at the intersection of domain boundaries promotes aggregation of PLD growth species, resulting in the growthmore » of the single-crystalline nanobrush architecture. This study proposes a model for the relationship between defect creation and growth mode in nonequilibrium environments, which enables application of this growth method to novel nanostructure design in a broad range of materials.« less

Electronic structure and photoabsorption of Ti 3+ ions in reduced anatase and rutile TiO 2

DOE PAGES

Wen, Bo; Hao, Qunqing; Yin, Wen-Jin; ...

2018-01-01

We have used two-photon photoemission (2PPE) spectroscopy and first-principles density functional theory calculations to investigate the electronic structure and photoabsorption of the reduced anatase TiO 2 (101) and rutile TiO 2 (110) surfaces.

Ab-initio calculation and experimental observation of room temperature ferromagnetism in 50 keV nitrogen implanted rutile TiO2

NASA Astrophysics Data System (ADS)

Luitel, Homnath; Chakrabarti, Mahuya; Sarkar, A.; Dechoudhury, S.; Bhowmick, D.; Naik, V.; Sanyal, D.

2018-02-01

Room temperature magnetic properties of 50 keV N4+ ion beam implanted rutile TiO2 have been theoretically and experimentally studied. Ab-initio calculation under the frame work of density functional theory has been carried out to study the magnetic properties of the different possible nitrogen related defects in TiO2. Spin polarized density of states calculation suggests that both Ninst and NO can induce ferromagnetic ordering in rutile TiO2. In both cases the 2p orbital electrons of nitrogen atom give rise to the magnetic moment in TiO2. The possibility of the formation of N2 molecule in TiO2 system is also studied but in this case no significant magnetic moment has been observed. The magnetic measurements, using SQUID magnetometer, results a ferromagnetic ordering even at room temperature for the 50 keV N4+ ion beam implanted rutile TiO2.

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

NASA Astrophysics Data System (ADS)

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

2006-11-01

We investigate an environmentally friendly aqueous solution system for rutile TiO2 violet color nanocrystalline thin films growth on ITO substrate at room temperature. Film shows considerable absorption in visible region with excitonic maxima at 434 nm. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected area electron diffraction (SAED), UV-vis, water surface contact angle and energy dispersive X-ray analysis (EDX) techniques in addition to actual photo-image that shows purely rutile phase of TiO2 with violet color, super-hydrophilic and densely packed nanometer-sized spherical grains of approximate diameter 3.15 ± 0.4 nm, characterize the films. Band gap energy of 4.61 eV for direct transition was obtained for the rutile TiO2 films. Film surface shows super-hydrophilic behavior, as exhibited water contact angle was 7°. Strong visible absorption (not due to chlorine) leaves future challenge to use these films in extremely thin absorber (ETA) solar cells.

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.

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...

Fabrication of TiO2 Crystalline Coatings by Combining Ti-6Al-4V Anodic Oxidation and Heat Treatments

PubMed Central

Schvezov, Carlos Enrique; Ares, Alicia Esther

2015-01-01

The bio- and hemocompatibility of titanium alloys are due to the formation of a TiO2 layer. This natural oxide may have fissures which are detrimental to its properties. Anodic oxidation is used to obtain thicker films. By means of this technique, at low voltages oxidation, amorphous and low roughness coatings are obtained, while, above a certain voltage, crystalline and porous coatings are obtained. According to the literature, the crystalline phases of TiO2, anatase, and rutile would present greater biocompatibility than the amorphous phase. On the other hand, for hemocompatible applications, smooth and homogeneous surfaces are required. One way to obtain crystalline and homogeneous coatings is by heat treatments after anodic oxidation. The aim of this study is to evaluate the influence of heat treatments on the thickness, morphology, and crystalline structure of the TiO2 anodic coatings. The characterization was performed by optical and scanning electron microscopy, X-ray diffraction, and X-ray reflectometry. Coatings with different colors of interference were obtained. There were no significant changes in the surface morphology and roughness after heat treatment of 500°C. Heat treated coatings have different proportions of the crystalline phases, depending on the voltage of anodic oxidation and the temperature of the heat treatment. PMID:25784939

Amorphous and crystalline TiO2 nanotube arrays for enhanced Li-ion intercalation properties.

PubMed

Guan, Dongsheng; Cai, Chuan; Wang, Ying

2011-04-01

We have employed a simple process of anodizing Ti foils to prepare TiO2 nanotube arrays which show enhanced electrochemical properties for applications as Li-ion battery electrode materials. The lengths and pore diameters of TiO2 nanotubes can be finely tuned by varying voltage, electrolyte composition, or anodization time. The as-prepared nanotubes are amorphous and can be converted into anatase nanotubes with heat treatment at 480 degrees C. Rutile crystallites emerge in the anatase nanotube when the annealing temperature is increased to 580 degrees C, resulting in TiO2 nanotubes of mixed phases. The morphological features of nanotubes remain unchanged after annealing. Li-ion insertion performance has been studied for amorphous and crystalline TiO2 nanotube arrays. Amorphous nanotubes with a length of 3.0 microm and an outer diameter of 125 nm deliver a capacity of 91.2 microA h cm(-2) at a current density of 400 microA cm(-2), while those with a length of 25 microm and an outer diameter of 158 nm display a capacity of 533 microA h cm-2. When the 3-microm long nanotubes become crystalline, they deliver lower capacities: the anatase nanotubes and nanotubes of mixed phases show capacities of 53.8 microA h cm-2 and 63.1 microA h cm(-2), respectively at the same current density. The amorphous nanotubes show excellent capacity retention ability over 50 cycles. The cycled nanotubes show little change in morphology compared to the nanotubes before electrochemical cycling. All the TiO2 nanotubes demonstrate higher capacities than amorphous TiO2 compact layer reported in literature. The amorphous TiO2 nanotubes with a length of 1.9 microm exhibit a capacity five times higher than that of TiO2 compact layer even when the nanotube array is cycled at a current density 80 times higher than that for the compact layer. These results suggest that anodic TiO2 nanotube arrays are promising electrode materials for rechargeable Li-ion batteries.

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.

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

PubMed

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

2015-11-18

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

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.

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.

Surface studies of anatase and rutile single crystals as model solar cell materials

NASA Astrophysics Data System (ADS)

Mallick, Asim K.

The adsorption of ionic and molecular species on anatase and rutile TiO[2] single crystals has been investigated using synchrotron radiation photoemission spectroscopy. For clean single crystal anatase (101) and (001), and rutile (110) surfaces, a resonant enhancement of the O 2p valence band photoemission intensity is observed as the photon energy is swept through the Ti 3p→3d and 3p→4s optical transition energy, which indicates strong hybridization between Ti and O ions. A small defect peak is observed around 1.1 eV binding energy (B.E.) with respect to the Fermi energy on both anatase (101) and (001) surfaces and at 0.9 eV B.E. on the rutile (110) surface following annealing to 650 °C in UHV. This indicates the surfaces are reduced giving rise to surface Ti[3+]. The adsorption of Cul on single crystal TiO[2] surfaces has been studied using resonant photoemission spectroscopy. The thickness of the Cul overlayer was estimated using core level photoemission via a simple two-layer model and through simulated Auger spectra using the Simulation of Electron Spectra for Surface Analysis (SESSA) database. Photoemission spectra taken at the Ti 3p→3d/4s and Cu 3p→3d/4s optical energies show evidence of strong resonances. In case of the Cu resonances, a particularly strong resonance of a satellite structure at 16 eV B.E. at a photon energy of 77 eV is observed. At the same photon energy an antiresonance is found for valence band features associated with the CuI overlayer indicating a strong ligand-hole screening effect. Band bending effects are observed at both CuI anatase and CuI rutile interfaces, consistent with the formation of a p - n junction. Water adsorption on the single crystal anatase TiO[2] (101) surface has been investigated using ultraviolet photoemission spectroscopy (UPS) at room temperature in order to understand the fundamental interaction of water with anatase surfaces. Following water adsorption the spectra contain features at 6.04 and 10.2 eV B

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.

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

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.

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.

Understanding the effects of Cr doping in rutile TiO2 by DFT calculations and X-ray spectroscopy.

PubMed

Vásquez, G Cristian; Maestre, David; Cremades, Ana; Ramírez-Castellanos, Julio; Magnano, Elena; Nappini, Silvia; Karazhanov, Smagul Zh

2018-06-07

The effects of Cr on local environment and electronic structure of rutile TiO 2 are studied combining theoretical and experimental approaches. Neutral and negatively charged substitutional Cr impurities Cr Ti 0 and Cr Ti 1- as well as Cr-oxygen vacancy complex 2Cr Ti  + V O are studied by the density functional theory (DFT) within the generalized gradient approximation (GGA) of Perdew-Burke-Ernzerhof (PBE) functional. Experimental results based on X-Ray absorption spectroscopy (XAS) and X-Ray photoelectron spectroscopy (XPS) performed on Cr doped TiO 2 at the Synchrotron facility were compared to the theoretical results. It is shown that the electrons of the oxygen vacancy tend to be localized at the t 2g states of the Cr ions in order to reach the stable oxidation state of Cr 3+ . Effects of Cr on crystal field (CF) and structural distortions in the rutile TiO 2 cell were analyzed by the DFT calculations and XAS spectra revealing that the CF and tetragonal distortions in TiO 2 are very sensitive to the concentration of Cr.

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.

Synthesis of TiO2 Nanoparticle and its phase Transition

NASA Astrophysics Data System (ADS)

Mangrola, M. H.; Joshi, V. G.; Parmar, B. H.

2011-12-01

Here we report the synthesis of titanium dioxide (TiO2) nanoparticles and study of its phase transition from anataze to rutile. Titanium dioxide (TiO2) nanoparticles have been prepared by hydrolysis of Titanium isopropoxide an aqueous solution with constant value of pH 2 and peptizing the resultant suspension gel(white-Blue) and calcinate gel at different temperature. Structures of synthetic samples of TiO2 have been examined by X-ray diffraction (XRD) and scanning electron microscope (SEM). The anatase-rutile transition has been a popular topic due to its interest to scientific and engineering fields. . Here we have seen that the 100 °C calcinate powder consist of anatase fine crystalline phase with a particle size 14 to 15 nm. The prepared TiO2 nanoparticles have uniform size and morphology, and the phase transformation kinetics of obtained material was studied by interpretation of the X-ray diffraction patterns peaks. The phase transform occurred from anatase to rutile at calcinate temperature up to 600 °C. A very fine network texture made from uniform nanoparticles was revealed by scanning electron microscopy (SEM) analyses.

NC-AFM observation of atomic scale structure of rutile-type TiO2(110) surface prepared by wet chemical process.

PubMed

Namai, Yoshimichi; Matsuoka, Osamu

2006-04-06

We succeeded in observing the atomic scale structure of a rutile-type TiO2(110) single-crystal surface prepared by the wet chemical method of chemical etching in an acid solution and surface annealing in air. Ultrahigh vacuum noncontact atomic force microscopy (UHV-NC-AFM) was used for observing the atomic scale structures of the surface. The UHV-NC-AFM measurements at 450 K, which is above a desorption temperature of molecularly adsorbed water on the TiO2(110) surface, enabled us to observe the atomic scale structure of the TiO2(110) surface prepared by the wet chemical method. In the UHV-NC-AFM measurements at room temperature (RT), however, the atomic scale structure of the TiO2(110) surface was not observed. The TiO2(110) surface may be covered with molecularly adsorbed water after the surface was prepared by the wet chemical method. The structure of the TiO2(110) surface that was prepared by the wet chemical method was consistent with the (1 x 1) bulk-terminated model of the TiO2(110) surface.

Preparation of atomically flat TiO2(001) surfaces

NASA Astrophysics Data System (ADS)

Wang, Yang; Weitering, Hanno H.; Snijders, Paul C.

2015-03-01

Transition metal oxides with the rutile structure (MO2, M = e.g. Ti, V, or Nb) have highly directional partially occupied t2g orbitals. Some of these orbitals form quasi-1D electronic bands along the rutile c-axis, and Peierls-like ordering phenomena have been observed in VO2 and NbO2. Tailoring the electronic properties of these materials via quantum confinement requires epitaxial growth on suitable substrates such as low index TiO2 surfaces. Because of the high surface energy of rutile TiO2(001), the standard approach of sputtering and annealing usually introduces faceting. Here we demonstrate a facile method to create atomically flat, non-faceted TiO2(001) surfaces. Using scanning tunneling microscopy we observe terraces with a width of approximately 150 nm. Step heights of approximately 0.3 nm are observed, consistent with the c lattice parameter of rutile TiO2. Low energy electron diffraction patterns reveal sharp diffraction spots with an in-plane lattice constant of 0.358 nm which is consistent with a (1x1) ordering of the (001) plane. These TiO2(001) single crystal surfaces can serve as an ideal substrate for further growth of rutile heterostructures. Research sponsored by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division.

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.

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

Origin of colossal dielectric permittivity of rutile Ti0.9In0.05Nb0.05O2: single crystal and polycrystalline

NASA Astrophysics Data System (ADS)

Song, Yongli; Wang, Xianjie; Sui, Yu; Liu, Ziyi; Zhang, Yu; Zhan, Hongsheng; Song, Bingqian; Liu, Zhiguo; Lv, Zhe; Tao, Lei; Tang, Jinke

2016-02-01

In this paper, we investigated the dielectric properties of (In + Nb) co-doped rutile TiO2 single crystal and polycrystalline ceramics. Both of them showed colossal, up to 104, dielectric permittivity at room temperature. The single crystal sample showed one dielectric relaxation process with a large dielectric loss. The voltage-dependence of dielectric permittivity and the impedance spectrum suggest that the high dielectric permittivity of single crystal originated from the surface barrier layer capacitor (SBLC). The impedance spectroscopy at different temperature confirmed that the (In + Nb) co-doped rutile TiO2 polycrystalline ceramic had semiconductor grains and insulating grain boundaries, and that the activation energies were calculated to be 0.052 eV and 0.35 eV for grain and grain boundary, respectively. The dielectric behavior and impedance spectrum of the polycrystalline ceramic sample indicated that the internal barrier layer capacitor (IBLC) mode made a major contribution to the high ceramic dielectric permittivity, instead of the electron-pinned defect-dipoles.

Analysis of Ti valence states in resistive switching regions of a rutile TiO2‑ x four-terminal memristive device

NASA Astrophysics Data System (ADS)

Yamaguchi, Kengo; Takeuchi, Shotaro; Tohei, Tetsuya; Ikarashi, Nobuyuki; Sakai, Akira

2018-06-01

We have performed Ti valence state analysis of our four-terminal rutile TiO2‑ x single-crystal memristors using scanning transmission electron microscopy–electron energy loss spectroscopy (STEM–EELS). Analysis of Ti-L2,3 edge EELS spectra revealed that the electrocolored region formed by the application of voltage includes a valence state reflecting highly reduced TiO2‑ x due to the accumulation of oxygen vacancies. Such a valence state mainly exists within ∼50 nm from the crystal surface and extends along specific crystal directions. These electrically reduced surface layers are considered to directly contribute to the resistive switching (RS) in the four-terminal device. The present results add new insights into the microscopic mechanisms of the RS phenomena and should contribute to further development and improvements of TiO2‑ x based memristive devices.

First-Principles Modeling of Polaron Formation in TiO2 Polymorphs.

PubMed

Elmaslmane, A R; Watkins, M B; McKenna, K P

2018-06-21

We present a computationally efficient and predictive methodology for modeling the formation and properties of electron and hole polarons in solids. Through a nonempirical and self-consistent optimization of the fraction of Hartree-Fock exchange (α) in a hybrid functional, we ensure the generalized Koopmans' condition is satisfied and self-interaction error is minimized. The approach is applied to model polaron formation in known stable and metastable phases of TiO 2 including anatase, rutile, brookite, TiO 2 (H), TiO 2 (R), and TiO 2 (B). Electron polarons are predicted to form in rutile, TiO 2 (H), and TiO 2 (R) (with trapping energies ranging from -0.02 eV to -0.35 eV). In rutile the electron localizes on a single Ti ion, whereas in TiO 2 (H) and TiO 2 (R) the electron is distributed across two neighboring Ti sites. Hole polarons are predicted to form in anatase, brookite, TiO 2 (H), TiO 2 (R), and TiO 2 (B) (with trapping energies ranging from -0.16 eV to -0.52 eV). In anatase, brookite, and TiO 2 (B) holes localize on a single O ion, whereas in TiO 2 (H) and TiO 2 (R) holes can also be distributed across two O sites. We find that the optimized α has a degree of transferability across the phases, with α = 0.115 describing all phases well. We also note the approach yields accurate band gaps, with anatase, rutile, and brookite within six percent of experimental values. We conclude our study with a comparison of the alignment of polaron charge transition levels across the different phases. Since the approach we describe is only two to three times more expensive than a standard density functional theory calculation, it is ideally suited to model charge trapping at complex defects (such as surfaces and interfaces) in a range of materials relevant for technological applications but previously inaccessible to predictive modeling.

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.

Rutile titanium dioxide films deposited with a vacuum arc at different temperatures

NASA Astrophysics Data System (ADS)

Arias, L. Franco; Kleiman, A.; Heredia, E.; Márquez, A.

2012-06-01

Rutile crystalline phase of TiO2 has been one of the most investigated materials for medical applications. Its implementation as a surface layer on biomedical implants has shown to improve hemocompatibility and biocompatibility. In this work, titanium dioxide coatings were deposited on glass and steel 316L substrates using cathodic arc deposition. The coatings were obtained at different substrate temperatures; varying from room temperature to 600°C. The crystalline structure of the films was identified by glancing angle X-ray diffraction. Depending on the substrate material and on its temperature during the deposition process, anatase, anatse+rutile and rutile structures were observed. It was determined that rutile films can be obtained below 600 °C with this deposition method.

Ordered Fe(II)Ti(IV)O3 Mixed Monolayer Oxide on Rutile TiO2(011).

PubMed

Halpegamage, Sandamali; Ding, Pan; Gong, Xue-Qing; Batzill, Matthias

2015-08-25

Oxide monolayers supported or intermixed with an oxide support are potential nanocatalysts whose properties are determined by the interplay with the support. For fundamental studies of monolayer oxides on metal oxide supports, well-defined systems are needed, but so far, the synthesis of monolayer oxides with long-range order on single-crystal oxide surfaces is rare. Here, we show by a combination of scanning tunneling microscopy, photoemission spectroscopy, and density functional theory (DFT)-based computational analysis that the rutile TiO2(011) surface supports the formation of an ordered mixed FeTiO3 monolayer. Deposition of iron in a slightly oxidizing atmosphere (10(-8) Torr O2) and annealing to 300 °C results in a well-ordered surface structure with Fe in a 2+ charge state and Ti in a 4+ charge states. Low-energy ion scattering suggests that the cation surface composition is close to half Fe and half Ti. This surface is stable in ultrahigh vacuum to annealing temperatures of 300 °C before the iron is reduced. DFT simulations confirm that a surface structure with coverage of 50% FeO units is stable and forms an ordered structure. Although distinct from known bulk phases of the iron-titanium oxide systems, the FeTiO3 monolayer exhibits some resemblance to the ilmenite structure, which may suggest that a variety of different mixed oxide phases (of systems that exist in a bulk ilmenite phase) may be synthesized in this way on the rutile TiO2(011) substrate.

Tunable photovoltaic performance of preferentially oriented rutile TiO₂ nanorod photoanodes based dye sensitized solar cells with quasi-state electrolyte.

PubMed

T C, Sabari Girisun; C, Jeganathan; N, Pavithra; Anandan, Sambandam

2017-12-20

Photoanodes made of highly oriented TiO2 nanorod arrays with different aspect ratios were synthesized via one-step hydrothermal technique. Preferentially oriented single crystalline rutile TiO2 was confirmed by the single peak in XRD pattern (2θ=63o, (0 0 2)). FESEM image evidence the growth of an array of nanorods having different geometry with respect to reaction time and solution refreshment rate. The length, diameter and aspect ratio of the nanorods increased with reaction time as 4 hours (1.98 μm, 121 nm, 15.32), 8 hours (4 μm, 185 nm, 22.70), 12 hours (5.6 μm, 242 nm, 27.24) and 16 hours (8 μm, 254 nm, 38.02) respectively. Unlike conventional Dye-Sensitized Solar Cell (DSSC) with a liquid electrolyte, DSSC were fabricated here using 1D rutile TiO2 nanorods based photoanodes, N719 dye and quasi-state electrolyte. The charge transport properties were investigated from current-voltage curves and fitted using one-diode model. Interestingly photovoltaic performance of DSSCs increased exponentially with the length of the nanorod and is attributed to the higher surface to volume ratio, more dye anchoring, and channelized electron transport. Higher photovoltaic performance (Jsc=5.99 mA/cm2, Voc=750 mV, η=3.08%) was observed with photoanodes (16 hours) made of densely packed longest TiO2 nanorods (8 µm, 254 nm). © 2017 IOP Publishing Ltd.

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

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

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 wellmore » 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.« less

Origin of colossal dielectric permittivity of rutile Ti 0.9In 0.05Nb 0.05O 2: single crystal and polycrystalline

DOE PAGES

Song, Yongli; Wang, Xianjie; Sui, Yu; ...

2016-02-12

Here in this article, we investigated the dielectric properties of (In + Nb) co-doped rutile TiO 2 single crystal and polycrystalline ceramics. Both of them showed colossal, up to 10 4, dielectric permittivity at room temperature. The single crystal sample showed one dielectric relaxation process with a large dielectric loss. The voltage-dependence of dielectric permittivity and the impedance spectrum suggest that the high dielectric permittivity of single crystal originated from the surface barrier layer capacitor (SBLC). The impedance spectroscopy at different temperature confirmed that the (In+Nb) co-doped rutile TiO 2 polycrystalline ceramic had semiconductor grains and insulating grain boundaries, andmore » that the activation energies were calculated to be 0.052 eV and 0.35 eV for grain and grain boundary, respectively. The dielectric behavior and impedance spectrum of the polycrystalline ceramic sample indicated that the internal barrier layer capacitor (IBLC) mode made a major contribution to the high ceramic dielectric permittivity, instead of the electron-pinned defect-dipoles.« less

Origin of colossal dielectric permittivity of rutile Ti0.9In0.05Nb0.05O2: single crystal and polycrystalline

PubMed Central

Song, Yongli; Wang, Xianjie; Sui, Yu; Liu, Ziyi; Zhang, Yu; Zhan, Hongsheng; Song, Bingqian; Liu, Zhiguo; Lv, Zhe; Tao, Lei; Tang, Jinke

2016-01-01

In this paper, we investigated the dielectric properties of (In + Nb) co-doped rutile TiO2 single crystal and polycrystalline ceramics. Both of them showed colossal, up to 104, dielectric permittivity at room temperature. The single crystal sample showed one dielectric relaxation process with a large dielectric loss. The voltage-dependence of dielectric permittivity and the impedance spectrum suggest that the high dielectric permittivity of single crystal originated from the surface barrier layer capacitor (SBLC). The impedance spectroscopy at different temperature confirmed that the (In + Nb) co-doped rutile TiO2 polycrystalline ceramic had semiconductor grains and insulating grain boundaries, and that the activation energies were calculated to be 0.052 eV and 0.35 eV for grain and grain boundary, respectively. The dielectric behavior and impedance spectrum of the polycrystalline ceramic sample indicated that the internal barrier layer capacitor (IBLC) mode made a major contribution to the high ceramic dielectric permittivity, instead of the electron-pinned defect-dipoles. PMID:26869187

Insights into effects and mechanism of pre-dispersant on surface morphologies of silica or alumina coated rutile TiO2 particles

NASA Astrophysics Data System (ADS)

Dong, Xiongbo; Sun, Zhiming; Liu, Yangyu; Jiang, Lei; Zheng, Shuilin

2018-05-01

Silica and alumina coated rutile TiO2 samples with various surface morphologies were fabricated using four different pre-dispersants. Using sodium silicate nonahydrate (SSNH) as pre-dispersant, the received sample displayed the best acidic stability. The addition of SSNH could induce layer-by-layer growth of hydrous silica via enhancing the dispersion of hydrous silica nucleus and accelerating the dehydration condensation rate of silica film. Alumina coated rutile TiO2 sample obtained by polyethyleneglycol 1000 (PEG) presented the highest dispersion stability. The existence of PEG can induce the formation of fibrous hydrous alumina film, which would increase the steric hindrance and the promotion of dispersion stability.

Polarization Dependent X-ray Absorption Spectroscopy of the TiO2 Polymorphs Anatase (001) and Rutile (001)

NASA Astrophysics Data System (ADS)

Ederer, D. L.; Ruzycki, N.; Schuler, T.; Zhang, G. P.; Callcott, T. A.; Nachimuthu, P.; Perera, R. C. C.

2002-03-01

Polarization Dependent X-ray Absorption Spectroscopy of the TiO2 Polymorphs Anatase (001) and Rutile (001) N. Ruzycki^a, T. Schuler^a, D.L. Ederer^a, T. A. Callcott^, G. P. Zhang^b, P. Nachimuthu^c,d, and R.C.C. Perera^c a-Tulane University, Department of Physics, New Orleans, LA, 70118 b- Univesity of Tennessee, Department of Physics and Astronomy, Knoxville, TN, 37996 c- Center for X-ray Optics, Lawrence Berkeley Laboratory, Berkeley, CA, d- Department of Chemistry, University of Nevada Las Vegas, Las Vegas NV, 89154 TiO2 is a useful industrial catalyst and has applications in gas sensing and photoelectric devices. All structures consist of octrahedrally-coordinated Ti atoms and three-fold coordinated O atoms. Anatase and rutile differ mainly in the amount of distortion in the octahedra. Because Soft X-ray Absorption Spectroscoy (SXAS) is sensitive to the ligand field, these small differences are reflected the spectra. In the experiment the electronic polarization vector was varied angulary along the equatorial and the longitudnal axes of the sixfold coordinated titanium atoms. This study showed a strong polarization dependence at the oxygen K-edge for rutile (001) and the anatase (001) in the t_2g and eg region for the equatorial bonds. The Titanium L-edge showed a smaller polarization dependence. There was no polarization dependence in the longitudinal direction for anatase (001) or rutile (001) in either the oxygen K-edge or the Ti-L edge. These data are compared with calculations of polarization-dependent matrix elements of the transitions.

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

USGS Publications Warehouse

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

2006-01-01

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

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

DOE PAGES

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

2015-08-11

Although the rutile structure of TiO 2 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 TiO 2 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 tomore » quartic, stabilizing the rutile phase at high temperatures. In these modes, the vibrational displacements of adjacent Ti and O atoms cause variations in hybridization of 3d electrons of Ti and 2p electrons of O atoms. Finally, with thermal expansion, the energy variation in this “phonon-tracked hybridization” flattens the bottom of the interatomic potential well between Ti and O atoms, and induces a quarticity in the phonon potential.« less

Growth of a sea urchin-like rutile TiO2 hierarchical microsphere film on Ti foil for a quasi-solid-state dye-sensitized solar cell.

PubMed

Ri, Jin Hyok; Wu, Shufang; Jin, Jingpeng; Peng, Tianyou

2017-11-30

A sea urchin-like rutile TiO 2 microsphere (RMS) film was fabricated on Ti foil via a hydrothermal process. The resulting rutile TiO 2 hierarchical microspheres with a diameter of 5-6 μm are composed of nanorods with a diameter of ∼200 nm and a length of 1-2 μm. The sea urchin-like hierarchical structure leads to the Ti foil-based RMS film possessing much better light-scattering capability in the visible region than the bare Ti foil. By using it as an underlayer of a nanosized anatase TiO 2 film (bTPP3) derived from a commercially available paste (TPP3), the corresponding bilayer Ti foil-based quasi-solid-state dye-sensitized solar cell (DSSC) only gives a conversion efficiency of 4.05%, much lower than the single bTPP3 film-based one on Ti foil (5.97%). By spin-coating a diluted TPP3 paste (sTPP3) on the RMS film prior to scraping the bTPP3 film, the resulting RMS/sTPP3/bTPP3 film-based DSSC achieves a significantly enhanced efficiency (7.27%). The electrochemical impedance spectra (EIS) show that the RMS/sTPP3/bTPP3 film possesses better electron transport capability and longer electron lifetime than the bTPP3 film. This work not only provides the first example of directly growing rutile TiO 2 hierarchically structured microsphere film on Ti foil suitable for replacing the rigid, heavy and expensive transparent conductive oxide (TCO) glass substrate to serve as a light-scattering underlayer of Ti foil-based quasi-solid-state DSSCs, but also paves a new route to develop Ti foil-based flexible DSSCs with high efficiency, low cost and a wide application field through optimizing the composition and structure of the photoanode.

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 (...

Growth of rutile TiO2 on the convex surface of nanocylinders: from nanoneedles to nanorods and their electrochemical properties

NASA Astrophysics Data System (ADS)

Kong, Junhua; Wei, Yuefan; Zhao, Chenyang; Toh, Meng Yew; Yee, Wu Aik; Zhou, Dan; Phua, Si Lei; Dong, Yuliang; Lu, Xuehong

2014-03-01

In this work, bundles of rutile TiO2 nanoneedles/nanorods are hydrothermally grown on carbon nanofibers (CNFs), forming free-standing mats consisting of three dimensional hierarchical nanostructures (TiO2-on-CNFs). Morphologies and structures of the TiO2-on-CNFs are studied using a field-emission scanning electron microscope (FESEM), transmission electron microscope (TEM), X-ray diffractometer (XRD) and thermogravimetric analyzer (TGA). Their electrochemical properties as electrodes in lithium ion batteries (LIBs) are investigated and correlated with the morphologies and structures. It is shown that the lateral size of the TiO2 nanoneedles/nanorods ranges from a few nanometers to tens of nanometers, and increases with the hydrothermal temperature. Small interspaces are observed between individual nanoneedles/nanorods, which are due to the diverging arrangement of nanoneedles/nanorods induced by growing on the convex surface of nanocylinders. It is found that the growth process can be divided into two stages: initial growth on the CNF surface and further growth upon re-nucleation on the TiO2 bundles formed in the initial growth stage. In order to achieve good electrochemical performance in LIBs, the size of the TiO2 nanostructures needs to be small enough to ensure complete alloying and fast charge transport, while the further growth stage has to be avoided to realize direct attachment of TiO2 nanostructures on the CNFs, facilitating electron transport. The sample obtained after hydrothermal treatment at 130 °C for 2 h (TiO2-130-2) shows the above features and hence exhibits the best cyclability and rate capacity among all samples; the cyclability and rate capacity of TiO2-130-2 are also superior to those of other rutile TiO2-based LIB electrodes.In this work, bundles of rutile TiO2 nanoneedles/nanorods are hydrothermally grown on carbon nanofibers (CNFs), forming free-standing mats consisting of three dimensional hierarchical nanostructures (TiO2-on

Control of interface between anatase TiO2 nanoparticles and rutile TiO2 nanorods for efficient photocatalytic H2 generation

NASA Astrophysics Data System (ADS)

Xia, Xiaohong; Peng, Shuai; Bao, Yuwen; Wang, Yu; Lei, Binglong; Wang, Zhuo; Huang, Zhongbing; Gao, Yun

2018-02-01

In recent years, production of H2 through photocatalytic water splitting has attracted considerable attention in the chemistry and material fields. In this work, TiO2 based heterojunction photocatalyst, which is consisted of rutile nanorods and anatase nanoparticles, is systematically studied by controlling the HCl concentration in hydrothermal process. With the help of loaded Pt, an interesting two-peak feature ("M" shape) is observed in the HCl-dependent H2 production efficiency. The peak values are 54.3 mmol h-1 g-1 and 74.4 mmol h-1 g-1, corresponding to 83.9% and 12% anatase phase, respectively. A detailed analysis based on the microstructure and photoluminescence (PL) spectra indicate that the "M" shape feature is directly linked to the HCl-controlled interface area. Moreover, an unexpected zero interface area is revealed at an intermediate HCl concentration. In terms of homogeneous and heterogeneous nucleations, an interface growth mechanism is proposed to clarify its HCl-sensitive character. This work provides a route to enhance the photocatalytic activity in TiO2 based photocatalyst via increasing the interface area.

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.

Rutile IrO2/TiO2 superlattices: A hyperconnected analog to the Ruddelsden-Popper structure

NASA Astrophysics Data System (ADS)

Kawasaki, Jason K.; Baek, David; Paik, Hanjong; Nair, Hari P.; Kourkoutis, Lena F.; Schlom, Darrell G.; Shen, Kyle M.

2018-05-01

Dimensionality and connectivity among octahedra play important roles in determining the properties, electronic structure, and phase transitions of transition-metal oxides. Here we demonstrate the epitaxial growth of (110)-oriented alternating layers of IrO2 and TiO2, both of which have the rutile structure. These (IrO2)n/(TiO2)2 superlattices consist of IrO6 and TiO6 octahedra tiled in a hyperconnected, edge- and corner-sharing network. Despite the large lattice mismatch between constituent layers (Δ d∥=-2.1 % and Δ c =+6.6 % ), our reactive molecular-beam epitaxy-grown superlattices show high structural quality as determined by x-ray diffraction and sharp interfaces as observed by transmission electron microscopy. The large strain at the interface is accommodated by an ordered interfacial reconstruction. The superlattices show persistent metallicity down to n =3 atomic layers, and angle-resolved photoemission spectroscopy measurements reveal quantized sub-bands with signatures of IrO2-IrO2 interlayer coupling.

SiO2 Solubility in Rutile at High Pressure and Temperature

NASA Astrophysics Data System (ADS)

Ren, Y.; Fei, Y.; Yang, J.; Bai, W. J.; Xu, Z. Q.

2005-12-01

Silicon-bearing rutile has been found in nature. The extent of SiO2 solubility in rutile and the nature of its origin are still not clear. At high pressure, SiO2 takes rutile structure with 6-coordinated Si. The high-pressure phase of SiO2 may enhance its solubility in rutile because possible isovalent exchange in octahedral site. In this study, we report new experimental results on SiO2 solubility in rutile up to 23 GPa and 2273 K. Starting materials are mixtures of powdered TiO2 and SiO2, with compositions of (Ti0.5Si0.5)O2, (Ti0.93Si0.07)O2, and (Ti0.75Si0.25)O2. The mixtures were loaded into either a platinum capsules (for a 10/5 assembly) or a rhenium capsules (for an 8/3 assembly). The experiments were carried out using multi-anvil high-pressure apparatus with rhenium resistance heater. Sample temperatures were measured with a type-C thermocouple. The quenched samples were recovered and prepared for electron microprobe analyses. TiO2-rich and SiO2-rich phases are produced in all the quenched samples. The analyses showed that the solubility of SiO2 in rutile increases with increasing pressure, from 1.5 wt% SiO2 at 10 GPa to 3.8 wt% SiO2 at 23 GPa for a given temperature of 2073 K. The solubility also increases with increasing temperature, from 0.5 wt% SiO2 at 1773 K to 4.5 wt% SiO2 at 2273 K for a given pressure of 18 GPa. On the other hand, the solubility of TiO2 in coesite or stishovite is very limited, with an average of 0.6 wt% TiO2 over the experimental P-T ranges. Lower oxygen fugacity decreases the solubility of SiO2 in rutile, whereas water has little effect on the solubility of SiO2 in rutile. Our experimental data are extreme useful for determine the depth of origin for the SiO2-bearing rutile in nature.

Vacancy identification in Co+ doped rutile TiO2 crystal with positron annihilation spectroscopy

NASA Astrophysics Data System (ADS)

Qin, X. B.; Zhang, P.; Liang, L. H.; Zhao, B. Z.; Yu, R. S.; Wang, B. Y.; Wu, W. M.

2011-01-01

Co-doped rutile TiO2 films were synthesized by ion implantation. Variable energy positron annihilation Doppler broadening spectroscopy and coincidence Doppler broadening measurements were performed for identification of the vacancies. A newly formed type of vacancy can be concluded by the S-W plot and the CDB results indicated that the oxygen vacancy (VO) complex Ti-Co-VO and/or Ti-VO are formed with Co ions implantation and the vacancy concentration is increased with increase of dopant dose.

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

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

Kim, Boseong; Dohnálek, Zdenek; Szanyi, János

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)more » 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

Temperature-programmed desorption study of NO reactions on rutile TiO 2(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 TiO 2(110)-1 × 1 surface reveal several distinct reaction channels in a temperature range of 50–500 K. NO readily reacts on TiO 2(110) to form N 2O, which desorbs between 50 and 200 K (LT N 2O channels), which leaves the TiO 2 surface populated with adsorbed oxygen atoms (O a) as a by-product of N 2O formation. In addition, we observe simultaneous desorption peaks of NO and N 2O at 270 K (HT1 N 2O) and 400 K (HT2 N 2O), respectively, both ofmore » which are attributed to reaction-limited processes. No N-derived reaction product desorbs from TiO 2(110) surface above 500 K or higher, while the surface may be populated with Oa's and oxidized products such as NO 2 and NO 3. The adsorbate-free TiO 2 surface with oxygen vacancies can be regenerated by prolonged annealing at 850 K or higher. Detailed analysis of the three N 2O desorption yields reveals that the surface species for the HT channels are likely to be various forms of NO dimers.« less

Electrochemical synthesis of self-organized TiO2 crystalline nanotubes without annealing

NASA Astrophysics Data System (ADS)

Giorgi, Leonardo; Dikonimos, Theodoros; Giorgi, Rossella; Buonocore, Francesco; Faggio, Giuliana; Messina, Giacomo; Lisi, Nicola

2018-03-01

This work demonstrates that upon anodic polarization in an aqueous fluoride-containing electrolyte, TiO2 nanotube array films can be formed with a well-defined crystalline phase, rather than an amorphous one. The crystalline phase was obtained avoiding any high temperature annealing. We studied the formation of nanotubes in an HF/H2O medium and the development of crystalline grains on the nanotube wall, and we found a facile way to achieve crystalline TiO2 nanotube arrays through a one-step anodization. The crystallinity of the film was influenced by the synthesis parameters, and the optimization of the electrolyte composition and anodization conditions (applied voltage and time) were carried out. For comparison purposes, crystalline anatase TiO2 nanotubes were also prepared by thermal treatment of amorphous nanotubes grown in an organic bath (ethylene glycol/NH4F/H2O). The morphology and the crystallinity of the nanotubes were studied by field emission gun-scanning electron microscopy (FEG-SEM) and Raman spectroscopy, whereas the electrochemical and semiconducting properties were analyzed by means of linear sweep voltammetry, impedance spectroscopy, and Mott-Schottky plots. X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS) allowed us to determine the surface composition and the electronic structure of the samples and to correlate them with the electrochemical data. The optimal conditions to achieve a crystalline phase with high donor concentration are defined.

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.

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

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

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

Balasubramanian, B; Kraemer, KL; Valloppilly, SR

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) moleculesmore » 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.« less

Band Alignment and Controllable Electron Migration between Rutile and Anatase TiO2

PubMed Central

Mi, Yang; Weng, Yuxiang

2015-01-01

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

Structure and Formation Mechanism of Black TiO 2 Nanoparticles

DOE PAGES

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

2015-10-27

The remarkable properties of black TiO 2 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 TiO 2 nanoparticles consists of a disordered Ti 2O 3 shell. The measurements show a transition region that connects the disordered Ti 2O 3 shell to the perfect rutile core consisting first of four to five monolayers of defective rutile, containing clearly visible Ti interstitialmore » 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 Ti 2O 3 layers form by interstitial diffusion of Ti ions. In contrast to recent reports that attribute TiO 2 band-gap narrowing to the synergistic action of oxygen vacancies and surface disorder of nonspecific origin, our results point to Ti 2O 3, which is a narrow-band-gap semiconductor. In conclusion, as a stoichiometric compound of the lower oxidation state Ti 3+ it is expected to be a more robust atomic structure than oxygen-deficient TiO 2 for preserving and stabilizing Ti 3+ surface species that are the key to the enhanced photocatalytic activity of black TiO 2.« less

Polaron-mediated surface reconstruction in the reduced Rutile TiO2 (110) surface

NASA Astrophysics Data System (ADS)

Reticcioli, Michele; Setvin, Martin; Hao, Xianfeng; Diebold, Ulrike; Franchini, Cesare

The role of polarons is of key importance for the understanding of the fundamental properties and functionalities of TiO2. We use density functional theory with an on-site Coulomb interaction and molecular dynamics to study the formation and dynamics of small polarons in the reduced rutile (110) surface. We show that excess electrons donated by oxygen-vacancies (VO) form mobile small polarons that hop easily in subsurface and surface Ti-sites. The polaron formation becomes more favorable by increasing the VO concentration level (up to 20%) due to the progressively lower energy cost needed to distort the lattice. However, at higher VO concentration the shortening of the averaged polaron-polaron distance leads to an increased Coulomb repulsion among the trapped charges at the Ti-sites, which weakens this trend. This instability is overtaken by means of a structural 1 × 2 surface reconstruction, characterized by a distinctively more favorable polaron distribution. The calculations are validated by a direct comparison with experimental AFM and STM data. Our study identifies a fundamentally novel mechanism to drive surface reconstructions and resolves a long standing issue on the origin of the reconstruction in rutile (110) surface.

Photochemical Grafting of Organic Alkenes to Single-Crystal TiO2 Surfaces: A Mechanistic Study

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

Franking, Ryan A.; Kim, Heesuk; Chambers, Scott A.

2012-08-21

The UV-induced photochemical grafting of terminal alkenes has emerged as a versatile way to form molecular layers on semiconductor surfaces. Recent studies have shown that grafting reactions can be initiated by photoelectron emission into the reactant liquid as well as by excitation across the semiconductor bandgap, but the relative importance of these two processes is expected to depend on the nature of the semiconductor and the reactant alkene and the excitation wavelength. Here we report a study of the wavelength-dependent photochemical grafting of alkenes onto single-crystal TiO2 samples. Trifluoroacetamide-protected 10-aminododec-1-ene (TFAAD), 10-N-BOC-aminodec-1-ene (t-BOC) and 1-dodecene were used as model alkenes.more » On rutile(110), photons with energy above the bandgap but below the expected work function are not effective at inducing grafting, while photons with energy sufficient to induce electronic transitions from the TiO2 Fermi level to electronic acceptor states of the reactant molecules induce grafting. A comparison of rutile (110), rutile(001), anatase (001), and anatase(101) samples shows slightly enhanced grafting for rutile but no difference between crystal faces for a given crystal phase. Hydroxylation of the surface increases the reaction rate by lowering the work function and thereby facilitating photoelectron ejection into the adjacent alkene. These results demonstrate that photoelectron emission is the dominant mechanism responsible for grafting when using short-wavelength (~254 nm) light and suggest that photoemission events beginning on mid-gap states may play a crucial role.« less

Improving the activity of rutile titanium dioxide with reduced graphene oxide

NASA Astrophysics Data System (ADS)

Yuliati, Leny; Alim, Nor Shuhada; Lintang, Hendrik O.

2017-11-01

Among titanium dioxide (TiO2), rutile is the most stable polymorph of TiO2 at all temperatures. However, its application as photocatalyst is less explored since generally anatase and anatase-rutile mixture show better photocatalytic activity than the rutile structure. In this study, we successfully improved the photocatalytic activity of rutile up to four times higher when it was modified with reduced graphene oxide (rGO). The rGO-TiO2 composites were prepared by photocatalytic reduction of graphene oxide (GO) at room temperature under ultraviolet (UV) light irradiation in the presence of rutile TiO2. The amount of GO which was prepared by oxidation of graphite flakes via the Hummers' method was varied from 0.5 to 5 wt%. The properties of the obtained composites were investigated by several characterization methods. X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopies revealed that the rGO-TiO2 composites could be prepared without disrupting the structure of rutile TiO2. The fluorescence spectroscopy confirmed that the presence of rGO decreased the emission intensity of rutile TiO2, suggesting that the interactions between the rGO and the rutile TiO2 might cause the decrease in electron-hole recombination on the TiO2. The activity of the composites was evaluated for degradation of phenol under UV light irradiation for 3 h. It was observed that the addition of small amount of rGO (1 wt% GO) significantly improved the photocatalytic activity of rutile TiO2.

Growth of rutile TiO2 nanorods in Ti and Cu ion sequentially implanted SiO2 and the involved mechanisms

NASA Astrophysics Data System (ADS)

Mu, Xiaoyu; Liu, Xiaoyu; Wang, Xiaohu; Dai, Haitao; Liu, Changlong

2018-01-01

TiO2 in nanoscale exhibits unique physicochemical and optoelectronic properties and has attracted much more interest of the researchers. In this work, TiO2 nanostructures are synthesized in amorphous SiO2 slices by implanting Ti ions, or sequentially implanting Ti and Cu ions combined with annealing at high temperature. The morphology, structure, spatial distribution and optical properties of the formed nanostructures have been investigated in detail. Our results clearly show that the thermal growth of TiO2 nanostructures in SiO2 substrate is significantly enhanced by presence of post Cu ion implantation, which depends strongly on the applied Cu ion fluence, as well as the annealing atmosphere. Due to the formation of Cu2O in the substrate, rutile TiO2 nanorods of large size have been well fabricated in the Ti and Cu sequentially implanted SiO2 after annealing in N2 atmosphere, in which Cu2O plays a role as a catalyst. Moreover, the sample with well-fabricated TiO2 nanorods exhibits a narrowed band gap, an enhanced optical absorption in visible region, and catalase-/peroxidase-like catalytic characteristics. Our findings provide an effective route to fabricate functional TiO2 nanorods in SiO2 via ion implantation.

Tuning Phase Composition of TiO2 by Sn(4+) Doping for Efficient Photocatalytic Hydrogen Generation.

PubMed

Wang, Fenglong; Ho, Jie Hui; Jiang, Yijiao; Amal, Rose

2015-11-04

The anatase-rutile mixed-phase photocatalysts have attracted extensive research interest because of the superior activity compared to their single phase counterparts. In this study, doping of Sn(4+) ions into the lattice of TiO2 facilitates the phase transformation from anatase to rutile at a lower temperature while maintaining the same crystal sizes compared to the conventional annealling approach. The mass ratios between anatase and rutile phases can be easily manipulated by varying the Sn-dopant content. Characterization results reveal that the Sn(4+) ions entered into the lattice of TiO2 by substituting some of the Ti(4+) ions and distributed evenly in the matrix of TiO2. The substitution induced the distortion of the lattice structure, which realized the phase transformation from anatase to rutile at a lower temperature and the close-contact phase junctions were consequently formed between anatase and rutile, accounting for the efficient charge separations. The mixed-phase catalysts prepared by doping Sn(4+) ions into the TiO2 exhibit superior activity for photocatalytic hydrogen generation in the presence of Au nanoparticles, relatively to their counterparts prepared by the conventional annealling at higher temperatures. The band allignment between anatase and rutile phases is established based on the valence band X-ray photoelectron spectra and diffuse reflectance spectra to understand the spatial charge separation process at the heterojunction between the two phases. The study provides a new route for the synthesis of mixed-phase TiO2 catalysts for photocatalytic applications and advances the understanding on the enhanced photocatalytic properties of anatase-rutile mixtures.

Genotoxic potential of TiO2 on bottlenose dolphin leukocytes.

PubMed

Bernardeschi, Margherita; Guidi, Patrizia; Scarcelli, Vittoria; Frenzilli, Giada; Nigro, Marco

2010-01-01

Titanium dioxide is extensively used in a variety of products, including industrial materials and cosmetics. Studies mainly performed on human cell lines and in vivo exposure on experimental animals have raised concern about the toxic effects of ultrafine titanium dioxide; however, scarce information is available about its impact on aquatic life. The aim of this article was to assess the genotoxic potential of TiO(2) (anatase and rutile) on bottlenose dolphin leukocytes. Blood samples were obtained from four male and one female specimens reared at the Adriatic SeaWorld "Oltremare" (Riccione, Italy). Leukocytes were isolated by the lyses procedure and in vitro exposed to TiO(2) in RPMI. Experimental solutions were sonicated immediately before dosing the cells. Three exposure times (4, 24 and 48 h) and three doses (20, 50 and 100 microg/ml) were tested. Genotoxicity was detected by the single-cell gel electrophoresis (or comet assay) at pH > or = 13, assessing single/double-strand breaks and alkali-labile sites. Cytotoxicity was also detected by the Trypan blue exclusion method. Results showed that both the crystalline forms of TiO(2) were genotoxic for bottlenose dolphin leukocytes, with a statistically significant increase of DNA fragmentation after exposure to 50 and 100 microg/ml for 24 and 48 h. Although preliminary, these are the first data regarding the genetic susceptibility of toothed cetaceans toward an "emerging" pollutant, such as TiO(2) particles.

Ab Initio Study of the Atomic Level Structure of the Rutile TiO2(110)-Titanium Nitride (TiN) Interface.

PubMed

Gutiérrez Moreno, José Julio; Nolan, Michael

2017-11-01

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 TiO 2 -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 TiO 2 (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 TiO 2 -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 TiO 2 region, which are preferentially located next to the interface region as well as the rotation of the rutile TiO 2 octahedra in the interface structure. The DFT+U TiO 2 electronic density of states (EDOS) shows localized Ti 3+ defect states forming in the midgap between the top edge of the valence and the bottom of the conduction band. We increase the complexity of our models by the introduction of nonstoichiometric compositions. Although the vacancy formation energies for Ti in TiN (E vac (Ti) ≥ 4.03 eV) or O in the oxide (E vac (O) ≥ 3.40 eV) are quite high relative to perfect TiO 2 -TiN, defects are known to form during the oxide growth and can therefore be present after TiO 2 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 TiO 2 introduces N 2p states localized between the top edge of the O 2p valence states and the midgap Ti 3+ 3d states, thus reducing the band gap in the TiO 2 region for the exchanged O/N interface EDOS. The outcomes of these simulations give us a most comprehensive

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

Improved metal-insulator-transition characteristics of ultrathin VO2 epitaxial films by optimized surface preparation of rutile TiO2 substrates

NASA Astrophysics Data System (ADS)

Martens, Koen; Aetukuri, Nagaphani; Jeong, Jaewoo; Samant, Mahesh G.; Parkin, Stuart S. P.

2014-02-01

Key to the growth of epitaxial, atomically thin films is the preparation of the substrates on which they are deposited. Here, we report the growth of atomically smooth, ultrathin films of VO2 (001), only ˜2 nm thick, which exhibit pronounced metal-insulator transitions, with a change in resistivity of ˜500 times, at a temperature that is close to that of films five times thicker. These films were prepared by pulsed laser deposition on single crystalline TiO2(001) substrates that were treated by dipping in acetone, HCl and HF in successive order, followed by an anneal at 700-750 °C in flowing oxygen. This pretreatment removes surface contaminants, TiO2 defects, and provides a terraced, atomically smooth surface.

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...

Elementary photocatalytic chemistry on TiO2 surfaces.

PubMed

Guo, Qing; Zhou, Chuanyao; Ma, Zhibo; Ren, Zefeng; Fan, Hongjun; Yang, Xueming

2016-07-07

Photocatalytic hydrogen production and pollutant degradation provided both great opportunities and challenges in the field of sustainable energy and environmental science. Over the past few decades, we have witnessed fast growing interest and efforts in developing new photocatalysts, improving catalytic efficiency and exploring the reaction mechanism at the atomic and molecular levels. Owing to its relatively high efficiency, nontoxicity, low cost and high stability, TiO2 becomes one of the most extensively investigated metal oxides in semiconductor photocatalysis. Fundamental studies on well characterized single crystals using ultrahigh vacuum based surface science techniques could provide key microscopic insight into the underlying mechanism of photocatalysis. In this review, we have summarized recent progress in the photocatalytic chemistry of hydrogen, water, oxygen, carbon monoxide, alcohols, aldehydes, ketones and carboxylic acids on TiO2 surfaces. We focused this review mainly on the rutile TiO2(110) surface, but some results on the rutile TiO2(011), anatase TiO2(101) and (001) surfaces are also discussed. These studies provided fundamental insights into surface photocatalysis as well as stimulated new investigations in this exciting field. At the end of this review, we have discussed how these studies can help us to develop new photocatalysis models.

Rutile TiO2 nanorods/MWCNT composites for enhanced simultaneous photocatalytic oxidation of organic dyes and reduction of metal ions

NASA Astrophysics Data System (ADS)

Mohamed, Hanan H.; Mohamed, Sahar K.

2018-01-01

This work aims to enhance the charge separation and the photocatalytic performance of TiO2 by combining two ways of modification synthesizing TiO2 Nanorods with modified morphology and anchoring on the surface of multi-walled carbon nanotubes (MWCNT). Simple hydrothermal method is performed to synthesize pure rutile TiO2 Nanorods/MWCNT composite. The photocatalytic activity of the nanocomposite is evaluated for the degradation of the organic dye Bromophenol blue (BPB). An enhancement in the photocatalytic activity is observed using TiO2 Nanorods/MWCNT composite as compared to pure TiO2 Nanorods. A synergism between the MWCNT and the TiO2 Nanorods is expected to suppress the recombination of photogenerated electron-hole pairs and hence the photocatalytic activity. Moreover, simultaneous degradation of BPB and reduction of Ag(I) is studied using TiO2 Nanorods/MWCNT nanocomposite. Enhancement in the photocatalytic degradation of BPB is observed in the presence of Ag(I) as compared to O2 as electron acceptor due to higher TiO2 electron transfer reaction rate to the Ag(I) ion as compared to its rate to the dissolved O2. The results provide an effective method for dual benefits for the wastewater purification from organic and inorganic pollutants.

Investigating the Unrevealed Photocatalytic Activity and Stability of Nanostructured Brookite TiO2 Film as an Environmental Photocatalyst.

PubMed

Choi, Mingi; Lim, Jonghun; Baek, Minki; Choi, Wonyong; Kim, Wooyul; Yong, Kijung

2017-05-17

Among three polymorphs of TiO 2 , the brookite is the least known phase in many aspects of its properties and photoactivities (especially comparable to anatase and rutile) because it is the rarest phase to be synthesized in the standard environment among the TiO 2 polymorphs. In this study, we address the unrevealed photocatalytic properties of pure brookite TiO 2 film as an environmental photocatalyst. Highly crystalline brookite nanostructures were synthesized on titanium foil using a well-designed hydrothermal reaction, without harmful precursors and selective etching of anatase, to afford pure brookite. The photocatalytic degradation of rhodamine B, tetramethylammonium chloride, and 4-chlorophenol on UV-illuminated pure brookite were investigated and compared with those on anatase and rutile TiO 2 . The present research explores the generation of OH radicals as main oxidants on brookite. In addition, tetramethylammonium, as a mobile OH radical indicator, was degraded over both pure anatase and brookite phases, but not rutile. The brookite phase showed much higher photoactivity among TiO 2 polymorphs, despite its smaller surface area compared with anatase. This result can be ascribed to the following properties of the brookite TiO 2 film: (i) the higher driving force with more negative flat-band potential, (ii) the efficient charge transfer kinetics with low resistance, and (iii) the generation of more hydroxyl radicals, including mobile OH radicals. The brookite-nanostructured TiO 2 electrode facilitates photocatalyst collection and recycling with excellent stability, and readily controls photocatalytic degradation rates with facile input of additional potential.

Nanometer Scale Confined Growth of Single-Crystalline Gold Nanowires via Photocatalytic Reduction.

PubMed

Lee, Seonhee; Bae, Changdeuck; Shin, Hyunjung

2018-06-20

Single-crystalline gold nanowires (Au NWs) are directly synthesized by the photocatalytic reduction of an aqueous HAuCl 4 solution inside high-aspect-ratio TiO 2 nanotubes (NTs). Crystalline TiO 2 (anatase) NTs are prepared by the template-assisted atomic layer deposition technique with a subsequent annealing. Under the irradiation of ultraviolet light, photoexcited electrons are formed on the surfaces of TiO 2 NTs and could reduce Au ions to create nuclei without using any surfactant, reducing agent, and/or seed. Once nucleation occurred, high-aspect-ratio Au NWs are grown inside the TiO 2 NTs in a diffusion-controlled manner. As the solution pH increased, the nucleation/growth rate decreased and twin-free (or not observed), single-crystalline Au NWs are formed. At a pH above 6, the nucleation/growth rates increased and Au nanoparticles are observed both inside and outside of the TiO 2 NTs. The confined nanoscale geometries of the interior of the TiO 2 NTs are found to play a key role in the controlled diffusion of Au species and in determining the crystal morphology of the resulting Au NWs.

Structure of a model TiO2 photocatalytic interface

NASA Astrophysics Data System (ADS)

Hussain, H.; Tocci, G.; Woolcot, T.; Torrelles, X.; Pang, C. L.; Humphrey, D. S.; Yim, C. M.; Grinter, D. C.; Cabailh, G.; Bikondoa, O.; Lindsay, R.; Zegenhagen, J.; Michaelides, A.; Thornton, G.

2017-04-01

The interaction of water with TiO2 is crucial to many of its practical applications, including photocatalytic water splitting. Following the first demonstration of this phenomenon 40 years ago there have been numerous studies of the rutile single-crystal TiO2(110) interface with water. This has provided an atomic-level understanding of the water-TiO2 interaction. However, nearly all of the previous studies of water/TiO2 interfaces involve water in the vapour phase. Here, we explore the interfacial structure between liquid water and a rutile TiO2(110) surface pre-characterized at the atomic level. Scanning tunnelling microscopy and surface X-ray diffraction are used to determine the structure, which is comprised of an ordered array of hydroxyl molecules with molecular water in the second layer. Static and dynamic density functional theory calculations suggest that a possible mechanism for formation of the hydroxyl overlayer involves the mixed adsorption of O2 and H2O on a partially defected surface. The quantitative structural properties derived here provide a basis with which to explore the atomistic properties and hence mechanisms involved in TiO2 photocatalysis.

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.

Origin of colossal dielectric permittivity of rutile Ti₀.₉In₀.₀₅Nb₀.₀₅O₂: single crystal and polycrystalline.

PubMed

Song, Yongli; Wang, Xianjie; Sui, Yu; Liu, Ziyi; Zhang, Yu; Zhan, Hongsheng; Song, Bingqian; Liu, Zhiguo; Lv, Zhe; Tao, Lei; Tang, Jinke

2016-02-12

In this paper, we investigated the dielectric properties of (In + Nb) co-doped rutile TiO2 single crystal and polycrystalline ceramics. Both of them showed colossal, up to 10(4), dielectric permittivity at room temperature. The single crystal sample showed one dielectric relaxation process with a large dielectric loss. The voltage-dependence of dielectric permittivity and the impedance spectrum suggest that the high dielectric permittivity of single crystal originated from the surface barrier layer capacitor (SBLC). The impedance spectroscopy at different temperature confirmed that the (In + Nb) co-doped rutile TiO2 polycrystalline ceramic had semiconductor grains and insulating grain boundaries, and that the activation energies were calculated to be 0.052 eV and 0.35 eV for grain and grain boundary, respectively. The dielectric behavior and impedance spectrum of the polycrystalline ceramic sample indicated that the internal barrier layer capacitor (IBLC) mode made a major contribution to the high ceramic dielectric permittivity, instead of the electron-pinned defect-dipoles.

Toward Eco-Friendly and Highly Efficient Solar Water Splitting Using In2S3/Anatase/Rutile TiO2 Dual-Staggered-Heterojunction Nanodendrite Array Photoanode.

PubMed

Yang, Jih-Sheng; Wu, Jih-Jen

2018-01-31

The TiO 2 -based heterojunction nanodendrite (ND) array composed of anatase nanoparticles (ANPs) on the surface of the rutile ND (RND) array is selected as the model photoanode to demonstrate the strategies toward eco-friendly and efficient solar water splitting using neutral electrolyte and seawater. Compared with the performances in alkaline electrolyte, a non-negligible potential drop across the electrolyte as well as impeded charge injection and charge separation is monitored in the ANP/RND array photoanode with neutral electrolyte, which are, respectively, ascribed to the series resistance of neutral electrolyte, the fundamentally pH-dependent water oxidation mechanism on TiO 2 surface, as well as the less band bending at the interface of TiO 2 and neutral electrolyte. Accordingly, a TiO 2 -based dual-staggered heterojunction ND array photoanode is further designed in this work to overcome the issue of less band bending with the neutral electrolyte. The improvement of charge separation efficiency is realized by the deposition of a transparent In 2 S 3 layer on the ANP/RND array photoanode for constructing additional staggered heterojunction. Under illumination of AM 1.5G (100 mW cm -2 ), the improved photocurrent densities acquired both in neutral electrolyte and seawater at 1.23 V vs reversible hydrogen electrode (RHE), which approach the theoretical value for rutile TiO 2 , are demonstrated in the dual-staggered-heterojunction ND array photoanode. Faradaic efficiencies of ∼95 and ∼32% for solar water oxidation in neutral electrolyte and solar seawater oxidation for 2 h are acquired at 1.23 V vs RHE, respectively.

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.

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.

Tuning TiO2 nanoparticle morphology in graphene-TiO2 hybrids by graphene surface modification

NASA Astrophysics Data System (ADS)

Sordello, Fabrizio; Zeb, Gul; Hu, Kaiwen; Calza, Paola; Minero, Claudio; Szkopek, Thomas; Cerruti, Marta

2014-05-01

We report the hydrothermal synthesis of graphene (GNP)-TiO2 nanoparticle (NP) hybrids using COOH and NH2 functionalized GNP as a shape controller. Anatase was the only TiO2 crystalline phase nucleated on the functionalized GNP, whereas traces of rutile were detected on unfunctionalized GNP. X-Ray Photoelectron spectroscopy (XPS) showed C-Ti bonds on all hybrids, thus confirming heterogeneous nucleation. GNP functionalization induced the nucleation of TiO2 NPs with specific shapes and crystalline facets exposed. COOH functionalization directed the synthesis of anatase truncated bipyramids, bonded to graphene sheets via the {101} facets, while NH2 functionalization induced the formation of belted truncated bipyramids, bonded to graphene via the {100} facets. Belted truncated bipyramids formed on unfunctionalized GNP too, however the NPs were more irregular and rounded. These effects were ascribed to pH variations in the proximity of the functionalized GNP sheets, due to the high density of COOH or NH2 groups. Because of the different reactivity of anatase {100} and {101} crystalline facets, we hypothesize that the hybrid materials will behave differently as photocatalysts, and that the COOH-GNP-TiO2 hybrids will be better photocatalysts for water splitting and H2 production.We report the hydrothermal synthesis of graphene (GNP)-TiO2 nanoparticle (NP) hybrids using COOH and NH2 functionalized GNP as a shape controller. Anatase was the only TiO2 crystalline phase nucleated on the functionalized GNP, whereas traces of rutile were detected on unfunctionalized GNP. X-Ray Photoelectron spectroscopy (XPS) showed C-Ti bonds on all hybrids, thus confirming heterogeneous nucleation. GNP functionalization induced the nucleation of TiO2 NPs with specific shapes and crystalline facets exposed. COOH functionalization directed the synthesis of anatase truncated bipyramids, bonded to graphene sheets via the {101} facets, while NH2 functionalization induced the formation of belted

Structure of a model TiO2 photocatalytic interface.

PubMed

Hussain, H; Tocci, G; Woolcot, T; Torrelles, X; Pang, C L; Humphrey, D S; Yim, C M; Grinter, D C; Cabailh, G; Bikondoa, O; Lindsay, R; Zegenhagen, J; Michaelides, A; Thornton, G

2017-04-01

The interaction of water with TiO 2 is crucial to many of its practical applications, including photocatalytic water splitting. Following the first demonstration of this phenomenon 40 years ago there have been numerous studies of the rutile single-crystal TiO 2 (110) interface with water. This has provided an atomic-level understanding of the water-TiO 2 interaction. However, nearly all of the previous studies of water/TiO 2 interfaces involve water in the vapour phase. Here, we explore the interfacial structure between liquid water and a rutile TiO 2 (110) surface pre-characterized at the atomic level. Scanning tunnelling microscopy and surface X-ray diffraction are used to determine the structure, which is comprised of an ordered array of hydroxyl molecules with molecular water in the second layer. Static and dynamic density functional theory calculations suggest that a possible mechanism for formation of the hydroxyl overlayer involves the mixed adsorption of O 2 and H 2 O on a partially defected surface. The quantitative structural properties derived here provide a basis with which to explore the atomistic properties and hence mechanisms involved in TiO 2 photocatalysis.

Low-energy ion irradiation in HiPIMS to enable anatase TiO2 selective growth

NASA Astrophysics Data System (ADS)

Cemin, Felipe; Tsukamoto, Makoto; Keraudy, Julien; Antunes, Vinícius Gabriel; Helmersson, Ulf; Alvarez, Fernando; Minea, Tiberiu; Lundin, Daniel

2018-06-01

High power impulse magnetron sputtering (HiPIMS) has already demonstrated great potential for synthesizing the high-energy crystalline phase of titanium dioxide (rutile TiO2) due to large quantities of highly energetic ions present in the discharge. In this work, it is shown that the metastable anatase phase can also be obtained by HiPIMS. The required deposition conditions have been identified by systematically studying the phase formation, microstructure and chemical composition as a function of mode of target operation as well as of substrate temperature, working pressure, and peak current density. It is found that films deposited in the metal and transition modes are predominantly amorphous and contain substoichiometric TiO x compounds, while in compound mode they are well-crystallized and present only O2‑ ions bound to Ti4+, i.e. pure TiO2. Anatase TiO2 films are obtained for working pressures between 1 and 2 Pa, a peak current density of ~1 A cm‑2 and deposition temperatures lower than 300 °C. Rutile is favored at lower pressures (<1 Pa) and higher peak current densities (>2 A cm‑2), while amorphous films are obtained at higher pressures (5 Pa). Microstructural characterization of selected films is also presented.

Low temperature synthesis of polyaniline-crystalline TiO2-halloysite composite nanotubes with enhanced visible light photocatalytic activity.

PubMed

Li, Cuiping; Wang, Jie; Guo, Hong; Ding, Shujiang

2015-11-15

A series of one-dimensional polyaniline-crystalline TiO2-halloysite composite nanotubes with different mass ratio of polyaniline to TiO2 are facilely prepared by employing the low-temperature synthesis of crystalline TiO2 on halloysite nanotubes. The halloysite nanotubes can adsorb TiO2/polyaniline precursors and induce TiO2 nanocrystals/polyaniline to grow on the support in situ simultaneously. By simply adjusting the acidity of reaction system, PANI-crystalline TiO2-HA composite nanotubes composed of anatase, a mixed phase TiO2 and different PANI redox state are obtained. The XRD and UV-vis results show that the surface polyaniline sensitization has no effect on the crystalline structure of halloysite and TiO2 and the light response of TiO2 is extended to visible-light regions. Photocatalysis test results reveal the photocatalytic activity will be affected by the pH value and the volume ratio of ANI to TTIP. The highest photocatalytic activity is achieved with the composite photocatalysts prepared at pH 0.5 and 1% volume ratio of ANI and TTIP owing to the sensitizing effect of polyaniline and the charge transfer from the photoexcited PANI sensitizer to TiO2. Moreover, the PANI-TiO2-HA composite nanotubes synthesized by one-step at pH 0.5 with 1% volume ratio of ANI to TTIP exhibit higher visible light photocatalytic activity than those synthesized by the two-step. Heterogeneous PANI-TiO2-HA composite nanotubes prepared at pH 0.5 exhibit a higher degradation activity than that prepared at pH 1.5. The redoped experiment proves that the PANI redox state plays the main contribution to the enhanced visible light catalytic degradation efficiency of PANI-TiO2-HA prepared at pH 0.5. Furthermore, the heterogeneous PANI-crystalline TiO2-HA nanotubes have good photocatalytic stability and can be reused four times with only gradual loss of activity under visible light irradiation. Copyright © 2015 Elsevier Inc. All rights reserved.

Electronic structures of rutile (011)(2 × 1) surfaces: A many-body perturbation theory study.

PubMed

Liu, Guokui; Chen, Tingwei; Liu, Xiaobiao; Jin, Fan; Yuan, Shiling; Ma, Yuchen

2017-03-28

Using the GW method within many-body perturbation theory, we investigate the electronic properties of the rutile (011) surfaces with different reconstruction patterns. We find that keeping the Ti:O ratio on the reconstructedsurface to 1:2 enlarges the bandgap of the rutile (011) surface to ca. 4.0 eV. Increasing the content of O atoms in the surface can turn rutile into a semi-metal. For some surfaces, it is important to apply self-consistent GW calculation to get the correct charge distributions for the frontier orbitals, which are relevant to the photocatalytic behavior of TiO 2 .

Semiconductor-to-metal transition in rutile TiO 2 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 TiO 2 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 TiO 2 transitioning to metallic behavior under tensile strain. The transition reverses when strain is removed. Valence band XPS spectramore » show that 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

Improved light-induced cell detachment on rutile TiO₂ nanodot films.

PubMed

Cheng, Kui; Sun, Yu; Wan, Hongping; Wang, Xiaozhao; Weng, Wenjian; Lin, Jun; Wang, Huiming

2015-10-01

Anatase TiO2 nanodot films have been found to be able to release cells under light illumination with excellent efficiency and safety. In the present study, we investigated the effects of rutile contents in TiO2 nanodot films on such light induced cell detachment behavior. The results showed that TiO2 nanodot films with different contents of rutile phase have been prepared successfully. The content of rutile phase increased with the increase in calcination temperature. All films possessed good cell adhesion but there was a decrease in cell proliferation with the increasing content of rutile phase. Single cell detachment assay showed that the films with high rutile contents (calcined at 900°C and 1100°C) showed better cell detachment performance. That was ascribed to the changes of the secondary structure of extracellular proteins adsorbed on the nanodot surface after ultraviolet (365 nm, UV365) illumination. In addition, cell sheets detached through UV365 illumination maintained high activity and could be further used in tissue engineering. The present work showed that the existence of rutile phase is helpful in cell detachment behavior and it could be utilized to optimize light-induced cell detachment behavior. This work discovers that the presence of rutile phase in TiO2 nanodot films could improve the light-induced cell detachment behavior, although rutile phase is inferior to anatase phase on light induced superhydrophilicity. That strongly supported that the behaviors of adsorbed proteins are crucial in acquiring cell sheet with light illumination. In fact, the state and behavior of adsorbed protein greatly affect the interaction between biomaterials and living cells. Therefore, we consider this work is not only important in harvesting cells or cell sheets through light illumination, but also helpful in further understanding of interaction between biomaterials and cells. Copyright © 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

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 TiO 2 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.

The role of high oxygen vacancy concentration on modification of surface properties and H2S adsorption on the rutile TiO2 (110)

NASA Astrophysics Data System (ADS)

Wei, Shiqian; Wang, Fang; Dan, Meng; Zeng, Kaiyue; Zhou, Ying

2017-11-01

In this work, spin-polarized DFT + U method has been employed to investigate adsorption properties of H2S on the rutile TiO2 (110) surface with a high coverage of bridging oxygen vacancies (BOVs). The influence of different BOV coverage (θ-BOVs) on the surface electronic structure is examined. Defected states increase within the band gap with θ-BOVs increasing from 1/8 to 4/8 monolayer (ML). The high defected surface with θ-BOVs = 4/8 ML is determined to have a desired band structure and noticeable visible light response. In addition, H2S adsorption behaviors are noticeably affected by different H2S coverage (θ-H2S). Particularly, it is found molecular adsorption at θ-H2S ≤ 1/8 ML and dissociative adsorption at the higher θ-H2S. The maximization of spontaneous dissociation of H2S can be realized when the BOVs are all covered by H2S molecules. This work gains mechanistic insights into BOVs in tuning the surface properties and provides a guide for the effective utilization of the active surface sites on the rutile TiO2 (110) in the field of H2S splitting.

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).

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

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

Kim, Boseong; Li, Zhenjun; Kay, Bruce D.

2014-05-08

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

Adsorption of small hydrocarbons on rutile TiO 2(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 C 1–C 4) on rutile TiO 2(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 Ti 5c sites. Similar to previous studiesmore » 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 Ti 5c sites increase linearly with the chain length. The absolute saturation coverages of each hydrocarbon on Ti 5c sites were also determined. The saturation coverage of CH 4, is found to be ~ 2/3 monolayer (ML). The saturation coverages of C 2–C 4 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

Rutile solubility and titanium coordination in silicate melts

NASA Astrophysics Data System (ADS)

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

1985-11-01

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

Towards TiO2 nanotubes modified by WO3 species: influence of ex situ crystallization of precursor on the photocatalytic activities of WO3/TiO2 composites

NASA Astrophysics Data System (ADS)

Sun, Hui; Dong, Bohua; Su, Ge; Gao, Rongjie; Liu, Wei; Song, Liang; Cao, Lixin

2015-09-01

TiO2 nanotubes (TNT) crystallized at different temperatures were loaded with WO3 hydrate through the reaction between (NH4)6W7O24·6H2O and an aqueous solution of HCl. The photocatalytic activities of nanocomposites firstly increase and then decrease as a function of the crystallized temperature of the TNT precursor. The structural, morphologic and optical properties of WO3/TiO2 nanocomposites were also investigated in this study. The samples, initially anatase titania (573 K-773 K), presented phase transition to rutile titania at 873 K. With the crystallized temperature increasing, an evolution of samples morphology changing from nanotube-like structure to nanorod-like structure was observed. Meanwhile, the absorption edge of samples exhibited a red shift, and correspondingly their band gap decreased. Consistent with x-ray diffraction diffractograms, the existence of rutile titania as an impurity in the precursor TNT, crystallized at higher than 873 K, depressed photocatalytic activity evidently. As a result, the degradation rate of methyl orange (MO) increased with the samples crystallinity firstly, and then reduced due to the appearance of rutile titania. In our experimental conditions, the optimal photocatalytic activity was achieved for the sample crystalized at 773 K. Its degradation rate could reach 98.76% after 90 min UV light irradiation.

Spontaneous Synthesis of Highly Crystalline TiO2 Compact/Mesoporous Stacked Films by a Low-Temperature Steam-Annealing Method for Efficient Perovskite Solar Cells.

PubMed

Sanehira, Yoshitaka; Numata, Youhei; Ikegami, Masashi; Miyasaka, Tsutomu

2018-05-23

Highly crystalline TiO 2 nanostructured films were synthesized by a simple steam treatment of a TiCl 4 precursor film under a saturated water vapor atmosphere at 125 °C, here referred to as the steam-annealing method. In a single TiO 2 film preparation step, a bilayer structure comprising a compact bottom layer and a mesoporous surface layer was formed. The mesoporous layer was occupied by bipyramidal nanoparticles, with a composite phase of anatase and brookite crystals. Despite the low-temperature treatment process, the crystallinity of the TiO 2 film was high, comparable with that of the TiO 2 film sintered at 500 °C. The compact double-layered TiO 2 film was applied to perovskite solar cells (PSCs) as an electron-collecting layer. The PSC exhibited a maximum power conversion efficiency (PCE) of 18.9% with an open-circuit voltage ( V OC ) of 1.15 V. The PCE and V OC were higher than those of PSCs using a TiO 2 film formed by 500 °C sintering.

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...

Benzimidazole derivative vs. different phases of TiO2-physico-chemical approach.

PubMed

Karunakaran, C; Jayabharathi, J; Jayamoorthy, K

2013-10-01

1-Benzyl-2-phenyl-1H-benzo[d]imidazole (BPBI) has been synthesized by simple steps and characterized by spectral studies. Absorption and fluorescence spectral studies have been employed to investigate the interaction of BPBI with the anatase, hombikat, P25 and rutile phases of TiO2. The emission of the BPBI is efficiently quenched by anatase, hombikat and P25 TiO2 nanoparticles owing to charge injection from the excited singlet state of BPBI to the conduction band of the TiO2 nanoparticles. Surprisingly, rutile phase enhances the fluorescence which is likely due to lowering of LUMO and HOMO levels of the ligand on ducking of the benzimidazole moiety of the BPBI molecule into the void space of rutile TiO2. Electron injection from photoexcited BPBI to the TiO2 conduction band (S*→S(+)+e(-)(CB)) is likely to enhance the fluorescence. Copyright © 2013 Elsevier B.V. All rights reserved.

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.

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

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

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 rowsmore » 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)« less

Adsorption of small hydrocarbons on rutile TiO2(110)

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

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

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 tomore » 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.« less

Graphene-Rich Wrapped Petal-Like Rutile TiO2 tuned by Carbon Dots for High-Performance Sodium Storage.

PubMed

Zhang, Yan; Foster, Christopher W; Banks, Craig E; Shao, Lidong; Hou, Hongshuai; Zou, Guoqiang; Chen, Jun; Huang, Zhaodong; Ji, Xiaobo

2016-11-01

Carbon dots inducing petal-like rutile TiO 2 wrapped by ultrathin graphene-rich layers are proposed to fabricate superior anodes for sodium-ion batteries, featuring high-rate capabilities and long-term cyclelife, benefiting from promoted electron transport and a shortened Na + diffusion length. High capacities of 144.4 mA h g -1 (at 837.5 mA g -1 ) after 1100 cycles and 74.6 mA h g -1 (at 3350 mA g -1 ) after 4000 cycles are delivered outstandingly. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Facet-specific interaction between methanol and TiO2 probed by sum-frequency vibrational spectroscopy.

PubMed

Yang, Deheng; Li, Yadong; Liu, Xinyi; Cao, Yue; Gao, Yi; Shen, Y Ron; Liu, Wei-Tao

2018-04-24

The facet-specific interaction between molecules and crystalline catalysts, such as titanium dioxides (TiO 2 ), has attracted much attention due to possible facet-dependent reactivity. Using surface-sensitive sum-frequency vibrational spectroscopy, we have studied how methanol interacts with different common facets of crystalline TiO 2 , including rutile(110), (001), (100), and anatase(101), under ambient temperature and pressure. We found that methanol adsorbs predominantly in the molecular form on all of the four surfaces, while spontaneous dissociation into methoxy occurs preferentially when these surfaces become defective. Extraction of Fermi resonance coupling between stretch and bending modes of the methyl group in analyzing adsorbed methanol spectra allows determination of the methanol adsorption isotherm. The isotherms obtained for the four surfaces are nearly the same, yielding two adsorbed Gibbs free energies associated with two different adsorption configurations singled out by ab initio calculations. They are ( i ) ∼-20 kJ/mol for methanol with its oxygen attached to a low-coordinated surface titanium, and ( ii ) ∼-5 kJ/mol for methanol hydrogen-bonded to a surface oxygen and a neighboring methanol molecule. Despite similar adsorption energetics, the Fermi resonance coupling strength for adsorbed methanol appears to depend sensitively on the surface facet and coverage.

Oxygen vacancy and hole conduction in amorphous TiO2.

PubMed

Pham, Hieu H; Wang, Lin-Wang

2015-01-07

The amorphous titanium dioxide (a-TiO2) has drawn attention recently due to the finding that it holds promise for coating conventional photoelectrodes for corrosion protection while still allowing the holes to transport to the surface. The mechanism of hole conductivity at a level much higher than the edge of the valence band is still a mystery. In this work, an amorphous TiO2 model is obtained from molecular dynamics employing the "melt-and-quench" technique. The electronic properties, polaronic states and the hole conduction mechanism in amorphous structure were investigated by means of density functional theory with Hubbard's energy correction (DFT + U) and compared to those in crystalline (rutile) TiO2. The formation energy of the oxygen vacancy was found to reduce significantly (by a few eV) upon amorphization. Our theoretical study suggested that the oxygen vacancies and their defect states provide hopping channels, which are comparable to experimental observations and could be responsible for hole conduction in the "leaky" TiO2 recently discovered for the photochemical water-splitting applications.

Comparison of the Photodesorption Activities of cis-Butene, trans-Butene and Isobutene on the Rutile TiO 2(110) Surface

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

Henderson, Michael A.

2013-10-17

The chemical and photochemical properties of three butene molecules (cis-butene, trans-butene and isobutene) were explored on the clean rutile TiO 2(110) surface using temperature programmed desorption (TPD) and photon simulated desorption (PSD). At the low coverage limit, trans-butene was the most strongly bound butene on the TiO 2(110) surface, desorbing at ~ 210 K, however increased intermolecular repulsions between trans-butene molecules at higher coverage diminished its binding. Both cis-butene and isobutene saturated the first layer on TiO 2(110) at a coverage of ~0.50 ML in a single TPD feature at 184 and 192 K, respectively. In contrast, the maximum coveragemore » that trans-butene could achieve in its 210 K peak was ~1/3 ML, with higher coverages resulting a low temperature desorption at ~137 K. Coverages of these molecules above 0.50 ML resulted in population of second layer and multilayer states. The instability of trans-butene at a coverage of 0.5 ML on the surface was linked to the inversion center in its symmetry. In the absence of coadsorbed oxygen, the primary photochemical pathway of each butene molecule on TiO 2(110) was photodesorption. The photoactivities of these molecules on TiO 2(110) at an initial coverage of 0.50 ML followed the trend: isobutene > cis-butene > trans-butene. In contrast, the photoactivities of low coverages of cis-butene and trans-butene exceeded those measured at 0.50 ML. These data suggest that intermolecular interactions (repulsions) play a significant role in diminishing the photoactivities of weakly bound molecules on TiO 2 photocatalysts. Work reported here was supported by the U.S. Department of Energy, Office of Basic Energy Science, Division of Chemical Sciences, Geosciences, and Biosciences, and performed in the Williams R. Wiley Environmental Molecular Science Laboratory (EMSL), a Department of Energy user facility funded by the Office of Biological and Environmental Research. Pacific Northwest National

Toxicity assessment of anatase and rutile titanium dioxide nanoparticles: The role of degradation in different pH conditions and light exposure.

PubMed

De Matteis, Valeria; Cascione, Mariafrancesca; Brunetti, Virgilio; Toma, Chiara Cristina; Rinaldi, Rosaria

2016-12-01

Titanium dioxide nanoparticles (TiO 2 NPs), in the two crystalline forms, rutile and anatase, have been widely used in many industrial fields, especially in cosmetics. Therefore, a lot of details about their safety issues have been discussed by the scientific community. Many studies have led to a general agreement about TiO 2 NPs toxicity, in particular for anatase form, but no mechanism details have been proved yet. In this study, data confirm the different toxic potential of rutile and anatase TiO 2 NPs in two cell lines up to 5nM nanoparticles concentration. Moreover, we evaluated the role of titanium ions released by TiO 2 NPs in different conditions, at pH=4.5 (the typical lysosomal compartment pH) and at pH=5.5 (the skin physiological pH) in conditions of darkness and light, to mimic the dermal exposure of cosmetics. Anatase nanoparticles were proner to degradation both in the acidic conditions and at skin pH. Our study demonstrates that pH and sunlight are dominant factors to induce oxidative stress, TiO 2 NPs degradation and toxicity effects. Copyright © 2016 Elsevier B.V. All rights reserved.

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

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

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

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 formedmore » 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) .« less

Interaction of Formaldehyde with the Rutile TiO 2 (110) Surface: A Combined Experimental and Theoretical Study

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

Yu, Xiaojuan; Zhang, Zhenrong; Yang, Chengwu

2016-06-16

The adsorption and reaction of formaldehyde (CH 2O) on the oxidized rutile TiO 2(110) surface were studied by temperature programmed desorption (TPD), scanning tunneling microscopy (STM), infrared reflection-absorption spectroscopy (IRRAS) and density functional theory (DFT) calculations. The experimental and theoretical data reveal the presence of various species depending on the temperature and coverage. After formaldehyde adsorption on TiO 2(110) at 65 K, the multilayer CH 2O was detected, which desorbs completely upon heating to 120 K. The isolated CH 2O monomer was identified after submonolayer adsorption at low temperatures (45-65 K), in which CH 2O is bound to the surfacemore » Ti5c sites via σ-donation and adopts a tilted geometry. With heating to higher temperatures the CH 2O monomers remain stable up to 70 K and then undergo coupling reactions to form paraformaldehyde (polyoxymethylene, POM) at the Ti 5c rows. The POM chain is oriented primarily along the [001] direction in a slightly disordered configuration. POM becomes the predominant species at 120 K and is decomposed releasing CH 2O at about 250 K. In addition, dioxymethylene (DOM) was detected as minority species formed via reaction of Ti 5c-bound CH 2O with both neighboring O 2c along the [1-10] direction and oxygen adatoms (Oad) at Ti 5c sites along [001] on the oxidized TiO 2(110) surface.« less

Surface Structure of TiO2 Rutile (011) Exposed to Liquid Water

PubMed Central

2017-01-01

The rutile TiO2(011) surface exhibits a (2 × 1) reconstruction when prepared by standard techniques in ultrahigh vacuum (UHV). Here we report that a restructuring occurs upon exposing the surface to liquid water at room temperature. The experiment was performed in a dedicated UHV system, equipped for direct and clean transfer of samples between UHV and liquid environment. After exposure to liquid water, an overlayer with a (2 × 1) symmetry was observed containing two dissociated water molecules per unit cell. The two OH groups yield an apparent “c(2 × 1)” symmetry in scanning tunneling microscopy (STM) images. On the basis of STM analysis and density functional theory (DFT) calculations, this overlayer is attributed to dissociated water on top of the unreconstructed (1 × 1) surface. Investigation of possible adsorption structures and analysis of the domain boundaries in this structure provide strong evidence that the original (2 × 1) reconstruction is lifted. Unlike the (2 × 1) reconstruction, the (1 × 1) surface has an appropriate density and symmetry of adsorption sites. The possibility of contaminant-induced restructuring was excluded based on X-ray photoelectron spectroscopy (XPS) and low-energy He+ ion scattering (LEIS) measurements. PMID:29285204

Pr3+ doped biphasic TiO2 (rutile-brookite) nanorod arrays grown on activated carbon fibers: Hydrothermal synthesis and photocatalytic properties

NASA Astrophysics Data System (ADS)

Li, Min; Zhang, Xiaomei; Liu, Ying; Yang, Yi

2018-05-01

Praseodymium-doped biphasic TiO2 (rutile-brookite) nanorod arrays (Pr-TiO2 NRAs) were successfully prepared via a two-step hydrothermal reaction on activated carbon fibers (ACFs) which pre-coated with TiO2 nanoparticles at first step. The bicrystalline arrays grown on ACFs are primarily constructed by the well-aligned TiO2 nanorods growing along [0 0 1] direction, which were indicated by the results of SEM and XRD. The nanorods are uniform in diameter and length with about 250 nm and 2.5 μm. The composite photocatalyst with high specific surface area and well-aligned nanostructure are beneficial to enhance the adsorption capacity and even help to suppress electron-hole recombination effectively, which consequently revealed much better (2 times) catalytic performance than that of commercially available P25 TiO2 on methylene blue(MB) photodegradation. In addition, the existence of praseodymium in TiO2 gives rise to shift of absorption edge towards long wavelength, which was indicated by the results of UV-vis DRS. Photodegradation results reveal that Pr-doping significantly improves the activity of TiO2, which was 20% higher than that of undoped TiO2 NRAs for the photodegradation of MB in aqueous medium under visible light irradiation. Meanwhile, the doped amount of Pr had a tiny influence on the photocatalytic performance of the composites. In our experiment, 3% Pr-doped molar concentration was proven to be the relatively optimal dopant concentration for the doping of TiO2 NRAs. Moreover, the photocatalyst grown on ACFs substrates is favorable to reuse and photodegradation rate kept on 76% even after 4 times of reuse.

Oxygen vacancy induced phase formation and room temperature ferromagnetism in undoped and Co-doped TiO2 thin films

NASA Astrophysics Data System (ADS)

Mohanty, P.; Mishra, N. C.; Choudhary, R. J.; Banerjee, A.; Shripathi, T.; Lalla, N. P.; Annapoorni, S.; Rath, Chandana

2012-08-01

TiO2 and Co-doped TiO2 (CTO) thin films deposited at various oxygen partial pressures by pulsed laser deposition exhibit room temperature ferromagnetism (RTFM) independent of their phase. Films deposited at 0.1 mTorr oxygen partial pressure show a complete rutile phase confirmed from glancing angle x-ray diffraction and Raman spectroscopy. At the highest oxygen partial pressure, i.e. 300 mTorr, although the TiO2 film shows a complete anatase phase, a small peak corresponding to the rutile phase along with the anatase phase is identified in the case of CTO film. An increase in O to Ti/(Ti+Co) ratio with increase in oxygen partial pressure is observed from Rutherford backscattering spectroscopy. It is revealed from x-ray photoelectron spectroscopy (XPS) that oxygen vacancies are found to be higher in the CTO film than TiO2, while the valency of cobalt remains in the +2 state. Therefore, the CTO film deposited at 300 mTorr does not show a complete anatase phase unlike the TiO2 film deposited at the same partial pressure. We conclude that RTFM in both films is not due to impurities/contaminants, as confirmed from XPS depth profiling and cross-sectional transmission electron microscopy (TEM), but due to oxygen vacancies. The magnitude of moment, however, depends not only on the phase of TiO2 but also on the crystallinity of the films.

First-principles real-space study of electronic and optical excitations in rutile TiO 2 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 (G 0W 0) and ΔSCF method for NCs up to 24 and 64 TiO 2 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 upmore » to 64 TiO 2 units. For a NC containing only 2 TiO 2 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 G 0W 0 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 G 0W 0 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) TiO 2 NCs of subnanometer size.« less

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.

Role of hydrothermal temperature on crystallinity, photoluminescence, photocatalytic and gas sensing properties of TiO2 nanoparticles

NASA Astrophysics Data System (ADS)

Malligavathy, M.; Iyyapushpam, S.; Nishanthi, S. T.; Padiyan, D. Pathinettam

2018-04-01

TiO2 nanoparticles were synthesised by hydrothermal method. The degree of crystallinity and phase purity were confirmed from the Raman spectra and X-ray diffraction. By increasing the hydrothermal temperature, crystallinity and AC conductivity of the TiO2 nanoparticles increase. Nitrogen adsorption-desorption measurements confirmed that the samples were mesoporous with an average pore diameter of 4.4-7.45 nm. Photocatalytic activity of TiO2 nanoparticles was evaluated and the sample hydrothermally treated at 160°C has the highest photocatalytic activity. In gas sensing measurements, sensitivity increases as a function of concentration and the response to ethanol vapour was better compared to other gases for the sample synthesised at 160°C.

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

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

2016-03-01

Detailed EPR investigations on as-grown and annealed TiO 2 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: Ti 3+ , O - , adsorbed oxygen (O 2 - ) and oxygen vacancies. On the other hand, in as-grown rutile samples, there were observed EPR lines due to adsorbed oxygen (O 2 - ) and the Fe 3+ ions in both Ti 4+ 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 O 2 - ions enabling determination of their g-values with higher precision, as well as observation of hyperfine sextets due to Mn 2+ and Mn 4+ ions in anatase.

Investigation of energy band alignments and interfacial properties of rutile NMO2/TiO2 (NM = Ru, Rh, Os, and Ir) by first-principles calculations.

PubMed

Yang, Chen; Zhao, Zong-Yan

2017-11-08

In the field of photocatalysis, constructing hetero-structures is an efficient strategy to improve quantum efficiency. However, a lattice mismatch often induces unfavorable interfacial states that can act as recombination centers for photo-generated electron-hole pairs. If the hetero-structure's components have the same crystal structure, this disadvantage can be easily avoided. Conversely, in the process of loading a noble metal co-catalyst onto the TiO 2 surface, a transition layer of noble metal oxides is often formed between the TiO 2 layer and the noble metal layer. In this article, interfacial properties of hetero-structures composed of a noble metal dioxide and TiO 2 with a rutile crystal structure have been systematically investigated using first-principles calculations. In particular, the Schottky barrier height, band bending, and energy band alignments are studied to provide evidence for practical applications. In all cases, no interfacial states exist in the forbidden band of TiO 2 , and the interfacial formation energy is very small. A strong internal electric field generated by interfacial electron transfer leads to an efficient separation of photo-generated carriers and band bending. Because of the differences in the atomic properties of the components, RuO 2 /TiO 2 and OsO 2 /TiO 2 hetero-structures demonstrate band dividing, while RhO 2 /TiO 2 and IrO 2 /TiO 2 hetero-structures have a pseudo-gap near the Fermi energy level. Furthermore, NMO 2 /TiO 2 hetero-structures show upward band bending. Conversely, RuO 2 /TiO 2 and OsO 2 /TiO 2 hetero-structures present a relatively strong infrared light absorption, while RhO 2 /TiO 2 and IrO 2 /TiO 2 hetero-structures show an obvious absorption edge in the visible light region. Overall, considering all aspects of their properties, RuO 2 /TiO 2 and OsO 2 /TiO 2 hetero-structures are more suitable than others for improving the photocatalytic performance of TiO 2 . These findings will provide useful information

Large bandgap narrowing in rutile TiO2 aimed towards visible light applications and its correlation with vacancy-type defects history and transformation

NASA Astrophysics Data System (ADS)

Nair, Radhika V.; Gayathri, P. K.; Siva Gummaluri, Venkata; Nambissan, P. M. G.; Vijayan, C.

2018-01-01

Extension of photoactivity of TiO2 to the visible region is achievable via effective control over the intrinsic defects such as oxygen and Ti vacancies, which has several applications in visible photocatalysis and sensing. We present here the first observation of an apparent bandgap narrowing and bandgap tuning effect due to vacancy cluster transformation in rutile TiO2 structures to 1.84 eV from the bulk bandgap of 3 eV. A gradual transformation of divacancies (V Ti-O) to tri vacancies ({{V}Ti-O-T{{i-}}} ) achieved through a controlled solvothermal scheme appears to result in an apparent narrowing bandgap and tunability, as supported by positron annihilation lifetime and electron paramagnetic resonance spectroscopy measurements. Visible photocatalytic activity of the samples is demonstrated in terms of photodegradation of rhodamine B dye molecules.

Morphology and crystalline phase study of electrospun TiO2 SiO2 nanofibres

NASA Astrophysics Data System (ADS)

Ding, Bin; Kim, Hakyong; Kim, Chulki; Khil, Myungseob; Park, Soojin

2003-05-01

Nanofibres of TiO2-SiO2 (Ti:Si = 50: 50 mol%) with diameters of 50-400 nm were prepared by calcining electrospun nanofibres of polyvinyl acetate (PVac)/titania-silica composite as precursor. These PVac/titania-silica hybrid nanofibres were obtained from a homogenous solution of PVac with a sol-gel of titanium isopropoxide (TiP) and tetraethoxysilane by using the electrospinning technique. The nanofibres were characterized by scanning electron microscopy (SEM), wide-angle x-ray diffraction (WAXD), Fourier transform infrared (FTIR) spectroscopy and Brunauer-Emmett-Teller (BET) surface area. SEM, WAXD and FTIR results indicated that the morphology and crystalline phase of TiO2-SiO2 nanofibres were strongly influenced by the calcination temperature and the content of titania and silica in the nanofibres. Additionally, the BET results showed that the surface area of TiO2-SiO2 nanofibres was decreased with increasing calcination temperature and the content of titania and silica in nanofibres.

Photoreduction of CO2 on TiO2/SrTiO3 Heterojunction Network Film

NASA Astrophysics Data System (ADS)

Bi, Yongsheng; Zong, Lanlan; Li, Chen; Li, Qiuye; Yang, Jianjun

2015-08-01

Nanotube titanic acid (NTA) network film has a porous structure and large BET surface area, which lead them to possessing high utilization of the incident light and strong adsorption ability. We used NTA as the precursor to fabricate a TiO2/ SrTiO3 heterojunction film by the hydrothermal method. In the process of the reaction, part of NTA reacted with SrCl2 to form SrTiO3 nanocubes, and the remainder dehydrated to transform to the rutile TiO2. The ratio of TiO2 and SrTiO3 varied with the hydrothermal reaction time. SEM and TEM images indicated that SrTiO3 nanocubes dispersed uniformly on TiO2 film, and the particle size and crystallinity of SrTiO3 nanocubes increased with the reaction time prolonging. The TiO2/SrTiO3 heterojunction obtained by 1 h showed the best activity for CO2 photoreduction, where the mole ratio of TiO2 and SrTiO3 was 4:1. And the photo-conversion efficiency of CO2 to CH4 improved remarkably after the foreign electron traps of Pt and Pd nanoparticles were loaded. The highest photocatalytic production rate of CH4 reached 20.83 ppm/h cm2. In addition, the selectivity of photoreduction product of CO2 was also increased apparently when Pd acted as the cocatalyst on TiO2/SrTiO3 heterojunction film.

Rutile TiO2 Mesocrystals as Sulfur Host for High-Performance Lithium-Sulfur Batteries.

PubMed

Sun, Qingqing; Chen, Kaixiang; Liu, Yubin; Li, Yafeng; Wei, Mingdeng

2017-11-16

Although lithium-sulfur (Li-S) batteries are among the most promising rechargeable batteries in the field of energy-storage devices, their poor cycling performance restricts their potential applications. Polar materials can improve the cycling stability owing to their inherent strong chemical interaction with polysulfides. Herein, novel rutile TiO 2 mesocrystals (RTMs) are employed as the host for sulfur in Li-S batteries; the RTMs display a stable cycling performance with a capacity retention of 64 % and a small average capacity decay rate of 0.12 % per cycle over 300 cycles at 1 C rate. The good electrochemical properties are attributed to the interior ordered nanopores of the RTMs, which can effectively limit the dissolution of polysulfides, and the ultrafine nanowires in RTMs, which shorten the path for lithium-ion transport effectively. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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.

Crystalline TiO 2 grafted with poly(2-methacryloyloxyethyl phosphorylcholine) via surface-initiated atom-transfer radical polymerization

NASA Astrophysics Data System (ADS)

Zhao, Yuancong; Tu, Qiufen; Wang, Jin; Huang, Qiongjian; Huang, Nan

2010-12-01

Crystalline TiO 2 films were prepared by unbalanced magnetron sputtering and the structure was confirmed by XRD. An organic layer of 11-hydroxyundecylphosphonic acid (HUPA) was prepared on the TiO 2 films by self-assembling, and the HUPA on TiO 2 films was confirmed by FTIR analysis. Simultaneously, hydroxyl groups were introduced in the phosphonic acid molecules to provide a functionality for further chemical modification. 2-Methacryloyloxyethyl phosphorylcholine (MPC), a biomimetic monomer, was chemically grafted on the HUPA surfaces at room temperature by surface-initiated atom-transfer radical polymerization. The surface characters of TiO 2 films modified by poly-MPC were confirmed by FTIR, XPS and SEM analysis. Platelet adhesion experiment revealed that poly-MPC modified surface was effective to inhibit platelet adhesion in vitro.

The effects of nanostructures on the mechanical and tribological properties of TiO2 nanotubes.

PubMed

Yoon, Yeoungchin; Park, Jeongwon

2018-04-20

TiO 2 nanotubes were prepared by anodization on Ti substrates with a diameter variation of 30-100 nm, and the structure of the nanotubes were studied using x-ray diffraction and Raman spectroscopy, which confirmed the structure changes from the anatase phase to the rutile phase of TiO 2 at a diameter below 50 nm. The tribological behaviors of TiO 2 nanotubes were investigated with different diameters. The effectiveness of the rutile phase and the diameter size enhanced the frictional performance of TiO 2 nanotubes.

The effects of nanostructures on the mechanical and tribological properties of TiO2 nanotubes

NASA Astrophysics Data System (ADS)

Yoon, Yeoungchin; Park, Jeongwon

2018-04-01

TiO2 nanotubes were prepared by anodization on Ti substrates with a diameter variation of 30-100 nm, and the structure of the nanotubes were studied using x-ray diffraction and Raman spectroscopy, which confirmed the structure changes from the anatase phase to the rutile phase of TiO2 at a diameter below 50 nm. The tribological behaviors of TiO2 nanotubes were investigated with different diameters. The effectiveness of the rutile phase and the diameter size enhanced the frictional performance of TiO2 nanotubes.

Colossal permittivity behavior and its origin in rutile (Mg1/3Ta2/3)xTi1-xO2.

PubMed

Dong, Wen; Chen, Dehong; Hu, Wanbiao; Frankcombe, Terry J; Chen, Hua; Zhou, Chao; Fu, Zhenxiao; Wei, Xiaoyong; Xu, Zhuo; Liu, Zhifu; Li, Yongxiang; Liu, Yun

2017-08-30

This work investigates the synthesis, chemical composition, defect structures and associated dielectric properties of (Mg 2+ , Ta 5+ ) co-doped rutile TiO 2 polycrystalline ceramics with nominal compositions of (Mg 2+ 1/3 Ta 5+ 2/3 ) x Ti 1-x O 2 . Colossal permittivity (>7000) with a low dielectric loss (e.g. 0.002 at 1 kHz) across a broad frequency/temperature range can be achieved at x = 0.5% after careful optimization of process conditions. Both experimental and theoretical evidence indicates such a colossal permittivity and low dielectric loss intrinsically originate from the intragrain polarization that links to the electron-pinned [Formula: see text] defect clusters with a specific configuration, different from the defect cluster form previously reported in tri-/pent-valent ion co-doped rutile TiO 2 . This work extends the research on colossal permittivity and defect formation to bi-/penta-valent ion co-doped rutile TiO 2 and elucidates a likely defect cluster model for this system. We therefore believe these results will benefit further development of colossal permittivity materials and advance the understanding of defect chemistry in solids.

Solar physical vapor deposition preparation and microstructural characterization of TiO2 based nanophases for dye-sensitized solar cell applications.

PubMed

Negrea, Denis; Ducu, Catalin; Moga, Sorin; Malinovschi, Viorel; Monty, Claude J A; Vasile, Bogdan; Dorobantu, Dorel; Enachescu, Marian

2012-11-01

Titanium dioxide exists in three crystalline phases: anatase, rutile and brookite. Although rutile is thermodynamically more stable, anatase is considered as the most favorable phase for photocatalysis and solar energy conversion. Recent studies have shown a significant improvement of light harvesting and overall solar conversion efficiency of anatase nanoparticles in dye-sensitized solar cells (DSSCs) when using a mixture of anatase and rutile phases (10-15% rutile). TiO2 nanopowders have been prepared by a solar physical vapor deposition process (SPVD). This method has been developed in Odeillo-Font Romeu France using "heliotron" solar reactors working under concentrated sunlight in 2 kW solar furnaces. By controlling reactor's atmosphere type (air/argon) and gas pressure, several types of anatase/rutile nanophases have been obtained with slightly different microstructural properties and morphological characteristics. X-ray diffraction analyses (XRD) were performed on precursor and on the SPVD obtained nanopowders. Information concerning their phase composition and coherence diffraction domain (crystallites size and strain) was obtained. Nanopowders morphology has been studied by scanning electron microscopy (SEM) and transmission electron microscopy (TEM).

Study of the modes of adsorption and electronic structure of hydrogen peroxide and ethanol over TiO2 rutile (110) surface within the context of water splitting

NASA Astrophysics Data System (ADS)

Alghamdi, H.; Idriss, H.

2018-03-01

While photocatalytic water splitting over many materials is favourable thermodynamically the kinetic of the reaction is very slow. One of the proposed reasons linked to the slow oxidation reaction rate is H2O2 formation as a reaction intermediate. Using Density Functional Theory (DFT) H2O2 is investigated on TiO2 rutile (110) surface to determine its most stable adsorption modes: molecular, (H)O(H)O - (a), partially dissociated, (H)OO - (a), and fully dissociated (a) - OO - (a). We then compare H2O2 interaction to that of a fast hole scavenger molecule, ethanol. Geometry, electronic structure, charge density difference and work function determination of both adsorbates are presented and compared using DFT with different functionals (PBE, PBE-D, PBE-U, and HSE + D). H2O2 is found to be strongly adsorbed on TiO2 rutile (110) surface with adsorption energies reaching 0.95 eV, comparable to that of ethanol (0.89 eV); using GGA PBE. The negative changes in the work function upon adsorption were found to be highest for molecular adsorption ( - 1.23 eV) and lowest for the fully dissociated mode ( - 0.54 eV) of H2O2. This may indicate that electrons flow from the surface to the adsorbate in order to make O(s)-H partially offset the overall magnitude of the oxygen lone pair interaction (of H2O2) with Ti4+ cations. Examination of the electronic structure through density of states (DOS) at the PBE level of computation, indicates that the H2O2 highest occupied molecular orbital (HOMO) level is not overlapping with oxygen atoms of TiO2 surface at any of its adsorption modes and at any of the computation methods. Some overlap is seen using the HSE + D computational method. On the other hand the dissociated mode of ethanol (ethoxides) does overlap with all computational methods used. The high adsorption energy and the absence of overlapping of the HOMO level of H2O2 with TiO2 rutile (110) surface may explain why water splitting is slow.

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

Direction-specific van der Waals attraction between rutile TiO2 nanocrystals

NASA Astrophysics Data System (ADS)

Zhang, Xin; He, Yang; Sushko, Maria L.; Liu, Jia; Luo, Langli; De Yoreo, James J.; Mao, Scott X.; Wang, Chongmin; Rosso, Kevin M.

2017-04-01

Mutual lattice orientations dictate the types and magnitudes of forces between crystalline particles. When lattice polarizability is anisotropic, the van der Waals dispersion attraction can, in principle, contribute to this direction dependence. We report measurement of this attraction between rutile nanocrystals, as a function of their mutual orientation and surface hydration extent. At tens of nanometers of separation, the attraction is weak and shows no dependence on azimuthal alignment or surface hydration. At separations of approximately one hydration layer, the attraction is strongly dependent on azimuthal alignment and systematically decreases as intervening water density increases. Measured forces closely agree with predictions from Lifshitz theory and show that dispersion forces can generate a torque between particles interacting in solution and between grains in materials.

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. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Influence of annealing atmosphere on formation of electrically-active defects in rutile TiO2

NASA Astrophysics Data System (ADS)

Zimmermann, C.; Bonkerud, J.; Herklotz, F.; Sky, T. N.; Hupfer, A.; Monakhov, E.; Svensson, B. G.; Vines, L.

2018-04-01

Electronic states in the upper part of the bandgap of reduced and/or hydrogenated n-type rutile TiO2 single crystals have been studied by means of thermal admittance and deep-level transient spectroscopy measurements. The studies were performed at sample temperatures between 28 and 300 K. The results reveal limited charge carrier freeze-out even at 28 K and evidence the existence of dominant shallow donors with ionization energies below 25 meV. Interstitial atomic hydrogen is considered to be a major contributor to these shallow donors, substantiated by infrared absorption measurements. Three defect energy levels with positions of about 70 meV, 95 meV, and 120 meV below the conduction band edge occur in all the studied samples, irrespective of the sample production batch and the post-growth heat treatment used. The origin of these levels is discussed in terms of electron polarons, intrinsic point defects, and/or common residual impurities, where especially interstitial titanium atoms, oxygen vacancies, and complexes involving Al atoms appear as likely candidates. In contrast, no common deep-level defect, exhibiting a charge state transition in the 200-700 meV range below the conduction band edge, is found in different samples. This may possibly indicate a strong influence on deep-level defects by the post-growth heat treatments employed.

Thermally induced anchoring of a zinc-carboxyphenylporphyrin on rutile TiO2 (110)

NASA Astrophysics Data System (ADS)

Jöhr, Res; Hinaut, Antoine; Pawlak, Rémy; Zajac, Łukasz; Olszowski, Piotr; Such, Bartosz; Glatzel, Thilo; Zhang, Jun; Muntwiler, Matthias; Bergkamp, Jesse J.; Mateo, Luis-Manuel; Decurtins, Silvio; Liu, Shi-Xia; Meyer, Ernst

2017-05-01

Functionalization of surfaces has become of high interest for a wealth of applications such as sensors, hybrid photovoltaics, catalysis, and molecular electronics. Thereby molecule-surface interactions are of crucial importance for the understanding of interface properties. An especially relevant point is the anchoring of molecules to surfaces. In this work, we analyze this process for a zinc-porphyrin equipped with carboxylic acid anchoring groups on rutile TiO2 (110) using scanning probe microscopy. After evaporation, the porphyrins are not covalently bound to the surface. Upon annealing, the carboxylic acid anchors undergo deprotonation and bind to surface titanium atoms. The formation of covalent bonds is evident from the changed stability of the molecule on the surface as well as the adsorption configuration. Annealed porphyrins are rotated by 45° and adopt another adsorption site. The influence of binding on electronic coupling with the surface is investigated using photoelectron spectroscopy. The observed shifts of Zn 2p and N 1s levels to higher binding energies indicate charging of the porphyrin core, which is accompanied by a deformation of the macrocycle due to a strong interaction with the surface.

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.

Direction-specific van der Waals attraction between rutile TiO2 nanocrystals.

PubMed

Zhang, Xin; He, Yang; Sushko, Maria L; Liu, Jia; Luo, Langli; De Yoreo, James J; Mao, Scott X; Wang, Chongmin; Rosso, Kevin M

2017-04-28

Mutual lattice orientations dictate the types and magnitudes of forces between crystalline particles. When lattice polarizability is anisotropic, the van der Waals dispersion attraction can, in principle, contribute to this direction dependence. We report measurement of this attraction between rutile nanocrystals, as a function of their mutual orientation and surface hydration extent. At tens of nanometers of separation, the attraction is weak and shows no dependence on azimuthal alignment or surface hydration. At separations of approximately one hydration layer, the attraction is strongly dependent on azimuthal alignment and systematically decreases as intervening water density increases. Measured forces closely agree with predictions from Lifshitz theory and show that dispersion forces can generate a torque between particles interacting in solution and between grains in materials. Copyright © 2017, American Association for the Advancement of Science.

Direction-specific van der Waals attraction between rutile TiO 2 nanocrystals

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

Zhang, Xin; He, Yang; Sushko, Maria L.

Mutual lattice orientations dictate the types and magnitudes of forces between crystalline particles. When lattice polarizability is anisotropic, the van der Waals dispersion attraction can, in principle, contribute to this direction dependence. Here we report direct measurement of this attraction between rutile nanocrystals, as a function of their mutual orientation and surface hydration extent. At tens of nanometers of separation the attraction is weak and shows no dependence on azimuthal alignment nor surface hydration. At separations of approximately one hydration layer the attraction is strongly dependent on azimuthal alignment, and systematically decreases as intervening water density increases. Measured forces aremore » in close agreement with predictions from Lifshitz theory, and show that dispersion forces are capable of generating a torque between particles interacting in solution and between grains in materials.« less

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

PubMed Central

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

2010-01-01

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 (JSC), the open-circuit voltage (VOC), the fill factor (FF), and the overall efficiency (η) were 14.45 mA/cm2, 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. PMID:24198470

Structural transformation study of TiO2 nanoparticles annealing at different temperatures and the photodegradation process of eosin-Y

NASA Astrophysics Data System (ADS)

Pandi, P.; Gopinathan, C.

2018-04-01

Hydrothermal method was used to prepare TiO2 nanoparticles with annealing temperature at 500 °C-700 °C. The mixture of anatase-rutile phase was investigated by powerful tool of X-ray diffraction (XRD). The structural parameters of anatase and rutile mixture phaseTiO2 nanoparticles were calculated from the Rietveld refinement. The transformation rate of rutile was increased linearly with an annealing temperature of 500 °C-700 °C. The spherical morphology of the anatase and rutile mixed phase were obtained by scanning electron microscope and transmission electron microscope. The spherical particle of the anatase and rutile TiO2 shows with great aggregation with different size and within the range of few tens nm. The EDAX study revealed the presence of titanium and oxygen. The best photocatalytic activity was identified as the 87.04% of anatase and 12.96% of rutile mixer phase of TiO2. Various factors could be involved for a better photocatalytic activity.

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.

Tunable top-down fabrication and functional surface coating of single-crystal titanium dioxide nanostructures and nanoparticles

NASA Astrophysics Data System (ADS)

Ha, Seungkyu; Janissen, Richard; Ussembayev, Yera Ye.; van Oene, Maarten M.; Solano, Belen; Dekker, Nynke H.

2016-05-01

Titanium dioxide (TiO2) is a key component of diverse optical and electronic applications that exploit its exceptional material properties. In particular, the use of TiO2 in its single-crystalline phase can offer substantial advantages over its amorphous and polycrystalline phases for existing and yet-to-be-developed applications. However, the implementation of single-crystal TiO2 has been hampered by challenges in its fabrication and subsequent surface functionalization. Here, we introduce a novel top-down approach that allows for batch fabrication of uniform high-aspect-ratio single-crystal TiO2 nanostructures with targeted sidewall profiles. We complement our fabrication approach with a functionalization strategy that achieves dense, uniform, and area-selective coating with a variety of biomolecules. This allows us to fabricate single-crystal rutile TiO2 nanocylinders tethered with individual DNA molecules for use as force- and torque-transducers in an optical torque wrench. These developments provide the means for increased exploitation of the superior material properties of single-crystal TiO2 at the nanoscale.Titanium dioxide (TiO2) is a key component of diverse optical and electronic applications that exploit its exceptional material properties. In particular, the use of TiO2 in its single-crystalline phase can offer substantial advantages over its amorphous and polycrystalline phases for existing and yet-to-be-developed applications. However, the implementation of single-crystal TiO2 has been hampered by challenges in its fabrication and subsequent surface functionalization. Here, we introduce a novel top-down approach that allows for batch fabrication of uniform high-aspect-ratio single-crystal TiO2 nanostructures with targeted sidewall profiles. We complement our fabrication approach with a functionalization strategy that achieves dense, uniform, and area-selective coating with a variety of biomolecules. This allows us to fabricate single-crystal rutile

Band gap enhancement of glancing angle deposited TiO2 nanowire array

NASA Astrophysics Data System (ADS)

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

2012-09-01

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

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

NASA Astrophysics Data System (ADS)

Shi, Li-Bin; Wang, Yong Ping

2016-05-01

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

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

NASA Astrophysics Data System (ADS)

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

2012-12-01

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

Scanning electron microscopy of heat treated TiO2 nanotubes arrays obtained by anodic oxidation

NASA Astrophysics Data System (ADS)

Naranjo, D. I.; García-Vergara, S. J.; Blanco, S.

2017-12-01

Scanning electron microscopy was used to investigate the anatase-rutile transformation of self-organized TiO2 nanotubes obtained on titanium foil by anodizing and subsequent heat treatment. The anodizing was carried out at 20V in an 1% v/v HF acid and ethylene glycol:water (50:50) electrolyte at room temperature. The anodized samples were initially pre-heat treated at 450°C for 4 hours to modify the amorphous structure of TiO2 nanotubes into anatase structure. Then, the samples were heated between 600 to 800°C for different times, in order to promote the transformation to rutile structure. The formation of TiO2 nanotubes is evident by SEM images. Notably, when the samples are treated at high temperature, the formation of rutile crystals starts to become evident at the nanotubes located on the originally grain boundaries of the titanium. Thus, the anatase - rutile transformation has a close relationship with the microstructure of the titanium, more exactly with grain boundaries.

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

Single-Nanoparticle Photoelectrochemistry at a Nanoparticulate TiO2 -Filmed Ultramicroelectrode.

PubMed

Peng, Yue-Yi; Ma, Hui; Ma, Wei; Long, Yi-Tao; Tian, He

2018-03-26

An ultrasensitive photoelectrochemical method for achieving real-time detection of single nanoparticle collision events is presented. Using a micrometer-thick nanoparticulate TiO 2 -filmed Au ultra-microelectrode (TiO 2 @Au UME), a sub-millisecond photocurrent transient was observed for an individual N719-tagged TiO 2 (N719@TiO 2 ) nanoparticle and is due to the instantaneous collision process. Owing to a trap-limited electron diffusion process as the rate-limiting step, a random three-dimensional diffusion model was developed to simulate electron transport dynamics in TiO 2 film. The combination of theoretical simulation and high-resolution photocurrent measurement allow electron-transfer information of a single N719@TiO 2 nanoparticle to be quantified at single-molecule accuracy and the electron diffusivity and the electron-collection efficiency of TiO 2 @Au UME to be estimated. This method provides a test for studies of photoinduced electron transfer at the single-nanoparticle level. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Charge storage in oxygen deficient phases of TiO2: defect Physics without defects.

PubMed

Padilha, A C M; Raebiger, H; Rocha, A R; Dalpian, G M

2016-07-01

Defects in semiconductors can exhibit multiple charge states, which can be used for charge storage applications. Here we consider such charge storage in a series of oxygen deficient phases of TiO2, known as Magnéli phases. These Magnéli phases (TinO2n-1) present well-defined crystalline structures, i.e., their deviation from stoichiometry is accommodated by changes in space group as opposed to point defects. We show that these phases exhibit intermediate bands with an electronic quadruple donor transitions akin to interstitial Ti defect levels in rutile TiO2. Thus, the Magnéli phases behave as if they contained a very large pseudo-defect density: ½ per formula unit TinO2n-1. Depending on the Fermi Energy the whole material will become charged. These crystals are natural charge storage materials with a storage capacity that rivals the best known supercapacitors.

Effect of different alcohols, gelatinizing times, calcination and microwave on characteristics of TiO2 nanoparticles synthesized by sol-gel method

NASA Astrophysics Data System (ADS)

Bahar, Mahmoud; Mozaffari, Masoud; Esmaeili, Sahar

2017-03-01

In this work, nanoparticles of titanium dioxide (TiO2) were synthesized by means of TiCl4 as precursor. Effects of alcohol type, calcination, gelatinizing time and microwave exposure on the particle size, morphology, crystallinity and particle phase are studied using XRD patterns and SEM images. Results showed that alcohols such as ethanol increased the particle size; calcination increased the particle size and improved the crystallinity of particles. Microwave exposure of particles resulted in smaller particles; adding water increased the impact of microwave. Effect of microwave exposure in rutile phase formation is also observed during this study.

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

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

Zhu, Ke; Xia, Yaobiao; Tang, Miru

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 ofmore » 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.« less

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.

Structure and Properties of VO2 and Titanium Dioxide Based Epitaxial Heterostructures Integrated with Silicon and Sapphire Substrates

NASA Astrophysics Data System (ADS)

Bayati, Mohammad Reza

application in environmental remediation was taken into account. The photochemical efficiency of the samples was evaluated under ultraviolet and visible illuminations. I was able to establish a correlation between the growth conditions and the photocatalytic activity of single crystalline TiO 2 thin films. Visible-light-responsive TiO2 films were fabricated via vacuum annealing of the samples where point defects, namely oxygen vacancies and titanium interstitial, are surmised to play a critical role. An ultrafast switching was observed in wetting characteristics of the single crystalline rutile TiO2 films from a hydrophobic state to a superhydrophilic state by single pulsed excimer laser annealing. It was observed that the laser annealing almost doubles the photocatalytic efficiency of the anatase epitaxial thin films. I was able to measure the photochemical properties of the rutile and the anatase TiO2 heterostructures in a controlled way due to the single crystalline nature of the films. Second, the rutile TiO2 epilayers with different out-of-plane orientations were deposited and used as a platform for VO2 based epitaxial heterostructures with the aim of manipulating of microstructure and electrical properties of the VO 2 films. Vanadium dioxide (VO2) is an interesting material due to the abrupt change in electrical resistivity and infrared transmittance at about 68 °C. The transition temperature can be tuned through microstructural engineering. It was the idea behind using rutile TiO2 with different crystallographic orientations as a template to tune the semiconductor to metal transition characteristics of the VO2 top layer. I successfully grew VO2(001), VO2(100), and VO2(2¯01) epitaxial thin films on TiO2(100)/c-sapphire, TiO2(101)/r-sapphire, and TiO2(001)/ m-sapphire platforms, respectively. It was observed that tetragonal phase of VO2 was stabilized at lower temperatures leading to a significant decrease in the semiconductor to metal transition temperature. In other

Heterogeneous activation of H2O2 by defect-engineered TiO(2-x) single crystals for refractory pollutants degradation: A Fenton-like mechanism.

PubMed

Zhang, Ai-Yong; Lin, Tan; He, Yuan-Yi; Mou, Yu-Xuan

2016-07-05

The heterogeneous catalyst plays a key role in Fenton-like reaction for advanced oxidation of refractory pollutants in water treatment. Titanium dioxide (TiO2) is a typical semiconductor with high industrial importance due to its earth abundance, low cost and no toxicity. In this work, it is found that TiO2 can heterogeneously activate hydrogen peroxide (H2O2, E°=1.78 eV), a common chemical oxidant, to efficiently generate highly-powerful hydroxyl radical, OH (E(0)=2.80 eV), for advanced water treatment, when its crystal shape, exposed facet and oxygen-stoichiometry are finely tuned. The defect-engineered TiO2 single crystals exposed by high-energy {001} facets exhibited an excellent Fenton-like activity and stability for degrading typical refractory organic pollutants such as methyl orange and p-nitrophenol. Its defect-centered Fenton-like superiority is mainly attributed to the crystal oxygen-vacancy, single-crystalline structure and exposed polar {001} facet. Our findings could provide new chance to utilize TiO2 for Fenton-like technology, and develop novel heterogeneous catalyst for advanced water treatment. Copyright © 2016 Elsevier B.V. All rights reserved.

Silver doped TiO2 nano crystallites for dye-sensitized solar cell (DSSC) applications

NASA Astrophysics Data System (ADS)

Sakthivel, T.; Ashok Kumar, K.; Ramanathan, Rajajeyaganthan; Senthilselvan, J.; Jagannathan, K.

2017-12-01

This communication deals with the synthesis of Ag doped TiO2 nanoparticles with different doping concentrations prepared by reduction method for the possible usage of photo anode material in DSSC. The prepared nanoparticles are characterized by x-ray diffraction to study their structural properties which confirms the formation of mixed anatase-rutile crystalline phases. The particulate size, shape and surface morphology are examined using FESEM which indicates agglomerated nanostructures with the average particle size of 20-25 nm. The UV-visible absorption spectra showed enhanced absorption in the visible range in accordance with the doping concentration of Ag with a red shift in their absorption edge. The interfacial charge transport phenomena of the DSSCs are determined by electrochemical impedance spectroscopy (EIS) and the corresponding efficiencies are calculated using J-V curve. In the present work, the UV active TiO2 and Ag doped TiO2 nanoparticles are employed as photoanode for the fabrication of DSSCs based on N3 dye and maximum power conversion efficiency of 1.544% is realized.

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.

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.

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

NASA Astrophysics Data System (ADS)

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

2015-04-01

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

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

NASA Astrophysics Data System (ADS)

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

2016-05-01

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

The Effects of Leaching Process to the TiO2 Synthesis from Bangka Ilmenite

NASA Astrophysics Data System (ADS)

Wahyuningsih, S.; Ramelan, A. H.; Pramono, E.; Argawan, P.; Djatisulistya, A.; Firdiyono, F.; Sulistiyono, E.; Sari, P. P.

2018-03-01

Ilmenite mineral is a naturally occurring iron titanate (FeTiO3) and is abundant in nature. The separation of components into TiO2 and Fe2O3 must be expand. The purpose of this research is to synthesis TiO2 nanoparticles from the filtrate of Bangka ilmenite leaching process. Leaching of ilmenite was done with H2SO4 and HCl at various concentrations. The formation of TiO2 crystal determined by hydrolysis conditions and condensation reaction. TiO2 synthesized from the filtrate of sulfuric acid leaching that produced from TiO2 anatase phase when hydrolyzed in an aquaregia solvent and low concentrations of HCl (0.1M). Hydrolysis conditions at higher concentrations of HCl (1M) was produced TiO2 anatase-rutile phase. The synthesis of TiO2 from the filtrate of hydrochloric acid leaching was produced anatase phase. While the condition under the alcoholic solvent (2-propanol: H2O (v/v) = 9: 1) anatase phase crystallites grow in the temperature range up to 550 °C, above this temperature, TiO2 transform into rutile phase.

A TiO2/FeMnP Core/Shell Nanorod Array Photoanode for Efficient Photoelectrochemical Oxygen Evolution.

PubMed

Schipper, Desmond E; Zhao, Zhenhuan; Leitner, Andrew P; Xie, Lixin; Qin, Fan; Alam, Md Kamrul; Chen, Shuo; Wang, Dezhi; Ren, Zhifeng; Wang, Zhiming; Bao, Jiming; Whitmire, Kenton H

2017-04-25

A variety of catalysts have recently been developed for electrocatalytic oxygen evolution, but very few of them can be readily integrated with semiconducting light absorbers for photoelectrochemical or photocatalytic water splitting. Here, we demonstrate an efficient core/shell photoanode with a highly active oxygen evolution electrocatalyst shell (FeMnP) and semiconductor core (rutile TiO 2 ) for photoelectrochemical oxygen evolution reaction. Metal-organic chemical vapor deposition from a single-source precursor was used to ensure good contact between the FeMnP and the TiO 2 . The TiO 2 /FeMnP core/shell photoanode reaches the theoretical photocurrent density for rutile TiO 2 of 1.8 mA cm -2 at 1.23 V vs reversible hydrogen electrode under simulated 100 mW cm -2 (1 sun) irradiation. The dramatic enhancement is a result of the synergistic effects of the high oxygen evolution reaction activity of FeMnP (delivering an overpotential of 300 mV with a Tafel slope of 65 mV dec -1 in 1 M KOH) and the conductive interlayer between the surface active sites and semiconductor core which boosts the interfacial charge transfer and photocarrier collection. The facile fabrication of the TiO 2 /FeMnP core/shell nanorod array photoanode offers a compelling strategy for preparing highly efficient photoelectrochemical solar energy conversion devices.

Structure reconstruction of TiO2-based multi-wall nanotubes: first-principles calculations.

PubMed

Bandura, A V; Evarestov, R A; Lukyanov, S I

2014-07-28

A new method of theoretical modelling of polyhedral single-walled nanotubes based on the consolidation of walls in the rolled-up multi-walled nanotubes is proposed. Molecular mechanics and ab initio quantum mechanics methods are applied to investigate the merging of walls in nanotubes constructed from the different phases of titania. The combination of two methods allows us to simulate the structures which are difficult to find only by ab initio calculations. For nanotube folding we have used (1) the 3-plane fluorite TiO2 layer; (2) the anatase (101) 6-plane layer; (3) the rutile (110) 6-plane layer; and (4) the 6-plane layer with lepidocrocite morphology. The symmetry of the resulting single-walled nanotubes is significantly lower than the symmetry of initial coaxial cylindrical double- or triple-walled nanotubes. These merged nanotubes acquire higher stability in comparison with the initial multi-walled nanotubes. The wall thickness of the merged nanotubes exceeds 1 nm and approaches the corresponding parameter of the experimental patterns. The present investigation demonstrates that the merged nanotubes can integrate the two different crystalline phases in one and the same wall structure.

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

PubMed

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

2015-04-28

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

Instability of Hydrogenated TiO2

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

Nandasiri, Manjula I.; Shutthanandan, V.; Manandhar, Sandeep

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 depthmore » (~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.« less

Degradation of selected industrial dyes using Mg-doped TiO2 polyscales under natural sun light as an alternative driving energy

NASA Astrophysics Data System (ADS)

Shivaraju, H. P.; Midhun, G.; Anil Kumar, K. M.; Pallavi, S.; Pallavi, N.; Behzad, Shahmoradi

2017-11-01

Designing photocatalytic materials with modified functionalities for the utilization of renewable energy sources as an alternative driving energy has attracted much attention in the area of sustainable wastewater treatment applications. Catalyst-assisted advanced oxidation process is an emerging treatment technology for organic pollutants and toxicants in industrial wastewater. Preparation of visible-light-responsive photocatalyst such as Mg-doped TiO2 polyscales was carried out under mild sol-gel technique. Mg-doped TiO2 polyscales were characterized by powder XRD, SEM, FTIR, and optical and photocatalytic activity techniques. The Mg-doped TiO2 showed a mixed phase of anatase and rutile with an excellent crystallinity, structural elucidations, polyscales morphology, consequent shifting of bandgap energy and adequate photocatalytic activities under visible range of light. Mg-doped TiO2 polyscales were investigated for their efficiencies in the degradation of most commonly used industrial dyes in the real-time textile wastewater. Mg-doped TiO2 polyscales showed excellent photocatalytic degradation efficiency in both model industrial dyes (65-95%) and textile wastewater (92%) under natural sunlight as an alternative and renewable driving energy.

Effect of porphyrin on photocatalytic activity of TiO2 nanoparticles toward Rhodamine B photodegradation.

PubMed

Ahmed, M A; Abou-Gamra, Z M; Medien, H A A; Hamza, M A

2017-11-01

As known, porphyrins have central role in photosynthesis, biological oxidation and reduction and oxygen transport beside to their intensive color which qualify them to be good photosensitizers. Herein, tetra (4-carboxyphenyl) porphyrin (TCPP) was prepared by a simple one-pot synthesis to use as a visible antenna for TiO 2 nanoparticles that were prepared via a simple template-free sol-gel method. Various loading percentages of TCPP (0.05-1%) were incorporated on the surface of TiO 2 as photosensitizer for photocatalytic degradation of Rhodamine B (Rh B) dye as a primary cationic pollutant model. Among them, 0.1% TCPP-TiO 2 was the most reactive sample. It was found that the photoactivity of 0.1% TCPP-TiO 2 sample (0.5g/L) was approximately 1.5 times greater than that of pure TiO 2 (0.5g/L) toward the degradation of Rh B (1×10 -5 M) under UV-A irradiation. Transient fluorescence decay measurements showed that the life time of TiO 2 excited state has doubled after anchoring TCPP, thus the probability of electron-hole recombination has decreased. The samples were characterized by XRD, HR-TEM, DRS and N 2 adsorption-desorption isotherms. The XRD patterns confirmed the successful preparation of TiO 2 nanoparticles with average crystalline size of 25.7nm. Also, XRD patterns suggested the presence of mixed phase TiO 2 nanoparticles of 77% anatase and 23% rutile. DRS showed that the characteristic peaks of TCPP covered the whole visible range 400-700nm. HR-TEM images showed the spheroids shape of TiO 2 nanoparticles and confirmed the presence of anatase and rutile phases as suggested from XRD data. The different parameters affecting the photodegradation of Rh B dye such as catalyst dose, dye concentration and pH were studied to obtain the optimum conditions. Almost complete degradation of Rh B was obtained which confirmed by HPLC and TOC measurements. The effect of scavengers was studied to indicate the most active species. TCPP-TiO 2 gave a good response toward the

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

Effect of cobalt doping on the phase transformation of TiO2 nanoparticles.

PubMed

Barakat, M A; Hayes, G; Shah, S Ismat

2005-05-01

Co-doped TiO2 nanoparticles containing 0.0085, 0.017, 0.0255, 0.034, and 0.085 mol % Co(III) ion dopant were synthesized via sol-gel and dip-coating techniques. The effects of metal ion doping on the transformation of anatase to the rutile phase have been investigated. Several analytical tools, such as X-ray diffraction (XRD), transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS), and energy dispersive X-ray analysis (EDAX) were used to investigate the nanoparticle structure, size distribution, and composition. Results obtained revealed that the rutile to anatase concentration ratio increases with increase of the cobalt dopant concentration and annealing temperature. The typical composition of Co-doped TiO2 was Ti(1-x)Co(x)O2, where x values ranged from 0.0085 to 0.085. The activation energy for the phase transformation from anatase to rutile was measured to be 229, 222, 211, and 195 kJ/mole for 0.0085, 0.017, 0.0255, and 0.034 mol % Co in TiO2, respectively.

ESR investigation of ROS generated by H2O2 bleaching with TiO2 coated HAp.

PubMed

Saita, Makiko; Kobayashi, Kyo; Kobatashi, Kyou; Yoshino, Fumihiko; Hase, Hiriko; Nonami, Toru; Kimoto, Katsuhiko; Lee, Masaichi-Chang-il

2012-01-01

It is well known that clinical bleaching can be achieved with a solution of 30% hydrogen peroxide (H2O2) or H2O2/titanium dioxide (TiO2) combination. This study examined the hypothesis that TiO2 coated with hydroxyapatite (HAp-TiO2) can generate reactive oxygen species (ROS). ROS are generated via photocatalysis using electron spin resonance (ESR). The bleaching properties of HAp-TiO2 in the presence of H2O2 can be measured using hematoporphyrin litmus paper and extracted teeth. We demonstrate that superoxides (O2(•-)) and hydroxyl radicals (HO(•)) can be generated through excitation of anatase TiO2, rutile TiO2, anatase HAp-TiO2, and rutile HAp-TiO2 in the presence of H2O2. The combination of R HAp-TiO2 with H2O2 produced the highest level of HO(•) generation and the most marked bleaching effects of all the samples. The superior bleaching effects exhibited by R HAp-TiO2 with H2O2 suggest that this combination may lead to novel methods for the clinical application of bleaching treatments.

Effects of TiO2 crystal structure on the luminescence quenching of [Ru(bpy)2(dppz)]2 +-intercalated into DNA

NASA Astrophysics Data System (ADS)

Chen, Linlin; Wang, Yi; Huang, Minggao; Li, Xiaodan; Zhu, Licai; Li, Hong

2017-06-01

The intercalation of [Ru(bpy)2(dppz)]2 + labeled as Ru(II) (bpy = 2,2‧-bipyridine and dppz = dipyrido[3,2,-a:2‧,3‧-c]phenazine) into herring sperm DNA leads to the formation of emissive Ru(II)-DNA dyads, which can be quenched by TiO2 nanoparticles (NPs) and sol-gel silica matrices at heterogeneous interfaces. The calcinations temperature exhibits a remarkable influence on the luminescence quenching of the Ru(II)-DNA dyads by TiO2 NPs. With increasing calcinations temperature in the range from 200 to 850 °C, the anatase-to-rutile TiO2 crystal structure transformation increases the average particle size and hydrodynamic diameter of TiO2 and DNA@TiO2. The anatase TiO2 has the stronger ability to unbind the Ru(II)-DNA dyads than the rutile TiO2 at room temperature. The TiO2 NPs and sol-gel silica matrices can quench the luminescence of the Ru(II) complex intercalated into DNA by selectively capturing the negatively DNA and positively charged Ru(II) complex to unbind the dyads, respectively. This present results provide new insights into the luminescence quenching and competitive binding of dye-labeled DNA dyads by inorganic NPs.

Synergistic Effects of Sm and C Co-Doped Mixed Phase Crystalline TiO2 for Visible Light Photocatalytic Activity

PubMed Central

Peng, Fuchang; Gao, Honglin; Zhang, Genlin; Zhu, Zhongqi; Zhang, Jin; Liu, Qingju

2017-01-01

Mixed phase TiO2 nanoparticles with element doping by Sm and C were prepared via a facile sol-gel procedure. The UV-Vis light-diffuse reflectance spectroscopy analysis showed that the absorption region of co-doped TiO2 was shifted to the visible-light region, which was attributed to incorporation of samarium and carbon into the TiO2 lattice during high-temperature reaction. Samarium effectively decreased the anatase-rutile phase transformation. The grain size can be controlled by Sm doping to achieve a large specific surface area useful for the enhancement of photocatalytic activity. The photocatalytic activities under visible light irradiation were evaluated by photocatalytic degradation of methylene blue (MB). The degradation rate of MB over the Sm-C co-doped TiO2 sample was the best. Additionally, first-order apparent rate constants increased by about 4.3 times compared to that of commercial Degusssa P25 under the same experimental conditions. Using different types of scavengers, the results indicated that the electrons, holes, and •OH radicals are the main active species for the MB degradation. The high visible-light photocatalytic activity was attributed to low recombination of the photo-generated electrons and holes which originated from the synergistic effect of the co-doped ions and the heterostructure. PMID:28772569

Phase Equilibrium of TiO2 Nanocrystals in Flame-Assisted Chemical Vapor Deposition.

PubMed

Liu, Changran; Camacho, Joaquin; Wang, Hai

2018-01-19

Nano-scale titanium oxide (TiO 2 ) is a material useful for a wide range of applications. In a previous study, we showed that TiO 2 nanoparticles of both rutile and anatase crystal phases could be synthesized over the size range of 5 to 20 nm in flame-assisted chemical vapor deposition. Rutile was unexpectedly dominant in oxygen-lean synthesis conditions, whereas anatase is the preferred phase in oxygen-rich gases. The observation is in contrast to the 14 nm rutile-anatase crossover size derived from the existing crystal-phase equilibrium model. In the present work, we made additional measurements over a wider range of synthesis conditions; the results confirm the earlier observations. We propose an improved model for the surface energy that considers the role of oxygen desorption at high temperatures. The model successfully explains the observations made in the current and previous work. The current results provide a useful path to designing flame-assisted chemical vapor deposition of TiO 2 nanocrystals with controllable crystal phases. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of stable TiO2 nanotubes: effect of hydrothermal treatment, acid washing and annealing temperature.

PubMed

López Zavala, Miguel Ángel; Lozano Morales, Samuel Alejandro; Ávila-Santos, Manuel

2017-11-01

Effect of hydrothermal treatment, acid washing and annealing temperature on the structure and morphology of TiO 2 nanotubes during the formation process was assessed. X-ray diffraction, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy analysis were conducted to describe the formation and characterization of the structure and morphology of nanotubes. Hydrothermal treatment of TiO 2 precursor nanoparticles and acid washing are fundamental to form and define the nanotubes structure. Hydrothermal treatment causes a change in the crystallinity of the precursor nanoparticles from anatase phase to a monoclinic phase, which characterizes the TiO 2 nanosheets structure. The acid washing promotes the formation of high purity nanotubes due to Na + is exchanged from the titanate structure to the hydrochloric acid (HCl) solution. The annealing temperature affects the dimensions, structure and the morphology of the nanotubes. Annealing temperatures in the range of 400 °C and 600 °C are optimum to maintain a highly stable tubular morphology of nanotubes. Additionally, nanotubes conserve the physicochemical properties of the precursor Degussa P25 nanoparticles. Temperatures greater than 600 °C alter the morphology of nanotubes from tubular to an irregular structure of nanoparticles, which are bigger than those of the precursor material, i.e., the crystallinity turn from anatase phase to rutile phase inducing the collapse of the nanotubes.

TiO2-SnS2 nanocomposites: solar-active photocatalytic materials for water treatment.

PubMed

Kovacic, Marin; Kusic, Hrvoje; Fanetti, Mattia; Stangar, Urska Lavrencic; Valant, Matjaz; Dionysiou, Dionysios D; Bozic, Ana Loncaric

2017-08-01

The study is aimed at evaluating TiO 2 -SnS 2 composites as effective solar-active photocatalysts for water treatment. Two strategies for the preparation of TiO 2 -SnS 2 composites were examined: (i) in-situ chemical synthesis followed by immobilization on glass plates and (ii) binding of two components (TiO 2 and SnS 2 ) within the immobilization step. The as-prepared TiO 2 -SnS 2 composites and their sole components (TiO 2 or SnS 2 ) were inspected for composition, crystallinity, and morphology using Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), X-ray diffraction (XRD), and scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM/EDX) analyses. Diffuse reflectance spectroscopy (DRS) was used to determine band gaps of immobilized TiO 2 -SnS 2 and to establish the changes in comparison to respective sole components. The activity of immobilized TiO 2 -SnS 2 composites was tested for the removal of diclofenac (DCF) in aqueous solution under simulated solar irradiation and compared with that of single component photocatalysts. In situ chemical synthesis yielded materials of high crystallinity, while their morphology and composition strongly depended on synthesis conditions applied. TiO 2 -SnS 2 composites exhibited higher activity toward DCF removal and conversion in comparison to their sole components at acidic pH, while only in situ synthesized TiO 2 -SnS 2 composites showed higher activity at neutral pH.

[Preparation and photocatalytic activity of boron doped CeO2/TiO2 mixed oxides].

PubMed

Tang, Xin-hu; Wei, Chao-hai; Liang, Jie-rong; Wang, Bo-guang

2006-07-01

Boron doped CeO2/TiO2 mixed oxides photocatalysts were prepared by adding boric acid and cerous nitrate during the hydrolyzation of titanium trichloride and tetrabutyl titanate. XRD, UV-Vis DRS and XPS techniques were used to characterize the crystalline structure, light absorbing ability and the chemical state of Boron element in the photocatalyst sample. The photocatalytic activities were evaluated by monitoring the degradation of acid red B under UV irradiation. These results indicate that the wavelengths at adsorbing edge are affected by the content of cerous nitrate and the maximum absorption wavelength is about 481 nm when the mole ratio of Ce/Ti is 1.0. For higher dosage of Cerium, the absorbance edge shifts to blue slightly. The prepared photocatalyst is composed of anatase TiO2 and cubic CeO2 when calcined at 500 degrees C. An increase in the calcination temperature transforms the crystalline structure of the titanium oxides from anatase to rutile, and has no obvious influence on crystalline structure of CeO2 but crystallites growth up. The absorbance edge decreases drastically with the increase of calcination temperature. With a view to the stability of photocatalyst and utilization of sun energy, 500 degrees C of calcination temperature is recommended. The XP spectrum for B1s exhibits that only a few boron ions dope into titania and ceria matrix, others exist in B2O3. The photocatalytic activity increases with increase of cerous nitrate dosage, and decreases drastically due to higher dosage (the mol ratio of Ce/Ti > 0.5). After 10 min UV irradiation, 96% of acid red B is degraded completely over photocatalyst under optimum reaction condition.

A recipe for the use of rutile in sedimentary provenance analysis

NASA Astrophysics Data System (ADS)

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

2012-12-01

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

Band Alignment-Driven Oxidative Injury to the Skin by Anatase/Rutile Mixed-Phase Titanium Dioxide Nanoparticles under Sunlight Exposure.

PubMed

Sun, Xiujuan; Chang, Yun; Cheng, Yan; Feng, Yanlin; Zhang, Haiyuan

2018-04-12

Anatase/rutile mixed-phase titanium dioxide (TiO2) nanoparticles (NPs) have been found in cosmetics and cotton textiles. Once exposed to sunlight, mixed-phase TiO2 NPs are even more toxic to cells than pure phase NPs, however, the underlying mechanism remains unclear. Considering the unique anatase/rutile heterojunction structure existing in mixed-phase NPs, the potent toxicity of mixed-phase TiO2 NPs probably originates from the high reactive oxygen species (ROS) production because the anatase/rutile heterojunction is constituted by the staggered energy bands that facilitate the electron-hole separation at the interface due to the band alignment. In the present study, a library of mixed-phase TiO2 NPs with different anatase/rutile ratios was established to investigate the potential property-activity relationship and further clarify the underlying molecular mechanism. Under sunlight exposure, these mixed-phase TiO2 NPs could produce significant abiotic ROS and induce hierarchical oxidative stress to HaCaT skin cells and mice skin. The ROS magnitude and toxicity potential of these NPs were found to be proportional to their energy band bending (BB) levels. This means that the toxicity of mixed-phase TiO2 NPs can be correlated to their heterojunction density, and the toxicity potential of mixed-phase TiO2 NPs can be weighed by their BB levels.

Spontaneous formation of suboxidic coordination around Co in ferromagnetic rutile Ti 0.95Co 0.5O 2 film

DOE PAGES

Hu, Wen; Hayaski, Kouichi; Fukumura, Tomoteru; ...

2015-06-02

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

Toxicogenomics analysis of mouse lung responses following exposure to titanium dioxide nanomaterials reveal their disease potential at high doses

PubMed Central

Rahman, Luna; Wu, Dongmei; Johnston, Michael; William, Andrew; Halappanavar, Sabina

2017-01-01

Titanium dioxide nanoparticles (TiO2NPs) induce lung inflammation in experimental animals. In this study, we conducted a comprehensive toxicogenomic analysis of lung responses in mice exposed to six individual TiO2NPs exhibiting different sizes (8, 20 and 300nm), crystalline structure (anatase, rutile or anatase/rutile) and surface modifications (hydrophobic or hydrophilic) to investigate whether the mechanisms leading to TiO2NP-induced lung inflammation are property specific. A detailed histopathological analysis was conducted to investigate the long-term disease implications of acute exposure to TiO2NPs. C57BL/6 mice were exposed to 18, 54, 162 or 486 µg of TiO2NPs/mouse via single intratracheal instillation. Controls were exposed to dispersion medium only. Bronchoalveolar lavage fluid (BALF) and lung tissue were sampled on 1, 28 and 90 days post-exposure. Although all TiO2NPs induced lung inflammation as measured by the neutrophil influx in BALF, rutile-type TiO2NPs induced higher inflammation with the hydrophilic rutile TiO2NP showing the maximum increase. Accordingly, the rutile TiO2NPs induced higher number of differentially expressed genes. Histopathological analysis of lung sections on Day 90 post-exposure showed increased collagen staining and fibrosis-like changes following exposure to the rutile TiO2NPs at the highest dose tested. Among the anatase, the smallest TiO2NP of 8nm showed the maximum response. The anatase TiO2NP of 300nm was the least responsive of all. The results suggest that the severity of lung inflammation is property specific; however, the underlying mechanisms (genes and pathways perturbed) leading to inflammation were the same for all particle types. While the particle size clearly influenced the overall acute lung responses, a combination of small size, crystalline structure and hydrophilic surface contributed to the long-term pathological effects observed at the highest dose (486 µg/mouse). Although the dose at which the

Rutile TiO2 Flocculent Ripples with High Antireflectivity and Superhydrophobicity on the Surface of Titanium under 10 ns Laser Irradiation without Focusing.

PubMed

Pan, Aifei; Wang, Wenjun; Mei, Xuesong; Wang, Kedian; Yang, Xianbin

2017-09-26

We report on the formation of rutile TiO 2 flocculent laser-induced periodic surface structures (LIPSSs) with high antireflectivity and superhydrophobicity on the surface of titanium under 10 ns 1064 nm laser irradiation without focusing. The center part of the Gaussian laser beam is used to deposit flocculent structure and the edge part used to produce LIPSSs. The melt and modification thresholds of titanium were determined first, and then, the melt and modification spot-overlap numbers, several responsible for the formation of flocculent structure and LIPSSs, were introduced. It is found that both the melt and modification spot-overlap numbers increase with an increase in laser fluence and spot-overlap number, contributing to the production of flocculent LIPSSs. LIPSSs are obtained with the modification spot-overlap number above 300, and the amount of flocculent structures increases with an increase in the peak laser fluence and spot-overlap number. Then, considering that the fine adjustment of the melt and modification spot-overlop numbers in one-time line scanning is quite difficult, the composite structure, of which both LIPSSs and flocculent structures are distinct, was optimized using laser line scanning twice. On this basis, a characterization test shows the sample full of the flocculent LIPSSs represents best antireflectivity with the value around 10% in the waveband between 260 and 2600 nm (advance 5 times in infrared wavelengths compared to the initial titanium surface), and shows the no-stick hydrophobicity with the contact angle of 160° and roll-off angle of 25° because of the pure rutile phase of TiO 2 .

Thermostable photocatalytically active TiO2 anatase nanoparticles

NASA Astrophysics Data System (ADS)

Qi, Fei; Moiseev, Anna; Deubener, Joachim; Weber, Alfred

2011-03-01

Anatase is the low-temperature (300-550 °C) crystalline polymorph of TiO2 and it transforms to rutile upon heating. For applications utilizing the photocatalytic properties of nanoscale anatase at elevated temperatures (over 600 °C) the issue of phase stabilisation is of major interest. In this study, binary TiO2/SiO2 particles were synthesized by a flame aerosol process with TiCl4 and SiCl4 as precursors. The theoretical Si/Ti ratio was varied in the range of 0.7-1.3 mol/mol. The synthesized TiO2/SiO2 samples were heat treated at 900 and 1,000 °C for 3 h to determine the thermostability of anatase. Pyrogenic TiO2 P25 (from Evonik/Degussa, Germany) widely applied as photocatalyst was used as non-thermostabilized reference material for comparison of photocatalytic activity of powders. Both the non-calcinated and calcinated powders were characterized by means of XRD, TEM and BET. Photocatalytic activity was examined with dichloroacetic acid (DCA) chosen as a model compound. It was found that SiO2 stabilized the material retarding the collapse of catalyst surface area during calcination. The weighted anatase content of 85% remains completely unchanged even after calcination at 1,000 °C. The presence of SiO2 layer/bridge as spacer between TiO2 particles freezes the grain growth: the average crystallite size increased negligibly from 17 to 18 nm even during the calcination at 1,000 °C. Due to the stabilizing effect of SiO2 the titania nanoparticles calcinated at 900 and 1,000 °C show significant photocatalytic activity. Furthermore, the increase in photocatalytic activity with calcination temperature indicates that the titania surface becomes more accessible either due to intensified cracking of the SiO2 layer or due to enhanced transport of SiO2 into the necks thus releasing additional titania surface.

A floating macro/mesoporous crystalline anatase TiO2 ceramic with enhanced photocatalytic performance for recalcitrant wastewater degradation.

PubMed

Xing, Zipeng; Zhou, Wei; Du, Fan; Qu, Yang; Tian, Guohui; Pan, Kai; Tian, Chungui; Fu, Honggang

2014-01-14

A macro/mesoporous anatase TiO2 ceramic floating photocatalyst has been successfully synthesized using highly thermally stable mesoporous TiO2 powder as a precursor, followed by a camphene-based freeze-casting process and high-temperature calcinations. The ceramics are characterized in detail by X-ray diffraction, Raman spectra, scanning electron microscopy, transmission electron microscopy and N2 adsorption-desorption isotherms. The results indicate that the TiO2 ceramics present hierarchical macro/mesoporous structures, which maintain high porosity and high compressive strength at the optimal sintering temperature of 800 °C. The ordered mesoporous TiO2 network still possesses high thermal stability and inhibits the anatase-to-rutile phase transformation during calcinations. The obtained ceramics exhibit good adsorptive and photocatalytic activity for the degradation of octane and rhodamine B, and the total organic carbon removal ratio is up to 98.8% and 98.6% after photodegradation for 3 h, respectively. The roles of active species in the photocatalytic process are compared using different types of active species scavengers, and the degradation mechanism is also proposed. Furthermore, the ceramics are recyclable, and no clear changes are observed after ten cycles. In addition, the ceramics are also active in the photodegradation of phenol, thiobencarb, and atrazine. Therefore, these novel floating photocatalysts will have wide applications, including the removal of floating organic pollutants from the wastewater surfaces or the removal of soluble organic pollutants from wastewater.

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

The Influence of Cr3+ on TiO2 Crystal Growth and Photoactivity Properties

NASA Astrophysics Data System (ADS)

Wahyuningsih, S.; Hidayatika, W. N.; Sari, P. L.; Sari, P. P.; Hidayat, R.; Munawaroh, H.; Ramelan, A. H.

2018-03-01

The photocatalyst technology is an integrated combination of photochemical processes and catalysis in order to carry out a chemical transformation reaction. One of the semiconductor materials that have good photocatalytic activity is TiO2 anatase. This study aim to determine the effect of the Cr3+ addition on the growth of TiO2 rutile crystal and the increasing of TiO2 photoactivity. Diffractogram X-Ray of the samples showed that the synthesized TiO2 at 400 °C has been produced 100% TiO2 anatase. Synthesis of TiO2 doped Cr3+ composite was using wet impregnation method. The TiO2 doped Cr3+ composites have beed grown by annealed at a temperature of 300, 400, 500, 600 and 700 °C, respectively Annealing process have capabled to gain to the TiO2 doped Cr3+ nanocomposite. The result product annealed at 500 °C only appear anatase phase due to the Cr3+ addition influence that was able to suppress the growth of rutile. Identification of TiO2 doped Cr3+ composite using Fourier Transform Infra-Red (FT-IR) showed O-Cr vibration at 2283.72 cm-1. The TiO2 doped Cr3+ photoactivity was studied to degrade Rhodamin B. The best result on photodegradation of Rhodamin B was performed by using TiO2 doped Cr3+ composite which was annealed at 700 °C i.e. 74.71%.

Electrical response of electron selective atomic layer deposited TiO2‑x heterocontacts on crystalline silicon substrates

NASA Astrophysics Data System (ADS)

Ahiboz, Doğuşcan; Nasser, Hisham; Aygün, Ezgi; Bek, Alpan; Turan, Raşit

2018-04-01

Integration of oxygen deficient sub-stoichiometric titanium dioxide (TiO2‑x) thin films as the electron transporting-hole blocking layer in solar cell designs are expected to reduce fabrication costs by eliminating high temperature processes while maintaining high conversion efficiencies. In this paper, we conducted a study to reveal the electrical properties of TiO2‑x thin films grown on crystalline silicon (c-Si) substrates by atomic layer deposition (ALD) technique. Effect of ALD substrate temperature, post deposition annealing, and doping type of the c-Si substrate on the interface states and TiO2‑x bulk properties were extracted by performing admittance (C-V, G-V) and current-voltage (J-V) measurements. Moreover, the asymmetry in C-V and J-V measurements between the p-n type and n-n TiO2‑x-c-Si heterojunction types were examined and the electron transport selectivity of TiO2‑x was revealed.

SnO 2 nanowires decorated with forsythia-like TiO 2 for photoenergy conversion

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

Park, Ik Jae; Park, Sangbaek; Kim, Dong Hoe

Here, we report forsythia-like TiO 2-decorated SnO 2 nanowires on fluorine-doped SnO 2 electrode as a photoelectrode of dye-sensitized solar cells. When SnO 2 nanowires grown via vapor-liquid-solid reaction were soaked in TiCl 4 solution, leaf-shaped rutile TiO 2 was grown onto the surface of the nanowires. The TiO 2 decoration increases the short circuit current (J sc), open circuit voltage (V oc) and fill factor (FF) of dye-sensitized solar cells. Further, electron lifetime increased by employing an atomic-layer-deposited TiO 2 nanoshell between the TiO 2 leaves and the SnO 2 nanowire, due to preventing charge recombination at the nanowire/electrolytemore » interface.« less

SnO 2 nanowires decorated with forsythia-like TiO 2 for photoenergy conversion

DOE PAGES

Park, Ik Jae; Park, Sangbaek; Kim, Dong Hoe; ...

2017-05-17

Here, we report forsythia-like TiO 2-decorated SnO 2 nanowires on fluorine-doped SnO 2 electrode as a photoelectrode of dye-sensitized solar cells. When SnO 2 nanowires grown via vapor-liquid-solid reaction were soaked in TiCl 4 solution, leaf-shaped rutile TiO 2 was grown onto the surface of the nanowires. The TiO 2 decoration increases the short circuit current (J sc), open circuit voltage (V oc) and fill factor (FF) of dye-sensitized solar cells. Further, electron lifetime increased by employing an atomic-layer-deposited TiO 2 nanoshell between the TiO 2 leaves and the SnO 2 nanowire, due to preventing charge recombination at the nanowire/electrolytemore » interface.« less

Three-dimensional ruthenium-doped TiO 2 sea urchins for enhanced visible-light-responsive H 2 production

DOE PAGES

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

2016-05-23

Here, three-dimensional (3D) monodispersed sea urchin-like Ru-doped rutile TiO 2 hierarchical architectures composed of radially aligned, densely-packed TiO 2 nanorods have been successfully synthesized via an acid-hydrothermal method at low temperature without the assistance of any structure-directing agent and post annealing treatment. The addition of a minuscule concentration of ruthenium dopants remarkably catalyzes the formation of the 3D urchin structure and drives the enhanced photocatalytic H 2 production under visible light irradiation, not possible on undoped and bulk rutile TiO 2. Increasing ruthenium doping dosage not only increases the surface area up to 166 m 2 g –1 but alsomore » induces enhanced photoresponse in the regime of visible and near infrared light. The doping introduces defect impurity levels, i.e. oxygen vacancy and under-coordinated Ti 3+, significantly below the conduction band of TiO 2, and ruthenium species act as electron donors/acceptors that accelerate the photogenerated hole and electron transfer and efficiently suppress the rapid charge recombination, therefore improving the visible-light-driven activity.« less

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.

Facile synthesis of GO@SnO2/TiO2 nanofibers and their behavior in photovoltaics.

PubMed

Mohamed, Ibrahim M A; Dao, Van-Duong; Yasin, Ahmed S; Choi, Ho-Suk; Khalil, KhalilAbdelrazek; Barakat, Nasser A M

2017-03-15

Chemical doping is a widely-used strategy to improve the performance of TiO 2 for the dye-sensitized solar cells (DSCs). However, the effect of two efficient dopants has been rarely investigated. We present the synthesis of GO@SnO 2 /TiO 2 nanofibers (NFs) by a facile method using electrospinning and hydrothermal processes. The synthesized NFs are described in terms of morphology, crystallinity and chemistry through FESEM, TEM, HR-TEM, XRD, EDX, XPS, FT-IR and Raman spectra. As the results, the axial ratio and the average diameter of NFs decreased after the hydrothermal treatment and calcination process, respectively. The prepared Titania-based nanofibers have 81.82% anatase and 18.18% rutile-structure. The developed materials are applied as working electrodes of DSCs. The photovoltaic performances showed that the efficiency of the device employed GO@SnO 2 /TiO 2 photoanode gave 5.41%, which was higher than those of cells fabricated with SnO 2 /TiO 2 NFs (3.41%) and GO@TiO 2 NFs (4.52%) photoanodes. The photovoltaic parameters such as J sc , V oc , FF and R ct are calculated and found to be 11.19mAcm -2 , 0.72V, 0.67 and 9.26Ω, respectively. The high photovoltaic response of DSC based of GO@SnO 2 /TiO 2 NFs may be attributed to the large surface area of the NFs, and the low electron recombination. Furthermore, the start-stop switches of the cell devices with the developed photoanode affirmed the stability and photovoltaic performance of the cell. Copyright © 2016 Elsevier Inc. All rights reserved.

Raman Microspectroscopic Mapping with Multivariate Curve Resolution-Alternating Least Squares (MCR-ALS) Applied to the High-Pressure Polymorph of Titanium Dioxide, TiO2-II.

PubMed

Smith, Joseph P; Smith, Frank C; Ottaway, Joshua; Krull-Davatzes, Alexandra E; Simonson, Bruce M; Glass, Billy P; Booksh, Karl S

2017-08-01

The high-pressure, α-PbO 2 -structured polymorph of titanium dioxide (TiO 2 -II) was recently identified in micrometer-sized grains recovered from four Neoarchean spherule layers deposited between ∼2.65 and ∼2.54 billion years ago. Several lines of evidence support the interpretation that these layers represent distal impact ejecta layers. The presence of shock-induced TiO 2 -II provides physical evidence to further support an impact origin for these spherule layers. Detailed characterization of the distribution of TiO 2 -II in these grains may be useful for correlating the layers, estimating the paleodistances of the layers from their source craters, and providing insight into the formation of the TiO 2 -II. Here we report the investigation of TiO 2 -II-bearing grains from these four spherule layers using multivariate curve resolution-alternating least squares (MCR-ALS) applied to Raman microspectroscopic mapping. Raman spectra provide evidence of grains consisting primarily of rutile (TiO 2 ) and TiO 2 -II, as shown by Raman bands at 174 cm -1 (TiO 2 -II), 426 cm -1 (TiO 2 -II), 443 cm -1 (rutile), and 610 cm -1 (rutile). Principal component analysis (PCA) yielded a predominantly three-phase system comprised of rutile, TiO 2 -II, and substrate-adhesive epoxy. Scanning electron microscopy (SEM) suggests heterogeneous grains containing polydispersed micrometer- and submicrometer-sized particles. Multivariate curve resolution-alternating least squares applied to the Raman microspectroscopic mapping yielded up to five distinct chemical components: three phases of TiO 2 (rutile, TiO 2 -II, and anatase), quartz (SiO 2 ), and substrate-adhesive epoxy. Spectral profiles and spatially resolved chemical maps of the pure chemical components were generated using MCR-ALS applied to the Raman microspectroscopic maps. The spatial resolution of the Raman microspectroscopic maps was enhanced in comparable, cost-effective analysis times by limiting spectral resolution

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

PubMed

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

2016-09-28

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

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).

Donor defects and small polarons on the TiO2(110) surface

NASA Astrophysics Data System (ADS)

Moses, P. G.; Janotti, A.; Franchini, C.; Kresse, G.; Van de Walle, C. G.

2016-05-01

The role of defects in the chemical activity of the rutile TiO2(110) surface remains a rich topic of research, despite the rutile (110) being one of the most studied surfaces of transition-metal oxides. Here, we present results from hybrid functional calculations that reconcile apparently disparate views on the impact of donor defects, such as oxygen vacancies and hydrogen impurities, on the electronic structure of the (110) rutile surface. We find that the bridging oxygen vacancy and adsorbed or substitutional hydrogen are actually shallow donors, which do not induce gap states. The excess electrons from these donor centers tend to localize in the form of small polarons, which are the factual cause of the deep states ˜1 eV below the conduction band, often observed in photoelectron spectroscopy measurements. Our results offer a new framework for understanding the surface electronic structure of TiO2 and related oxides.

Synthesis and Characterization Hierarchical Three-Dimensional TiO2 Structure via Hydrothermal Method

NASA Astrophysics Data System (ADS)

Syuhada, N.; Yuliarto, B.; Nugraha

2018-05-01

TiO2 is one of the most potential candidates due to its fascinating properties for multi-discipline fields. One dimensional nanostructure TiO2 such as nanotube and nanorods has been widely used for many devices technology. Compare with one-dimensional nanostructure TiO2; the hierarchical TiO2 has not been widely applied. Three dimensional TiO2 play a promising role for application in many different fields such as photovoltaics, photocatalytic and a gas sensor. Herein, we report that the hierarchically structures TiO2 have been successfully obtained by the one-pot Hydrothermal process. The growth mechanism of Titania was controlled by Titanium (IV) isopropoxide (TTIP). Ethylene glycol (EG). Hydrochloric acid (HCl). Hexadecyltrimethylammonium bromide (CTAB) molar ratio. TTIP was used as titanium source and CTAB as a soft template. The molar ratio of TTIP. EG. HCl. CTAB was 0.1:0.2:0.4:0.001. Those samples were synthesized using the hydrothermal method at 180 °C for 20 h. The purpose of this work was focused on investigating morphology, crystallite size, crystalline phase, and particle size. The properties of these materials were characterized by XRay Diffraction, Energy Dispersive Spectroscopy and Scanning Electron Microscope. It was found all particles exhibited unique spherical morphology which arranged by nanorods and good distribution nanoparticle. The Average size of the sphere has range 1 µm to 3 µm with diameter nanorods 60 nm to 100 nm. The TiO2 spheres were constructed of interconnected nanorods and formed a three dimensional (3D) porous framework. XRD analysis confirmed that sample consisted of pure rutile crystal structure with crystallite size was 50 nm, and EDS revealed an elemental content of Ti 61.03 % and O 38.97 %.

He+ ion irradiation response of Fe–TiO2 multilayers

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

Anderoglu, O.; Zhou, M. J.; Zhang, J.

2013-04-01

The accumulation of radiation-induced defect clusters and He bubble formation in He+ ion irradiated nanocrystalline TiO2 and Fe–TiO2 multilayer thin films were investigated using transmission electron microscopy (TEM). Prior to ion irradiation it was found that the crystallinity of TiO2 layers depends on the individual layer thickness: While all TiO2 layers are amorphous at 5 nm individual layer thickness, at 100 nm they are crystalline with a rutile polymorph. After He+ irradiation up to ~6 dpa at room temperature, amorphization of TiO2 layers was not observed in both nanocrystalline TiO2 single layers and Fe–TiO2 multilayers. The suppression of radiation-induced amorphizationmore » in TiO2 is interpreted in terms of a high density of defect sinks in these nano-composites in the form of Fe–TiO2 interphase boundaries and columnar grains within each layer with nano-scale intercolumnar porosity. In addition, a high concentration of He is believed to be trapped at these interfaces in the form of sub-nanometer-scale clusters retarding the formation of relatively larger He bubbles that can be resolved in TEM.« less

Rutile solubility in hydrous rhyolite melts at 750-900 °C and 2 kbar, with application to titanium-in-quartz (TitaniQ) thermobarometry

NASA Astrophysics Data System (ADS)

Kularatne, Kanchana; Audétat, Andreas

2014-01-01

The solubility of rutile in water-saturated haplogranite melts with molar Al/(Na + K)-ratios ranging from 0.84 to 1.25 was determined at 750-900 °C and 2 kbar in cold-seal pressure vessel experiments. Due to the low diffusivity of Ti at these conditions a new method was developed to determine TiO2 solubility. In this method, glasses with TiO2 gradients were used as starting material, and after the experiments the TiO2 content was measured at the contact between rutile-bearing and rutile-free glass. The glasses were either directly equilibrated at the desired P-T conditions (i.e., crystallization experiments), or first treated at 50-150 °C lower temperatures and then subjected to the desired conditions (i.e., dissolution experiments). The results obtained in crystallization and dissolution experiments agree well with each other, suggesting that equilibrium was attained. Rutile solubility in peralkaline melts strongly increases with temperature and the amount of excess alkalies according to the relation: log TiO2 (wt%)=(1.8∗ΔANK-0.53)∗10,000/T-(12.8∗ΔANK-4.3) in which ΔANK is the deviation of the molar Al/(Na + K)-ratio from unity and T is given in Kelvin. Excess alumina does not seem to promote TiO2 solubility. For natural melt compositions it was found that if Ca, Mg and Fe are assumed to be 10 times less effective in promoting TiO2 solubility than excess Na and K, good fits to previous solubility data in silicic (⩾70 wt% SiO2) melts at upper crustal pressures (⩽10 kbar) are obtained. Application of this extended TiO2 solubility model to natural melt inclusions in quartz phenocrysts from five silicic volcanic systems returns TiO2 activities that are similar to those calculated with a previous experiment-based model and to those calculated from pairs of coexisting Fe-Ti-oxides, but are up to 2.9 times higher than those calculated with MELTS and rhyolite-MELTS. Pressures calculated from Ti concentrations in the host quartz using the most recent

Arsenic Sorption on TiO2 Nanoparticles: Size And Crystallinity Effects

EPA Science Inventory

Single solute As (III) and As (V) sorption on nano-sized amorphous and crystalline TiO₂ was investigated to determine: size and crystallinity effects on arsenic sorption capacities, possible As (III) oxidation, and the nature of surface complexes. Amorphous and cryst...

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

Single step synthesis of rutile TiO{sub 2} nanoflower array film by chemical bath deposition method

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

Dhandayuthapani, T.; Sivakumar, R.; Ilangovan, R., E-mail: rilangovan@yahoo.com

2016-05-06

Titanium oxide (TiO{sub 2}) 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 TiO{sub 2} nanoflower array films suitable for device applications has been reported. Rutile TiO{sub 2} 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 presencemore » of rutile phase polycrystalline TiO{sub 2}. Micro-Raman study revealed the presence of surface phonon mode at 105 cm{sup −1} due to the phonon confinement effect (finite size effect), in addition with the rutile Raman active modes of B{sub 1}g (143 cm{sup −1}), Eg (442 cm{sup −1}) and A{sub 1}g (607 cm{sup −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.« less

Highly branched RuO2 Nanorods on Electrospun TiO2 Nanofibers toward Electrochemical Catalysts

NASA Astrophysics Data System (ADS)

Cho, Yukyung; Kim, Su-Jin; Lee, Nam-Suk; Kim, Myung Hwa; Lee, Youngmi

2014-03-01

We report a facile growth route to synthesize hierarchically grown single crystalline metallic RuO2 nanorods on electrospun TiO2 nanofibers via a combination of a simple vapour phase transport process with an electrospinning process. This synthetic strategy could be very useful to design a variety of highly branched network architectures of the functional hetero-nanostructures for electrochemical applications. Particularly, Ruthenium oxide (RuO2) 1-dimensional nanostructures can be used as the effective catalysts or electrochemical electrode materials. Thus, we first synthesize TiO2 nanofibers from mixture of titanium isopropoxide precursor and polymer and then ruthenium hydroxide precursor on TiO2 nanofibers are transformed into RuO2 nanorods by thermal treatment at 250oC in air. The crystalline structures of products are confirmed using scanning electron microscopy (FE-SEM), X-ray diffraction (XRD) spectrum, Raman spectroscopy, and high resolution electron microscopy (HRTEM). The fundamental electrochemical performances are examined using cyclic voltammetry (CV).

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 TiO 2 (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.

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.

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

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

Kim, Boseong; Li, Zhenjun; Kay, Bruce D.

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 andmore » 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.« less

Absolute band structure determination on naturally occurring rutile with complex chemistry: Implications for mineral photocatalysis on both Earth and Mars

NASA Astrophysics Data System (ADS)

Li, Yan; Xu, Xiaoming; Li, Yanzhang; Ding, Cong; Wu, Jing; Lu, Anhuai; Ding, Hongrui; Qin, Shan; Wang, Changqiu

2018-05-01

Rutile is the most common and stable form of TiO2 that ubiquitously existing on Earth and other terrestrial planets like Mars. Semiconducting mineral such as rutile-based photoredox reactions have been considered to play important roles in geological times. However, due to the inherent complexity in chemistry, the precision determination on band structure of natural rutile and the theoretical explanation on its solar-driven photochemistry have been hardly seen yet. Considering the multiple minor and trace elements in natural rutile, we firstly obtained the single-crystal crystallography, mineralogical composition and defects characteristic of the rutile sample by using both powder and single crystal X-ray diffraction, electron microprobe analysis and X-ray photoelectron spectroscopy. Then, the band gap was accurately determined by synchrotron-based O K-edge X-ray absorption and emission spectra, which was firstly applied to natural rutile due to its robustness on compositions and defects. The absolute band edges of the rutile sample was calculated by considering the electronegativity of the atoms, band gap and point of zero charge. Besides, after detecting the defect energy levels by photoluminescence spectra, we drew the schematic band structure of natural rutile. The band gap (2.7 eV) of natural rutile was narrower than that of synthetic rutile (3.0 eV), and the conduction and valence band edges of natural rutile at pH = pHPZC were determined to be -0.04 V and 2.66 V (vs. NHE), respectively. The defect energy levels located at nearly the middle position of the forbidden band. Further, we used theoretical calculations to verify the isomorphous substitution of Fe and V for Ti gave rise to the distortion of TiO6 octahedron and created vacancy defects in natural rutile. Based on density functional theory, the narrowed band gap was interpreted to the contribution of Fe-3d and V-3d orbits, and the defect energy state was formed by hybridization of O-2p and Fe/V/Ti-3d

Enhanced photoelectrical performance of dye-sensitized solar cells with double-layer TiO2 on perovskite SrTiO3 substrate

NASA Astrophysics Data System (ADS)

Liu, Qiuhong; Sun, Qiong; Zhang, Min; Li, Yang; Zhao, Mei; Dong, Lifeng

2016-04-01

In this research, perovskite SrTiO3 particles are synthesized by a hydrothermal method, and TiO2 with a double-layer structure is grown on the SrTiO3 surface by a hydrolysis-condensation process. Structural characterizations reveal that TiO2 comprises of two phases: anatase film at the bottom and single-crystal rutile nanorods grown along the [110] direction on top. The TiO2-SrTiO3 composite film is investigated as photoanode material for dye-sensitized solar cells. In comparison with pure TiO2 and SrTiO3, the composite photoanode shows a much better performance in photoelectric conversion efficiency (1.35 %), which is about 2 and 100 times as efficient as pure TiO2 and SrTiO3, respectively. This indicates that the composite structure can facilitate charge carrier transfer and reduce electron-hole recombination to enhance photoelectrical properties of TiO2-based photoanode materials.

Fine-grained rutile in the Gulf of Maine: Diagenetic origin, source rocks, and sedimentary environment of deposition

USGS Publications Warehouse

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

1990-01-01

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

Crystallization of TiO2 Nanotubes by In Situ Heating TEM

PubMed Central

Casu, Alberto; Lamberti, Andrea

2018-01-01

The thermally-induced crystallization of anodically grown TiO2 amorphous nanotubes has been studied so far under ambient pressure conditions by techniques such as differential scanning calorimetry and in situ X-ray diffraction, then looking at the overall response of several thousands of nanotubes in a carpet arrangement. Here we report a study of this phenomenon based on an in situ transmission electron microscopy approach that uses a twofold strategy. First, a group of some tens of TiO2 amorphous nanotubes was heated looking at their electron diffraction pattern change versus temperature, in order to determine both the initial temperature of crystallization and the corresponding crystalline phases. Second, the experiment was repeated on groups of few nanotubes, imaging their structural evolution in the direct space by spherical aberration-corrected high resolution transmission electron microscopy. These studies showed that, differently from what happens under ambient pressure conditions, under the microscope’s high vacuum (p < 10−5 Pa) the crystallization of TiO2 amorphous nanotubes starts from local small seeds of rutile and brookite, which then grow up with the increasing temperature. Besides, the crystallization started at different temperatures, namely 450 and 380 °C, when the in situ heating was performed irradiating the sample with electron beam energy of 120 or 300 keV, respectively. This difference is due to atomic knock-on effects induced by the electron beam with diverse energy. PMID:29342894

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-

Uptake of TiO2 Nanoparticles into C. elegans Neurons Negatively Affects Axonal Growth and Worm Locomotion Behavior.

PubMed

Hu, Chun-Chih; Wu, Gong-Her; Hua, Tzu-En; Wagner, Oliver I; Yen, Ta-Jen

2018-03-14

We employ model organism Caenorhabditis elegans to effectively study the toxicology of anatase and rutile phase titanium dioxide (TiO 2 ) nanoparticles (NPs). The experimental results show that nematode C. elegans can take up fluorescein isothiocyanate-labeled TiO 2 NPs and that both anatase and rutile TiO 2 NPs can be detected in the cytoplasm of cultured primary neurons imaged by transmission electron microscopy. After TiO 2 NP exposure, these neurons also grow shorter axons, which may be related to the detected impeded worm locomotion behavior. Furthermore, anatase TiO 2 NPs did not affect the worm's body length; however, we determined that a concentration of 500 μg/mL of anatase TiO 2 NPs reduced the worm population by 50% within 72 h. Notably, rutile TiO 2 NPs negatively affect both the body size and worm population. Worms unable to enter the L4 larval stage explain a severe reduction in the worm population at TiO 2 NPs LC 50 /3d. To obtain a better understanding of the cellular mechanisms involved in TiO 2 NP intoxication, DNA microarray assays were employed to determine changes in gene expression in the presence or absence of TiO 2 NP exposure. Our data reveal that three genes (with significant changes in expression levels) were related to metal binding or metal detoxification (mtl-2, C45B2.2, and nhr-247), six genes were involved in fertility and reproduction (mtl-2, F26F2.3, ZK970.7, clec-70, K08C9.7, and C38C3.7), four genes were involved in worm growth and body morphogenesis (mtl-2, F26F2.3, C38C3.7, and nhr-247), and five genes were involved in neuronal function (C41G6.13, C45B2.2, srr-6, K08C9.7, and C38C3.7).

Improved hydrogen storage properties of MgH2 catalyzed with TiO2

NASA Astrophysics Data System (ADS)

Jangir, Mukesh; Meena, Priyanka; Jain, I. P.

2018-05-01

In order to improve the hydrogenation properties of the MgH2, various concentration of rutile Titanium Oxide (TiO2) (X wt%= 5, 10, 15 wt %) is added to MgH2 by ball milling and the catalytic effect of TiO2 on hydriding/dehydriding properties of MgH2 has been investigated. Result shows that the TiO2 significantly reduced onset temperature of desorption. Onset temperature as low as 190 °C were observed for the MgH2-15 wt% TiO2 sample which is 60 °C and 160 °C lower than the as-milled and as-received MgH2. Fromm the Kissinger plot the activation energy of 15 wt% TiO2 added sample is calculated to be -75.48 KJ/mol. These results indicate that the hydrogenation properties of MgH2-TiO2 have been improved compared to the as-milled and as-received MgH2. Furthermore, XRD and XPS were performed to characterize the structural evolution upon milling and dehydrogenation.

Few layer graphene wrapped mixed phase TiO2 nanofiber as a potential electrode material for high performance supercapacitor applications

NASA Astrophysics Data System (ADS)

Thirugnanam, Lavanya; Sundara, Ramaprabhu

2018-06-01

A combination of favorable composition and optimized anatase/rutile mixed-phase TiO2 (MPTNF)/Hydrogen exfoliated graphene (HEG) composite nanofibers (MPTNF/HEG) and anatase/rutile mixed-phase TiO2/reduced graphene oxide (rGO) composite nanofibers (MPTNF/rGO) have been reported to enhance the electrochemical properties for supercapacitor applications. These composite nanofibers have been synthesized by an efficient route of electrospinning together with the help of easy chemical methods. Both the composites exhibit good charge storage capability with enhanced pseudocapacitance and electric double-layer capacitance (EDLC) as confirmed by cyclic voltammetry studies. MPTNF/HEG composite showed maximum specific capacitance of 210.5 F/g at the current density of 1 A/g, which was mainly due to its availability of the more active sites for ions adsorption on a few layers of graphene wrapped TiO2 nanofiber surface. The synergistic effect of anatase/rutile mixed phase with one dimensional nanostructure and the electronic interaction between TiO2 and few layer graphene provided the subsequent improvement of ion adsorption capacity. Also exhibit excellent electrochemical performance to improve the capacitive properties of TiO2 electrode materials which is required for the development of flexible electrodes in energy storage devices and open up new opportunities for high performance supercapacitors.

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

PubMed

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

2013-11-01

Films of TiO2 nanotubes distributed over the inner surface of a discharge reactor cylinder (CTD) or adhered to a stainless steel electrode surface (PTD) in a discharge reactor were compared with a single-discharge (SD) system to investigate their efficiencies in phenol degradation. Morphology studies indicated that the TiO2 film was destroyed in the PTD system, but that there was no change in the CTD system after discharge. X-ray diffraction results revealed that the anatase phase of the original sample was preserved in the CTD system, but that an anatase-to-rutile phase transformation occurred in the PTD system after discharge. The highest efficiencies of phenol degradation and total organic carbon (TOC) mineralization were observed in the CTD system, and there was no decrease in phenol degradation efficiency upon reuse of a TiO2 film, indicating high catalysis activity and stability of the TiO2 photocatalysts in the combined treatment. TiO2 photocatalysts favored the formation of hydrogen peroxide and disfavored the formation of ozone. A greater degree of oxidation of intermediates and higher energy efficiency in phenol oxidation were observed with the TiO2-plasma systems, especially in the CTD system, compared to those with the SD system. Copyright © 2013 Elsevier Inc. All rights reserved.

Influence of microstructure and chemical composition of sputter deposited TiO2 thin films on in vitro bioactivity.

PubMed

Lilja, Mirjam; Genvad, Axel; Astrand, Maria; Strømme, Maria; Enqvist, Håkan

2011-12-01

Functionalisation of biomedical implants via surface modifications for tailored tissue response is a growing field of research. Crystalline TiO(2) has been proven to be a bone bioactive, non-resorbable material. In contact with body fluids a hydroxyapaptite (HA) layer forms on its surface facilitating the bone contact. Thus, the path of improving biomedical implants via deposition of crystalline TiO(2) on the surface is interesting to follow. In this study we have evaluated the influence of microstructure and chemical composition of sputter deposited titanium oxide thin films on the in vitro bioactivity. We find that both substrate bias, topography and the flow ratio of the gases used during sputtering affect the HA layer formed on the films after immersion in simulated body fluid at 37°C. A random distribution of anatase and rutile crystals, formed at negative substrate bias and low Ar to O(2) gas flow ratios, are shown to favor the growth of flat HA crystal structures whereas higher flow ratios and positive substrate bias induced growth of more spherical HA structures. These findings should provide valuable information when optimizing the bioactivity of titanium oxide coatings as well as for tailoring process parameters for sputtered-based production of bioactive titanium oxide implant surfaces.

Bulk magnetic terahertz metamaterial based on TiO2 microresonators(Conference Presentation)

NASA Astrophysics Data System (ADS)

Kadlec, Christelle; Sindler, Michal; Dominec, Filip; Němec, Hynek; Elissalde, Catherine; Mounaix, Patrick; Kuzel, Petr

2017-05-01

Dielectric spheres with high permittivity represent a Mie resonance-based metamaterial. Owing to its high far-infrared permittivity and low dielectric losses, TiO2 is a suitable material for the realization of magnetic metamaterials based on micro-resonators for the terahertz (THz) range. In a previous work, we experimentally demonstrated the magnetic effective response of TiO 2 microspheres dispersed in air, forming nearly a single-layer sample enclosed between two sapphire wafers [1]. Here we embedded the polycrystalline TiO2 microparticles into a polyethylene matrix, which enabled us to prepare a rigid bulk metamaterial with a controllable concentration of micro- resonators. TiO2 microspheres with a diameter of a few tens of micrometers were prepared by a bottom up approach. A liquid suspension of TiO2 nanoparticles was first spray-dried producing fragile TiO2 microspheres. These were subsequently sintered in a furnace at 1200° C for two hours, in order to consolidate individually each sphere. The particles show polycrystalline rutile structure with a porosity of 15%. The microspheres were finally sieved and sorted along their diameters in order to obtain a narrow size distribution. They were mixed with polyethylene powder and a pressure of 14 MPa was used to prepare rigid pellets with random spatial distribution of the TiO2 microspheres. Using finite-difference time-domain simulations, we investigated how the filling fraction and the ratio between the permittivities of the microspheres and the host matrix affect the position and the strength of the magnetic response associated with the lowest Mie mode. We found that a range of negative effective magnetic permeability can be achieved for sufficiently high filling factors and contrasts between the permittivities of the resonators and the embedding medium. Using time-domain THz spectroscopy we experimentally characterized the response of the realized structures and confirmed the magnetic character of their

Solvothermal synthesis of stable nanoporous polymeric bases-crystalline TiO2 nanocomposites: visible light active and efficient photocatalysts for water treatment

NASA Astrophysics Data System (ADS)

Liu, Fujian; Kong, Weiping; Wang, Liang; Noshadi, Iman; Zhang, Zhonghua; Qi, Chenze

2015-02-01

Visible light active and stable nanoporous polymeric base-crystalline TiO2 nanocomposites were solvothermally synthesized from in situ copolymerization of divinylbenzene (DVB) with 1-vinylimidazolate (VI) or 4-vinylpyridine (Py) in the presence of tetrabutyl titanate without the use of any other additives (PDVB-VI-TiO2-x, PDVB-Py-TiO2-x, where x stands for the molar ratio of TiO2 to VI or Py), which showed excellent activity with respect to catalyzing the degradation of organic pollutants of p-nitrophenol (PNP) and rhodamine-B (RhB). TEM and SEM images show that PDVB-VI-TiO2-x and PDVB-Py-TiO2-x have abundant nanopores, and TiO2 nanocrystals with a high degree of crystallinity were homogeneously embedded in the PDVB-VI-TiO2-x and PDVB-Py-TiO2-x, forming a stable ‘brick-and-mortar’ nanostructure. PDVB-VI and PDVB-Py supports act as the glue linking TiO2 nanocrystals to form nanopores and constraining the agglomeration of TiO2 nanocrystals. XPS spectra show evidence of unique interactions between TiO2 and basic sites in these samples. UV diffuse reflectance shows that PDVB-VI-TiO2-x and PDVB-Py-TiO2-x exhibit a unique response to visible light. Catalytic tests show that the PDVB-VI-TiO2-x and PDVB-Py-TiO2-x were active in catalyzing the degradation of PNP and RhB organic pollutants under visible light irradiation. The enhanced activities of the PDVB-VI-TiO2-x and PDVB-Py-TiO2-x were ascribed to synergistic effects between abundant nanopores and the unique optical adsorption of visible light in the samples.

Solvothermal synthesis of stable nanoporous polymeric bases-crystalline TiO2 nanocomposites: visible light active and efficient photocatalysts for water treatment.

PubMed

Liu, Fujian; Kong, Weiping; Wang, Liang; Noshadi, Iman; Zhang, Zhonghua; Qi, Chenze

2015-02-27

Visible light active and stable nanoporous polymeric base-crystalline TiO2 nanocomposites were solvothermally synthesized from in situ copolymerization of divinylbenzene (DVB) with 1-vinylimidazolate (VI) or 4-vinylpyridine (Py) in the presence of tetrabutyl titanate without the use of any other additives (PDVB-VI-TiO2-x, PDVB-Py-TiO2-x, where x stands for the molar ratio of TiO2 to VI or Py), which showed excellent activity with respect to catalyzing the degradation of organic pollutants of p-nitrophenol (PNP) and rhodamine-B (RhB). TEM and SEM images show that PDVB-VI-TiO2-x and PDVB-Py-TiO2-x have abundant nanopores, and TiO2 nanocrystals with a high degree of crystallinity were homogeneously embedded in the PDVB-VI-TiO2-x and PDVB-Py-TiO2-x, forming a stable 'brick-and-mortar' nanostructure. PDVB-VI and PDVB-Py supports act as the glue linking TiO2 nanocrystals to form nanopores and constraining the agglomeration of TiO2 nanocrystals. XPS spectra show evidence of unique interactions between TiO2 and basic sites in these samples. UV diffuse reflectance shows that PDVB-VI-TiO2-x and PDVB-Py-TiO2-x exhibit a unique response to visible light. Catalytic tests show that the PDVB-VI-TiO2-x and PDVB-Py-TiO2-x were active in catalyzing the degradation of PNP and RhB organic pollutants under visible light irradiation. The enhanced activities of the PDVB-VI-TiO2-x and PDVB-Py-TiO2-x were ascribed to synergistic effects between abundant nanopores and the unique optical adsorption of visible light in the samples.

The effect of amorphous TiO2 in P25 on dye-sensitized solar cell performance.

PubMed

Al-Attafi, Kadhim; Nattestad, Andrew; Wu, Qijie; Ide, Yusuke; Yamauchi, Yusuke; Dou, Shi Xue; Kim, Jung Ho

2018-01-04

P25 is one of the most widely used forms of titanium(iv) oxide (TiO 2 ), routinely utilised in dye-sensitised solar cells (DSCs), where it is often employed as a control, in spite of its poorly defined nature and the typically low device efficiency (or possibly because of this). Work by Park in 2000 and later by Lin et al. suggests that the rutile component might not be to blame for this, as has often been claimed. Recently it has been observed that P25 has quite a sizable amorphous content. A method to selectively remove this non-crystalline material has been developed, allowing for scrutiny of the role this amorphous material plays. Here we compare hydrothermally treated P25 (H-P25) with the as-received material, realizing solar-to-electric conversion efficiencies of 5.3% and 3.2% respectively. More importantly, this reveals important information about the detrimental effect of amorphous TiO 2 on DSC performance, with broader implications, as most researchers do not actively examine their synthesized materials for the presence of an amorphous component.

Characterization of nanosized TiO2 synthesized inside a porous glass ceramic monolith by metallo-organic decomposition process

NASA Astrophysics Data System (ADS)

Mazali, Italo Odone; Alves, Oswaldo Luiz

2005-01-01

This work reports the preparation of TiO2 by decomposition of a metallo-organic precursor (MOD process) in the pores of an α-NbPO5 glass-ceramic monolith (PGC-NbP) and the study of the TiO2 anatase-rutile transition phase. The impregnation of titanium di-(propoxy)-di-(2-ethylhexanoate) in the PGC-NbP was confirmed by diffuse reflectance infrared spectroscopy. In the restrictive porous environment the decomposition of the metallo-organic compound exhibits a lower initial decomposition temperature but a higher final decomposition temperature, in comparison to the free precursor. The pure TiO2 rutile phase is formed only above 700 °C when the titanium precursor is decomposed outside the pores. The TiO2 anatase obtained inside the PGC-NbP was stabilized up to 750 °C and exhibits a smaller average crystallite size in comparison with the MOD process performed without PGC-NbP. Furthemore, the temperature of the TiO2 anatase-rutile transformation depends on crystallite size, which was provided by XRD and Raman spectroscopy. The precursor impregnation-decomposition cycle revealed a linear mass increment inside PGC-NbP. Micro-Raman spectroscopy shows the presence of a gradient concentration of the TiO2 inside the PGC-NbP. The use of the MOD process in the PGC-NbP pores has several advantages: control of the amount and the nature of the phase formed and preservation of the pore structure of PGC-NbP for subsequent treatments and reactions.

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.

The effect of surfactant-free TiO2 surface hydroxyl groups on physicochemical, optical and self-cleaning properties of developed coatings on polycarbonate

NASA Astrophysics Data System (ADS)

Yaghoubi, H.; Dayerizadeh, A.; Han, S.; Mulaj, M.; Gao, W.; Li, X.; Muschol, M.; Ma, S.; Takshi, A.

2013-12-01

TiO2 is a prototypical transition metal oxide with physicochemical properties that can be modified more readily through sol-gel synthesis than through other techniques. Herein, we report on the change in the density of the hydroxyl groups on the surface of synthesized surfactant-free TiO2 nanoparticles in water due to varying the pH (7.3, 8.3, 9.3 and 10.3) of the peroxotitanium complex, i.e. the amorphous sol, prior to refluxing. This resulted in colloidal solutions with differing crystallinity, nanoparticle size, optical indirect bandgaps and photocatalytic activity. It was shown that increasing the density of hydroxyl groups on TiO2 particles coupled with low-temperature annealing (90 °C) induced an anatase to rutile transformation. Increasing the pH of the peroxotitanium complex interrupted the formation of anatase phase in crystalline sol, as evidenced by intensity increases of the Raman bands at ˜822 (Ti-O-H) and 906 cm-1 (vibrational Ti-O-H) and an intensity decrease of the band at 150 cm-1 (anatase photonic Eg). Films prepared from higher pH suspensions showed lower roughness. The reaction rate constants for photo-induced self-cleaning activity of TiO2 films prepared from colloidal solutions at pH 7.3, 8.3, 9.3 and 10.3 were estimated at 0.017 s-1, 0.014 s-1, 0.007 s-1 and 0.006 s-1, respectively.

Enhanced photovoltaic performance of novel TiO2 photoelectrode on TCO substrates for dye-sensitized solar cells.

PubMed

Nam, Jung Eun; Kwon, Soon Jin; Jo, Hyo Jeong; Yi, Kwang Bok; Kim, Dae-Hwan; Kang, Jin-Kyu

2014-12-01

In this study, we report synthesis and growth of rutile-anatase TiO2 thin film on fluorine-doped tin oxide (FTO) glass by a two-step hydrothermal method. The effects of additional treatments (i.e., TiCl4 post-treatment and seed layer formation were also studied. Photocurrent-voltage (I-V) measurement of rutile-anatase TiO2 thin film was performed under 1.5 G light illumination. Photovoltaic performance was investigated by incident photon-to-electron conversion efficiency (IPCE), electrochemical impedance spectroscopy (EIS), intensity-modulated photocurrent/photovoltage spectroscopy (IMVS/IMPS) and open-circuit photovoltage decay (OCVD).

Origin of colossal permittivity in (In1/2Nb1/2)TiO2via broadband dielectric spectroscopy.

PubMed

Zhao, Xiao-gang; Liu, Peng; Song, Yue-Chan; Zhang, An-ping; Chen, Xiao-ming; Zhou, Jian-ping

2015-09-21

(In1/2Nb1/2)TiO2 (IN-T) ceramics were prepared via a solid-state reaction route. X-ray diffraction (XRD) and Raman spectroscopy were used for the structural and compositional characterization of the synthesized compounds. The results indicated that the sintered ceramics have a single phase of rutile TiO2. Dielectric spectroscopy (frequency range from 20 Hz to 1 MHz and temperature range from 10 K to 270 K) was performed on these ceramics. The IN-T ceramics showed extremely high permittivities of up to ∼10(3), which can be referred to as colossal permittivity, with relatively low dielectric losses of ∼0.05. Most importantly, detailed impedance data analyses of IN-T demonstrated that electron-pinned defect-dipoles, interfacial polarization and polaron hopping polarization contribute to the colossal permittivity at high temperatures (270 K); however, only the complexes (pinned electron) and polaron hopping polarization are active at low temperatures (below 180 K), which is consistent with UDR analysis.

Rutile (β-)MnO2 surfaces and vacancy formation for high electrochemical and catalytic performance.

PubMed

Tompsett, David A; Parker, Stephen C; Islam, M Saiful

2014-01-29

MnO2 is a technologically important material for energy storage and catalysis. Recent investigations have demonstrated the success of nanostructuring for improving the performance of rutile MnO2 in Li-ion batteries and supercapacitors and as a catalyst. Motivated by this we have investigated the stability and electronic structure of rutile (β-)MnO2 surfaces using density functional theory. A Wulff construction from relaxed surface energies indicates a rod-like equilibrium morphology that is elongated along the c-axis, and is consistent with the large number of nanowire-type structures that are obtainable experimentally. The (110) surface dominates the crystallite surface area. Moreover, higher index surfaces than considered in previous work, for instance the (211) and (311) surfaces, are also expressed to cap the rod-like morphology. Broken coordinations at the surface result in enhanced magnetic moments at Mn sites that may play a role in catalytic activity. The calculated formation energies of oxygen vacancy defects and Mn reduction at key surfaces indicate facile formation at surfaces expressed in the equilibrium morphology. The formation energies are considerably lower than for comparable structures such as rutile TiO2 and are likely to be important to the high catalytic activity of rutile MnO2.

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

DOE PAGES

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

2006-01-01

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

Origin of colossal dielectric response in (In + Nb) co-doped TiO2 rutile ceramics: a potential electrothermal material.

PubMed

Ke, Shanming; Li, Tao; Ye, Mao; Lin, Peng; Yuan, Wenxiang; Zeng, Xierong; Chen, Lang; Huang, Haitao

2017-08-31

(In + Nb) co-doped TiO 2 (TINO) rutile is an emerging material with a colossal dielectric permittivity (CP) and a low dielectric loss over wide temperature and frequency ranges. The electrical inhomogeneous nature of TINO ceramics is demonstrated by direct local current probing with high-resolution conductive atomic force microscopy (cAFM). The CP response in TINO is found to originate from the electron-pinned defect dipole induced conductive cluster effect and the electrode effect. Two types of dielectric relaxations are simultaneously observed due to these two effects. With the given synthesis condition, we found TINO shows a highly leaky feature that impairs its application as a dielectric material. However, the fast-temperature-rising phenomenon found in this work may open a new door for TINO to be applied as a potential electrothermal material with high efficiency, oxidation-proof, high temperature stability, and energy saving.

Tuning the Phase and Microstructural Properties of TiO2 Films Through Pulsed Laser Deposition and Exploring Their Role as Buffer Layers for Conductive Films

NASA Astrophysics Data System (ADS)

Agarwal, S.; Haseman, M. S.; Leedy, K. D.; Winarski, D. J.; Saadatkia, P.; Doyle, E.; Zhang, L.; Dang, T.; Vasilyev, V. S.; Selim, F. A.

2018-04-01

Titanium oxide (TiO2) is a semiconducting oxide of increasing interest due to its chemical and thermal stability and broad applicability. In this study, thin films of TiO2 were deposited by pulsed laser deposition on sapphire and silicon substrates under various growth conditions, and characterized by x-ray diffraction (XRD), atomic force microscopy (AFM), optical absorption spectroscopy and Hall-effect measurements. XRD patterns revealed that a sapphire substrate is more suitable for the formation of the rutile phase in TiO2, while a silicon substrate yields a pure anatase phase, even at high-temperature growth. AFM images showed that the rutile TiO2 films grown at 805°C on a sapphire substrate have a smoother surface than anatase films grown at 620°C. Optical absorption spectra confirmed the band gap energy of 3.08 eV for the rutile phase and 3.29 eV for the anatase phase. All the deposited films exhibited the usual high resistivity of TiO2; however, when employed as a buffer layer, anatase TiO2 deposited on sapphire significantly improves the conductivity of indium gallium zinc oxide thin films. The study illustrates how to control the formation of TiO2 phases and reveals another interesting application for TiO2 as a buffer layer for transparent conducting oxides.

Self-organized TiO2 nanotube arrays in the photocatalytic degradation of methylene blue under UV light irradiation

NASA Astrophysics Data System (ADS)

Chung, Eun Hyuk; Baek, Seong Rim; Yu, Seong Mi; Kim, Jong Pil; Hong, Tae Eun; Kim, Hyun Gyu; Bae, Jong-Seong; Jeong, Euh Duck; Khan, F. Nawaz; Jung, Ok-sang

2015-04-01

Nanostructured titanium dioxide (NTiO2) is known to possess efficient photocatalytic activity and to have diverse applications in many fields due to its chemical stability, high surface area/volume ratio, high transmittance, and high refractive index in the visible and the near-ultraviolet regions. These facts prompted us to develop TiO2 nanotube (TiO2 NT) arrays through electrochemical anodic oxidation involving different electrolytes comprised of phosphoric acid — hydrofluoric acid aqueous systems by varying the voltage and the time. The annealing temperature of the nanotubes, TiO2 NTs, were varied to modify the surface morphology and were characterized by using X-ray diffraction and scanning electron microscopy. Scanning electron microscopy and X-ray diffraction results showed that the samples had uniform morphologies and good crystalline structures of the anatase phase at lower annealing temperatures and of the rutile phase at higher annealing temperatures. A secondary-ion mass-spectrometry analysis was used to investigate the surface atoms and to conduct a depth profile analysis of the TiO2 NTs. The efficiency of the photocatalytic activity of the TiO2 NT arrays in degrading methylene blue (MB) was investigated under UV-Vis light irradiation. The maximum photocatalytic activity was achieved for the samples with lower annealing temperatures due to their being in the anatase phase and having a higher surface area and a smaller crystal size, which play important roles in the degradation of organic pollutants.

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.

Sol-Gel Synthesis of Fe-Doped TiO2 Nanocrystals

NASA Astrophysics Data System (ADS)

Marami, Mohammad Bagher; Farahmandjou, Majid; Khoshnevisan, Bahram

2018-03-01

Fe-doped TiO2 powders were synthesized by the sol-gel method using titanium (IV) isopropoxide (TTIP) as the starting material, ethanol as solvent, and ethylene glycol (EG) as stabilizer. These prepared samples were characterized by x-ray diffractometer (XRD), field emission scanning electron microscope (FESEM), Fourier-transform infrared (FTIR) spectroscopy, diffuse reflection spectroscopy (DRS), energy-dispersive x-ray spectroscopy (EDX), and photoluminescence (PL) analyses to study their structure, morphology, and optical properties. The particle size of Fe-doped TiO2 was in the range of 18-39 nm and the minimum crystallite size was achieved for 4 mol.% of Fe. The XRD result of the samples that were doped with Fe showed a tetragonal structure. It also revealed the coexistence of the anatase and rutile phases, and showed that their ratio changed with various molar concentrations of Fe dopant. FTIR spectroscopy showed the presence of the Ti-O vibration band in the samples. PL analysis revealed the PL property in the UV region. Visible irradiation and the intensity of PL spectra were both reduced by doping TiO2 with 3 mol.% of Fe as compared to the pure variety. The spectra from the DRS showed a red shift and a reduction of 2.6 eV in the band gap energy for 4 mol.% Fe-doped TiO2. The optimum level of impurity (4 mol.%) for Fe-doped TiO2 nanoparticles (NPs), which improve the optical and electrical properties by using new precursors and can be used in solar cells and electronic devices, was determined. The novelty of this work consists of: the Fe/TiO2 NPs are synthesized by new precursors from sol-gel synthesis of iron and TTIP using acetic acid-catalyzed solvolysis (original idea) and the optical properties optimized with a mixture of phases (anatase/rutile) of Fe-doped TiO2 by this facile method.

Sol-Gel Synthesis of Fe-Doped TiO2 Nanocrystals

NASA Astrophysics Data System (ADS)

Marami, Mohammad Bagher; Farahmandjou, Majid; Khoshnevisan, Bahram

2018-07-01

Fe-doped TiO2 powders were synthesized by the sol-gel method using titanium (IV) isopropoxide (TTIP) as the starting material, ethanol as solvent, and ethylene glycol (EG) as stabilizer. These prepared samples were characterized by x-ray diffractometer (XRD), field emission scanning electron microscope (FESEM), Fourier-transform infrared (FTIR) spectroscopy, diffuse reflection spectroscopy (DRS), energy-dispersive x-ray spectroscopy (EDX), and photoluminescence (PL) analyses to study their structure, morphology, and optical properties. The particle size of Fe-doped TiO2 was in the range of 18-39 nm and the minimum crystallite size was achieved for 4 mol.% of Fe. The XRD result of the samples that were doped with Fe showed a tetragonal structure. It also revealed the coexistence of the anatase and rutile phases, and showed that their ratio changed with various molar concentrations of Fe dopant. FTIR spectroscopy showed the presence of the Ti-O vibration band in the samples. PL analysis revealed the PL property in the UV region. Visible irradiation and the intensity of PL spectra were both reduced by doping TiO2 with 3 mol.% of Fe as compared to the pure variety. The spectra from the DRS showed a red shift and a reduction of 2.6 eV in the band gap energy for 4 mol.% Fe-doped TiO2. The optimum level of impurity (4 mol.%) for Fe-doped TiO2 nanoparticles (NPs), which improve the optical and electrical properties by using new precursors and can be used in solar cells and electronic devices, was determined. The novelty of this work consists of: the Fe/TiO2 NPs are synthesized by new precursors from sol-gel synthesis of iron and TTIP using acetic acid-catalyzed solvolysis (original idea) and the optical properties optimized with a mixture of phases (anatase /rutile) of Fe-doped TiO2 by this facile method.

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

PubMed

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

2015-04-01

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

A study of the physical, chemical and biological properties of TiO2 coatings produced by micro-arc oxidation in a Ca-P-based electrolyte.

PubMed

dos Santos, Amanda; Araujo, Joyce R; Landi, Sandra M; Kuznetsov, Alexei; Granjeiro, José M; de Sena, Lidia Ágata; Achete, Carlos Alberto

2014-07-01

In this work, a porous and homogeneous titanium dioxide layer was grown on commercially pure titanium substrate using a micro-arc oxidation (MAO) process and Ca-P-based electrolyte. The structure and morphology of the TiO2 coatings were characterized by X-ray diffraction, scanning electron microscopy (SEM), transmission electron microscopy, and profilometry. The chemical properties were studied using electron dispersive X-ray spectroscopy (SEM-EDS) and X-ray photoelectron spectroscopy. The wettability of the coating was evaluated using contact angle measurements. During the MAO process, Ca and P ions were incorporated into the oxide layer. The TiO2 coating was composed of a mixture of crystalline and amorphous structures. The crystalline part of the sample consisted of a major anatase phase and a minor rutile phase. A cross-sectional image of the coating-substrate interface reveals the presence of voids elongated along the interface. An osteoblast culture was performed to verify the cytocompatibility of the anodized surface. The results of the cytotoxicity tests show satisfactory cell viability of the titanium dioxide films produced in this study.

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.

Electrical level of defects in single-layer two-dimensional TiO2

NASA Astrophysics Data System (ADS)

Song, X. F.; Hu, L. F.; Li, D. H.; Chen, L.; Sun, Q. Q.; Zhou, P.; Zhang, D. W.

2015-11-01

The remarkable properties of graphene and transition metal dichalcogenides (TMDCs) have attracted increasing attention on two-dimensional materials, but the gate oxide, one of the key components of two-dimensional electronic devices, has rarely reported. We found the single-layer oxide can be used as the two dimensional gate oxide in 2D electronic structure, such as TiO2. However, the electrical performance is seriously influenced by the defects existing in the single-layer oxide. In this paper, a nondestructive and noncontact solution based on spectroscopic ellipsometry has been used to detect the defect states and energy level of single-layer TiO2 films. By fitting the Lorentz oscillator model, the results indicate the exact position of defect energy levels depends on the estimated band gap and the charge state of the point defects of TiO2.

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

2017-07-05

Incorporating reduced graphene oxide (rGO) or Fe 3+ ions in TiO 2 photocatalyst could enhance photocatalytic degradation of organic contaminants in aqueous solutions. This study characterized the photocatalytic activities of TiO 2 -Fe and TiO 2 -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 TiO 2 -rGO and TiO 2 -Fe nanocomposites. Doping Fe into TiO 2 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 TiO 2 decreased significantly the intensity of TiO 2 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. TiO 2 -rGO exhibited higher photocatalytic activity for the degradation of pharmaceuticals under UV irradiation, while TiO 2 -Fe demonstrated more suitable for visible light oxidation. The results suggested that the enhanced photocatalytic performance of TiO 2 -rGO could be attributed to reduced recombination rate of photoexcited electrons-hole pairs, but for TiO 2 -Fe nanocomposite, narrower band gap would contribute to increased photocatalytic activity. Copyright © 2017 Elsevier B.V. All rights reserved.

Reaction Kinetics of Water Molecules with Oxygen Vacancies on Rutile TiO 2(110)

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

Petrik, Nikolay G.; Kimmel, Gregory A.

2015-09-16

The formation of bridging hydroxyls (OHb) via reactions of water molecules with oxygen vacancies (VO) on reduced TiO 2(110) surfaces is studied using infrared reflection-absorption spectroscopy (IRAS), electron-stimulated desorption (ESD), and photon-stimulated desorption (PSD). Narrow IRAS peaks at 2737 cm-1 and 3711 cm -1 are observed for stretching vibrations of OD b and OH b on TiO 2(110), respectively. IRAS measurements with s- and p-polarized light demonstrate that the bridging hydroxyls are oriented normal to the (110) surface. The IR peaks disappear after the sample is exposed to O 2 or annealed in the temperature range of 400 – 600more » K (correlating with the temperature at which pairs of OHb’s reform water and then desorb), which is consistent with their identification as bridging hydroxyls. We have studied the kinetics of water reacting with the vacancies by monitoring the formation of bridging hydroxyls (using IRAS) as a function of the annealing temperature for a small amount of water initially dosed on the TiO 2(110) at low temperature. Separate experiments have also monitored the loss of water molecules (using water ESD) and vacancies (using the CO photooxidation reaction) due to the reactions of water molecules with the vacancies. All three techniques show that the reaction rate becomes appreciable for T > 150 K and that the reactions largely complete for T > 250 K. The temperature-dependent water-VO reaction kinetics are consistent with a Gaussian distribution of activation energies with E a = 0.545 eV, ΔE a(FWHM) = 0.125 eV, and a “normal” prefactor, v = 10 12 s -1. In contrast, a single activation energy with a physically reasonable prefactor does not fit the data well. Our experimental activation energy is close to theoretical estimates for the diffusion of water molecules along the Ti 5c rows on the reduced TiO 2(110) surface, which suggests that the diffusion of water controls the water – V O reaction rate.« less

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

NASA Technical Reports Server (NTRS)

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

1972-01-01

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

Mesoporous titanium dioxide (TiO2) with hierarchically 3D dendrimeric architectures: formation mechanism and highly enhanced photocatalytic activity.

PubMed

Li, Xiao-Yun; Chen, Li-Hua; Rooke, Joanna Claire; Deng, Zhao; Hu, Zhi-Yi; Wang, Shao-Zhuan; Wang, Li; Li, Yu; Krief, Alain; Su, Bao-Lian

2013-03-15

Mesoporous TiO(2) with a hierarchically 3D dendrimeric nanostructure comprised of nanoribbon building units has been synthesized via a spontaneous self-formation process from various titanium alkoxides. These hierarchically 3D dendrimeric architectures can be obtained by a very facile, template-free method, by simply dropping a titanium butoxide precursor into methanol solution. The novel configuration of the mesoporous TiO(2) nanostructure in nanoribbon building units yields a high surface area. The calcined samples show significantly enhanced photocatalytic activity and degradation rates owing to the mesoporosity and their improved crystallinity after calcination. Furthermore, the 3D dendrimeric architectures can be preserved after phase transformation from amorphous TiO(2) to anatase or rutile, which occurs during calcination. In addition, the spontaneous self-formation process of mesoporous TiO(2) with hierarchically 3D dendrimeric architectures from the hydrolysis and condensation reaction of titanium butoxide in methanol has been followed by in situ optical microscopy (OM), revealing the secret on the formation of hierarchically 3D dendrimeric nanostructures. Moreover, mesoporous TiO(2) nanostructures with similar hierarchically 3D dendrimeric architectures can also be obtained using other titanium alkoxides. The porosities and nanostructures of the resultant products were characterized by SEM, TEM, XRD, and N(2) adsorption-desorption measurements. The present work provides a facile and reproducible method for the synthesis of novel mesoporous TiO(2) nanoarchitectures, which in turn could herald the fabrication of more efficient photocatalysts. Copyright © 2012 Elsevier Inc. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2012-10-01

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

D-sorbitol-induced phase control of TiO2 nanoparticles and its application for dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Shaikh, Shoyebmohamad F.; Mane, Rajaram S.; Min, Byoung Koun; Hwang, Yun Jeong; Joo, Oh-Shim

2016-02-01

Using a simple hydrothermal synthesis, the crystal structure of TiO2 nanoparticles was controlled from rutile to anatase using a sugar alcohol, D-sorbitol. Adding small amounts of D-sorbitol to an aqueous TiCl4 solution resulted in changes in the crystal phase, particle size, and surface area by affecting the hydrolysis rate of TiCl4. These changes led to improvements of the solar-to-electrical power conversion efficiency (η) of dye-sensitized solar cells (DSSC) fabricated using these nanoparticles. A postulated reaction mechanism concerning the role of D-sorbitol in the formation of rutile and anatase was proposed. Fourier-transform infrared spectroscopy, 13C NMR spectroscopy, and dynamic light scattering analyses were used to better understand the interaction between the Ti precursor and D-sorbitol. The crystal phase and size of the synthesized TiO2 nanocrystallites as well as photovoltaic performance of the DSSC were examined using X-ray diffraction, Raman spectroscopy, field-emission scanning electron microscopy, high-resolution transmission electron microscopy, and photocurrent density-applied voltage spectroscopy measurement techniques. The DSSC fabricated using the anatase TiO2 nanoparticles synthesized in the presence of D-sorbitol, exhibited an enhanced η (6%, 1.5-fold improvement) compared with the device fabricated using the rutile TiO2 synthesized without D-sorbitol.

Bi2O3 cocatalyst improving photocatalytic hydrogen evolution performance of TiO2

NASA Astrophysics Data System (ADS)

Xu, Difa; Hai, Yang; Zhang, Xiangchao; Zhang, Shiying; He, Rongan

2017-04-01

Photocatalytic hydrogen production using water splitting is of potential importance from the viewpoint of renewable energy development. Herein, Bi2O3-TiO2 composite photocatalysts presented as Bi-Bi2O3-anatase-rutile TiO2 multijunction were first fabricated by a simple impregnation-calcination method using Bi2O3 as H2-production cocatalysts. The obtained multijunction samples exhibit an obvious enhancement in photocatalytic H2 evolution activity in the presence of glycerol. The effect of Bi2O3 amount on H2-evolution activity of TiO2 was investigated and the optimal Bi2O3 content was found to be 0.89 mol%, achieving a H2-production rate of 920 μmol h-1, exceeding that of pure TiO2 by more than 73 times. The enhanced mechanism of photocatalytic H2-evolution activity is proposed. This study will provide new insight into the design and fabrication of TiO2-based hydrogen-production photocatalysts using low-cost Bi2O3 as cocatalyst.

Phase quantification by X-ray photoemission valence band analysis applied to mixed phase TiO2 powders

NASA Astrophysics Data System (ADS)

Breeson, Andrew C.; Sankar, Gopinathan; Goh, Gregory K. L.; Palgrave, Robert G.

2017-11-01

A method of quantitative phase analysis using valence band X-ray photoelectron spectra is presented and applied to the analysis of TiO2 anatase-rutile mixtures. The valence band spectra of pure TiO2 polymorphs were measured, and these spectral shapes used to fit valence band spectra from mixed phase samples. Given the surface sensitive nature of the technique, this yields a surface phase fraction. Mixed phase samples were prepared from high and low surface area anatase and rutile powders. In the samples studied here, the surface phase fraction of anatase was found to be linearly correlated with photocatalytic activity of the mixed phase samples, even for samples with very different anatase and rutile surface areas. We apply this method to determine the surface phase fraction of P25 powder. This method may be applied to other systems where a surface phase fraction is an important characteristic.

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.

Extremely enhanced photovoltaic properties of dye-sensitized solar cells by sintering mesoporous TiO2 photoanodes with crystalline titania chelated by acetic acid

NASA Astrophysics Data System (ADS)

Liu, Bo-Tau; Chou, Ya-Hui; Liu, Jin-Yan

2016-04-01

The study presents a significant improvement on the performance of dye-sensitized solar cells (DSSCs) through incorporating the crystalline titania chelated by acetic acid (TAc) into the mesoporous TiO2 photoanodes. The effects of TAc on the blocking layer, mesoporous TiO2 layer, and post-treatment have been investigated. The TAc blocking layer displays compact construction, revealing superior response time and resistance to suppress dark current compared to the blocking layer made from titanium(IV) isopropoxide (TTIP). The power conversion efficiency of DSSCs with the TAc treatment can reach as high as 10.49%, which is much higher than that of pristine DSSCs (5.67%) and that of DSSCs treated by TTIP (7.86%). We find that the TAc incorporation can lead to the decrease of charge transfer resistance and the increase of dye adsorption. The result may be attributed to the fact that the TAc possesses high crystallinity, exposed (101) planes, and acid groups chelated on surface, which are favorable for dye attachment and strong bonding at the FTO/TiO2 and the TiO2/TiO2 interfaces, These improvements result in the remarkable increase of photocurrent and thereby that of power conversion efficiency.

Nucleation and growth of hydroxyapatite on arc-deposited TiO2 surfaces studied by quartz crystal microbalance with dissipation

NASA Astrophysics Data System (ADS)

Lilja, Mirjam; Butt, Umer; Shen, Zhijian; Bjöörn, Dorota

2013-11-01

Understanding of nucleation and growth kinetics of biomimetically deposited hydroxyapatite (HA) on crystalline TiO2 surfaces is important with respect to the application and performance of HA as functional implant coatings. Arc-evaporation was used to deposit TiO2 coatings dominated by anatase phase, rutile phase or their mixtures. Subsequent formation of HA from phosphate buffered saline solution (PBS) was investigated in real-time using in situ quartz crystal microbalance with dissipation technique (QCM-D). Scanning electron microscopy (SEM) and X-ray diffraction (XRD) were employed to characterize the presence, morphology and crystal structure of TiO2 coatings and the formed HA. Increasing temperature of the PBS, increasing flow rate and applying a higher ion concentration in solution were found to accelerate HA nucleation process and hence affect growth kinetics. Lower PBS temperature resulted in the formation of HA coatings with flake-like morphology and increasing HA porosity. All TiO2 coatings under study enabled HA formation at body temperature, while in contrast Ti reference surfaces only supported HA nucleation and growth at elevated temperatures. QCM-D technique is a powerful tool for studying the impact of process parameters during biomimetic coating deposition on coating structure evolution in real time and provides valuable information for understanding, optimizing as well as tailoring the biomimetic HA growth processes.

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

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

Chen, Long; Li, Zhenjun; Smith, R. Scott

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 viamore » 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.« less

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.

Investigation of the dipole formation and growth behavior at In2O3|TiO2 heterojunctions using photoemission spectroscopy and atomic force microscopy

NASA Astrophysics Data System (ADS)

Schaefer, Michael; Halpegamage, Sandamali; Batzill, Matthias; Schlaf, Rudy

2016-02-01

This paper discusses the investigation of the dipole formation at In2O3|TiO2 heterojunctions depending on preparation conditions, i.e., cleaning methods. In2O3 films were deposited using atomic layer deposition (ALD) onto solvent and in situ cleaned anatase and rutile film substrates. The interface dipole strength and film thickness were evaluated by photoemission spectroscopy. Our results indicate the formation of a large intrinsic and film thickness dependent interface dipole that reaches its maximum strength at monolayer thick ALD films. In addition, it was observed that UV photoelectron spectroscopy measurements introduced UV induced surface hydroxylation, which resulted in dipole potentials of -0.70 eV and -0.50 eV on solvent cleaned anatase and rutile, respectively. The overlayers also introduced small amounts of band bending (˜0.10 eV) at the interfaces. Taking these effects into account, the total dipole strength at monolayer thick In2O3 films was determined to be -0.96 eV for solvent cleaned anatase and rutile and -0.81 eV for in situ cleaned rutile. The deposition of single ALD cycles on differently cleaned rutile substrates resulted in similar work function values, suggesting little influence of the sample preparation method prior to ALD deposition on the dipole formation. This was assigned to the fact that ALD oxides benefit from ambient water related contamination by integrating the molecules into the growing ALD layer. Highest initial growth was observed on solvent cleaned rutile, followed by in-situ cleaned rutile and solvent cleaned anatase. The In2O3 growth converged at 0.3 Å/c past the nucleation regime.

Effect of nanostructured TiO2 crystal phase on photoinduced apoptosis of breast cancer epithelial cells

PubMed Central

Lagopati, Nefeli; Tsilibary, Effie-Photini; Falaras, Polycarpos; Papazafiri, Panagiota; Pavlatou, Evangelia A; Kotsopoulou, Eleni; Kitsiou, Paraskevi

2014-01-01

Purpose The use of nanoparticles has seen exponential growth in the area of health care, due to the unique physicochemical properties of nanomaterials that make them desirable for medical applications. The aim of this study was to examine the effects of crystal phase-nanostructured titanium dioxide particles on bioactivity/cytotoxicity in breast cancer epithelial cells. Materials and methods Cultured Michigan Cancer Foundation (MCF)-7 and human breast adenocarcinoma (MDA-MB-468) breast cancer epithelial cells were exposed to ultraviolet A light (wavelength 350 nm) for 20 minutes in the presence of aqueous dispersions of two different nanostructured titanium dioxide (TiO2) crystal phases: anatase and an anatase–rutile mixture. Detailed characterization of each titanium dispersion was performed by dynamic light scattering. A 3-(4,5-dimethylthiazol-2-yl)-2,5 diphenyltetrazolium bromide (MTT) colorimetric assay was employed to estimate the percentage of viable cells after each treatment. Western blot analysis of protein expression and characterization, as well as a deoxyribonucleic acid (DNA)-laddering assay, were used to detect cell apoptosis. Results Our results documented that 100% anatase TiO2 nanoparticles (110–130 nm) exhibited significantly higher cytotoxicity in the highly malignant MDA-MB-468 cancer cells than anatase– rutile mixtures (75%/25%) with the same size. On the contrary, MCF-7 cells (characterized by low invasive properties) were not considerably affected. Exposure of MDA-MB-468 cells to pure anatase nanoparticles or anatase–rutile mixtures for 48 hours resulted in increased proapoptotic Bax expression, caspase-mediated poly(adenosine diphosphate ribose) polymerase (PARP) cleavage, DNA fragmentation, and programmed cell death/apoptosis. Conclusion The obtained results indicated that pure anatase TiO2 nanoparticles exhibit superior cytotoxic effects compared to anatase–rutile mixtures of the same size. The molecular mechanism of TiO2

Bi12TiO20 crystallization in a Bi2O3-TiO2-SiO2-Nd2O3 system

NASA Astrophysics Data System (ADS)

Slavov, S.; Jiao, Z.

2018-03-01

Polycrystalline mono-phase bismuth titanate was produced by free cooling from melts heated to 1170 °C. The control over the initial amounts in the starting compositions in the system Bi2O3/TiO2/SiO2/Nd2O3 and over the thermal gradient of the heat process resulted in the formation of specific structures and microstructures of monophase sillenite ceramics. The main phase Bi12TiO20 belongs to the amorphous network groups based on oxides of silicon, bismuth and titanium. In this work, we demonstrated a way to control the crystalline and amorphous phase formation in bulk poly-crystalline materials in the selected system.

Understanding and removing surface states limiting charge transport in TiO2 nanowire arrays for enhanced optoelectronic device performance.

PubMed

Sheng, Xia; Chen, Liping; Xu, Tao; Zhu, Kai; Feng, Xinjian

2016-03-01

Charge transport within electrode materials plays a key role in determining the optoelectronic device performance. Aligned single-crystal TiO 2 nanowire arrays offer an ideal electron transport path and are expected to have higher electron mobility. Unfortunately, their transport is found not to be superior to that in nanoparticle films. Here we show that the low electron transport in rutile TiO 2 nanowires is mainly caused by surface traps in relatively deep energy levels, which cannot be removed by conventional approaches, such as oxygen annealing treatment. Moreover, we demonstrate an effective wet-chemistry approach to minimize these trap states, leading to over 20-fold enhancement in electron diffusion coefficient and 62% improvement in solar cell performance. On the basis of our results, the potential of TiO 2 NWs can be developed and well-utilized, which is significantly important for their practical applications.

Photocatalytic and adsorption properties of TiO2-pillared montmorillonite obtained by hydrothermally activated intercalation of titanium polyhydroxo complexes

PubMed Central

Ovchinnikov, Nikolay L; Karasev, Nikita S; Kochkina, Nataliya E; Agafonov, Alexander V; Vinogradov, Alexandr V

2018-01-01

We report on a new approach for the synthesis of TiO2-pillared montmorillonite, where the pillars exhibit a high degree of crystallinity (nanocrystals) representing a mixture of anatase and rutile phases. The structures exhibit improved adsorption and photocatalytic activity as a result of hydrothermally activated intercalation of titanium polyhydroxo complexes (i.e., TiCl4 hydrolysis products) in a solution with a concentration close to the sol formation limit. The materials, produced at various annealing temperatures from the intercalated samples, were characterized by infrared spectroscopy, differential scanning calorimetry (DSC)/thermogravimetric analysis (TGA), X-ray diffraction, dynamic light scattering (DLS) measurements, and liquefied nitrogen adsorption/desorption. The photocatalytic activity of the TiO2-pillared materials was studied using the degradation of anionic (methyl orange, MO) and cationic (rhodamine B, RhB) dyes in water under UV irradiation. The combined effect of adsorption and photocatalysis resulted in removal of 100% MO and 97.5% RhB (with an initial concentration of 40 mg/L and a photocatalyst-sorbent concentration of 1 g/L) in about 100 minutes. The produced TiO2-pillared montmorillonite showed increased photocatalytic activity as compared to the commercially available photocatalyst Degussa P25. PMID:29515950

CNTs threaded (001) exposed TiO2 with high activity in photocatalytic NO oxidation.

PubMed

Xiao, Shuning; Zhu, Wei; Liu, Peijue; Liu, Fanfan; Dai, Wenrui; Zhang, Dieqing; Chen, Wei; Li, Hexing

2016-02-07

A microwave-ionothermal strategy was developed for in situ synthesis of CNTs threaded TiO2 single crystal with a tunable percentage of surface exposed (001) active facets. The CNTs were used as microwave antennas to create local "super hot" dots to induce Ti(3+) adsorption and hydrolysis, thereby leading to a good assembly of (001) facets exposed single crystalline TiO2 threaded by the CNTs in the presence of Hmim[BF4] ionic liquid. Due to the high percentage of the active (001) facets of single crystal TiO2 and the direct electron transfer property of the CNTs, the as-prepared CNTs-TiO2 composite showed a photocatalytic NO removal ratio of up to 76.8% under UV irradiation. In addition, with self-doped Ti(3+), the CNTs-TiO2 composite also exhibited an enhanced activity under irradiation with either solar lights or visible lights, showing good potential in practical applications for environmental remediation.

Study of phase development and thermal stability in as synthesized TiO2 nanoparticles by laser pyrolysis: ethylene uptake and oxygen enrichment

NASA Astrophysics Data System (ADS)

Ilie, Alina Georgiana; Scarisoreanu, Monica; Dutu, Elena; Dumitrache, Florian; Banici, Ana-Maria; Fleaca, Claudiu Teodor; Vasile, Eugenia; Mihailescu, Ion

2018-01-01

Laser pyrolysis has proven a viable and trustworthy method of TiO2 nanoparticles fabrication, ensuring good quality and wide variety of nanoparticle morphologies and sizes. This work is aimed to phase control, experimentally studied, by parameter modulation, during one step laser pyrolysis synthesis or in combination with thermal annealing. High phase purity anatase and rutile TiO2 nanoparticles, oxygen abundant, are synthesized from TiCl4 and C2H4 gas mixtures, in the presence of air as oxygen donor, under CO2 laser radiation. The nano-titania samples are analyzed by X-ray Diffraction, EDAX, TEM and Raman spectroscopy and reveal good phase stability and distinct morphology. This study extends the method applicability onto rutile majoritarian TiO2 synthesis and generation of thermally stable anatase titania, a well-known catalyst.

Quantitative evaluation of local pulmonary distribution of TiO2 in rats following single or multiple intratracheal administrations of TiO2 nanoparticles using X-ray fluorescence microscopy.

PubMed

Zhang, Guihua; Shinohara, Naohide; Kano, Hirokazu; Senoh, Hideki; Suzuki, Masaaki; Sasaki, Takeshi; Fukushima, Shoji; Gamo, Masashi

2016-10-01

Uneven pulmonary nanoparticle (NP) distribution has been described when using single-dose intratracheal administration tests. Multiple-dose intratracheal administrations with small quantities of NPs are expected to improve the unevenness of each dose. The differences in local pulmonary NP distribution (called microdistribution) between single- and multiple-dose administrations may cause differential pulmonary responses; however, this has not been evaluated. Here, we quantitatively evaluated the pulmonary microdistribution (per mesh: 100 μm × 100 μm) of TiO2 in lung sections from rats following one, two, three, or four doses of TiO2 NPs at a same total dosage of 10 mg kg(-1) using X-ray fluorescence microscopy. The results indicate that: (i) multiple-dose administrations show lower variations in TiO2 content (ng mesh(-1) ) for sections of each lobe; (ii) TiO2 appears to be deposited more in the right caudal and accessory lobes located downstream of the administration direction of NP suspensions, and less so in the right middle lobes, irrespective of the number of doses; (iii) there are not prominent differences in the pattern of pulmonary TiO2 microdistribution between rats following single and multiple doses of TiO2 NPs. Additionally, the estimation of pulmonary TiO2 deposition for multiple-dose administrations imply that every dose of TiO2 would be randomly deposited only in part of the fixed 30-50% of lung areas. The evidence suggests that multiple-dose administrations do not offer remarkable advantages over single-dose administration on the pulmonary NP microdistribution, although multiple-dose administrations may reduce variations in the TiO2 content for each lung lobe. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Nanostructured TiO2-based gas sensors with enhanced sensitivity to reducing gases

PubMed Central

Kusior, Anna; Trenczek-Zajac, Anita

2016-01-01

2D TiO2 thin films and 3D flower-like TiO2-based nanostructures, also decorated with SnO2, were prepared by chemical and thermal oxidation of Ti substrates, respectively. The crystal structure, morphology and gas sensing properties of the TiO2-based sensing materials were investigated. 2D TiO2 thin films crystallized mainly in the form of rutile, while the flower-like 3D nanostructures as anatase. The sensor based on the 2D TiO2 showed the best performance for H2 detection, while the flower-like 3D nanostructures exhibited enhanced selectivity to CO(CH3)2 after sensitization by SnO2 nanoparticles. The sensor response time was of the order of several seconds. Their fast response, high sensitivity to selected gas species, improved selectivity and stability suggest that the SnO2-decorated flower-like 3D nanostructures are a promising material for application as an acetone sensor. PMID:28144521