The Acute Liver Injury in Mice Caused by Nano-Anatase TiO2

NASA Astrophysics Data System (ADS)

Ma, Linglan; Zhao, Jinfang; Wang, Jue; Liu, Jie; Duan, Yanmei; Liu, Huiting; Li, Na; Yan, Jingying; Ruan, Jie; Wang, Han; Hong, Fashui

2009-11-01

Although it is known that nano-TiO2 or other nanoparticles can induce liver toxicities, the mechanisms and the molecular pathogenesis are still unclear. In this study, nano-anatase TiO2 (5 nm) was injected into the abdominal cavity of ICR mice for consecutive 14 days, and the inflammatory responses of liver of mice was investigated. The results showed the obvious titanium accumulation in liver DNA, histopathological changes and hepatocytes apoptosis of mice liver, and the liver function damaged by higher doses nano-anatase TiO2. The real-time quantitative RT-PCR and ELISA analyses showed that nano-anatase TiO2 can significantly alter the mRNA and protein expressions of several inflammatory cytokines, including nucleic factor-κB, macrophage migration inhibitory factor, tumor necrosis factor-α, interleukin-6, interleukin-1β, cross-reaction protein, interleukin-4, and interleukin-10. Our results also implied that the inflammatory responses and liver injury may be involved in nano-anatase TiO2-induced liver toxicity.

Effects of addition of supramolecular assembly on the anatase nanocrystalline precipitation of sol-gel derived SiO2-TiO2 coating films by hot-water treatment.

PubMed

Katagiri, Kiyofumi; Harada, Genki; Matsuda, Atsunori; Kogure, Toshihiro; Muto, Hiroyuki; Sakai, Mototsugu

2006-06-01

Effects of the addition of a supramolecular assembly of cetyltrimethylammonium bromide in SiO2-TiO2 gel films on the formation of anatase type TiO2 nanocrystals with hot-water treatment were investigated. Anatase nanocrystals were formed in the whole SiO2-TiO2 gel films with the addition of cetyltrimethylammonium bromide by the treatment, whereas the nanocrystals were formed only on the film surface in the case of gel films without cetyltrimethylammonium bromide. Cetyltrimethylammonium bromide molecules in the SiO2-TiO2 gel films were completely removed by the hot-water treatment and the following UV irradiation. In the usual procedure for preparation of porous materials, the removal of template molecular assemblies required high temperature treatment over 400 degrees C. In this system, all the processes were performed at temperatures less than 100 degrees C. Additionally, the porous structure produced by the removal of micellar assembly allowed anatase nanocrystals to be formed inside the films. Therefore, the method presented in this work provides us with the novel photocatalyst coatings of porous membrane with highly-dispersed TiO2 nanocrystals via low temperature process.

Impedance analysis and dielectric response of anatase TiO2 nanoparticles codoped with Mn and Co ions

NASA Astrophysics Data System (ADS)

Kumar, Anand; Kashyap, Manish K.; Sabharwal, Namita; Kumar, Sarvesh; Kumar, Ashok; Kumar, Parmod; Asokan, K.

2017-11-01

In order to elucidate the effect of transition metal (TM) doping, the impedance and dielectric responses of Co and/or Mn-doped TiO2 nanocrystalline powder samples with 3% doping concentration synthesized via sol gel technique, have been analyzed. X-ray diffraction (XRD) analysis confirms the formation of tetragonal TiO2 anatase phase for all studied samples without any extra impurity phase peaks. The variation in the grain size measured from field emission scanning electron microscope (FESEM) measurements for all the samples are in accordance with the change in crystallite size as obtained from XRD. The DC resistivity for pure TiO2 nanoparticles is the highest while codoped samples exhibit low resistivity. The temperature dependent dielectric constant and dielectric loss possess step like enhancement and show the relaxation behavior. At room temperature, the dielectric function and dielectric loss decrease rapidly with increase in frequency and become almost constant at the higher frequencies. Such a decrease in dielectric loss is suitable for energy storage devices.

Effect on Electron Structure and Magneto-Optic Property of Heavy W-Doped Anatase TiO2.

PubMed

Hou, Qingyu; Zhao, Chunwang; Guo, Shaoqiang; Mao, Fei; Zhang, Yue

2015-01-01

The spin or nonspin state of electrons in W-doped anatase TiO2 is very difficult to judge experimentally because of characterization method limitations. Hence, the effect on the microscopic mechanism underlying the visible-light effect of W-doped anatase TiO2 through the consideration of electronic spin or no-spin states is still unknown. To solve this problem, we establish supercell models of W-doped anatase TiO2 at different concentrations, followed by geometry optimization and energy calculation based on the first-principle planewave norm conserving pseudo-potential method of the density functional theory. Calculation results showed that under the condition of nonspin the doping concentration of W becomes heavier, the formation energy becomes greater, and doping becomes more difficult. Meanwhile, the total energy increases, the covalent weakens and ionic bonds strengthens, the stability of the W-doped anatase TiO2 decreases, the band gap increases, and the blue-shift becomes more significant with the increase of W doping concentration. However, under the condition of spin, after the band gap correction by the GGA+U method, it is found that the semimetal diluted magnetic semiconductors can be formed by heavy W-doped anatase TiO2. Especially, a conduction electron polarizability of as high as near 100% has been found for the first time in high concentration W-doped anatase TiO2. It will be able to be a promising new type of dilute magnetic semiconductor. And the heavy W-doped anatase TiO2 make the band gap becomes narrower and absorption spectrum red-shift.

Distinctive toxicity of TiO2 rutile/anatase mixed phase nanoparticles on Caco-2 cells.

PubMed

Gerloff, Kirsten; Fenoglio, Ivana; Carella, Emanuele; Kolling, Julia; Albrecht, Catrin; Boots, Agnes W; Förster, Irmgard; Schins, Roel P F

2012-03-19

Titanium dioxide has a long-standing use as a food additive. Micrometric powders are, e.g., applied as whiteners in confectionary or dairy products. Possible hazards of ingested nanometric TiO(2) particles for humans and the potential influence of varying specific surface area (SSA) are currently under discussion. Five TiO(2)-samples were analyzed for purity, crystallinity, primary particle size, SSA, ζ potential, and aggregation/agglomeration. Their potential to induce cytotoxicity, oxidative stress, and DNA damage was evaluated in human intestinal Caco-2 cells. Only anatase-rutile containing samples, in contrast to the pure anatase samples, induced significant LDH leakage or mild DNA damage (Fpg-comet assay). Evaluation of the metabolic competence of the cells (WST-1 assay) revealed a highly significant correlation between the SSA of the anatase samples and cytotoxicity. The anatase/rutile samples showed higher toxicity per unit surface area than the pure anatase powders. However, none of the samples affected cellular markers of oxidative stress. Our findings suggest that both SSA and crystallinity are critical determinants of TiO(2)-toxicity toward intestinal cells. © 2012 American Chemical Society

Oral administration of rutile and anatase TiO2 nanoparticles shifts mouse gut microbiota structure.

PubMed

Li, Juan; Yang, Shengmei; Lei, Runhong; Gu, Weihong; Qin, Yanxia; Ma, Sihan; Chen, Kui; Chang, Yanan; Bai, Xue; Xia, Shibo; Wu, Chongming; Xing, Gengmei

2018-04-26

The widespread application of TiO2 nanoparticles (NPs) as additives in foods such as gum, candy and puddings has dramatically increased the human ingestion and accumulation of these nanomaterials. Although the toxicity of TiO2 NPs has been extensively studied, their impact on gut microbiota in vivo still needs further research. In this study, TiO2 NPs with two main crystalline phases anatase and rutile were orally administrated to mice for 28 days. The dynamic influences of anatase and rutile on gut microbiota structures were investigated at doses equivalent to those consumed by people who love to eat candies. The results showed that titanium accumulated in the spleen, lung, and kidney but had no significant effects on organ histology. Gavage of rutile NPs but not anatase NPs resulted in longer intestinal villi and irregular arrangement of villus epithelial cells. Treatment with TiO2 NPs did not decrease gut microbiota diversity but shifted their structures in a time-dependent manner. Rutile NPs had a more pronounced influence on the gut microbiota than anatase NPs. The most influenced phylum was Proteobacteria, which was significantly increased by rutile but not by anatase. At the genus level, Prevotella was significantly decreased by both the TiO2 NPs, Rhodococcus was enriched by rutile NPs, and Bacteroides was increased by anatase NPs. Overall, these results suggested that chronic overconsumption of TiO2 NP-containing foods is likely to deteriorate the gastrointestinal tract and change the structures of microbiota. The crystalline phases may play an important role in mediating the intestinal impact of TiO2 NPs.

Effect on Electron Structure and Magneto-Optic Property of Heavy W-Doped Anatase TiO2

PubMed Central

Hou, Qingyu; Zhao, Chunwang; Guo, Shaoqiang; Mao, Fei; Zhang, Yue

2015-01-01

The spin or nonspin state of electrons in W-doped anatase TiO2 is very difficult to judge experimentally because of characterization method limitations. Hence, the effect on the microscopic mechanism underlying the visible-light effect of W-doped anatase TiO2 through the consideration of electronic spin or no-spin states is still unknown. To solve this problem, we establish supercell models of W-doped anatase TiO2 at different concentrations, followed by geometry optimization and energy calculation based on the first-principle planewave norm conserving pseudo-potential method of the density functional theory. Calculation results showed that under the condition of nonspin the doping concentration of W becomes heavier, the formation energy becomes greater, and doping becomes more difficult. Meanwhile, the total energy increases, the covalent weakens and ionic bonds strengthens, the stability of the W-doped anatase TiO2 decreases, the band gap increases, and the blue-shift becomes more significant with the increase of W doping concentration. However, under the condition of spin, after the band gap correction by the GGA+U method, it is found that the semimetal diluted magnetic semiconductors can be formed by heavy W-doped anatase TiO2. Especially, a conduction electron polarizability of as high as near 100% has been found for the first time in high concentration W-doped anatase TiO2. It will be able to be a promising new type of dilute magnetic semiconductor. And the heavy W-doped anatase TiO2 make the band gap becomes narrower and absorption spectrum red-shift. PMID:25955308

Efficient photodegradation of organic dye using anatase TiO2 plants as catalyst

NASA Astrophysics Data System (ADS)

Bahadur, Jitendra; Pal, Kaushik

2017-11-01

Anatase TiO2 hierarchical nanostructures with higher photocatalytic activity are of special importance in various applications. We have reported the synthesis of TiO2 as water chestnut plants like morphology via facile hydrothermal method, by using Titanium (IV) butoxide (TBOT) as a precursor solution. It is found that TiO2 nanoparticles work as seed and completely convert into water chestnut plants like structure or morphology, which are composed of crystallized anatase nanocrystals. X-ray diffraction spectra confirmed the presence of anatase phase of crystallized TiO2 plants (TPs). The average life time delay for generated charge carriers in TPs was calculated to be around 2.45 ns, which reflects slow recombination of charge carriers. The prepared TPs show excellent photocatalytic performance when applied in photo degradation of Rhodamine B organic dye. The unique features exhibited by TPs make them a promising candidate for vast potential applications in field such as solar cells, photocatalysis, supercapacitor, lithium ion batteries and some related fields.[Figure not available: see fulltext.

Equilibrium lithium-ion transport between nanocrystalline lithium-inserted anatase TiO2 and the electrolyte.

PubMed

Ganapathy, Swapna; van Eck, Ernst R H; Kentgens, Arno P M; Mulder, Fokko M; Wagemaker, Marnix

2011-12-23

The power density of lithium-ion batteries requires the fast transfer of ions between the electrode and electrolyte. The achievable power density is directly related to the spontaneous equilibrium exchange of charged lithium ions across the electrolyte/electrode interface. Direct and unique characterization of this charge-transfer process is very difficult if not impossible, and consequently little is known about the solid/liquid ion transfer in lithium-ion-battery materials. Herein we report the direct observation by solid-state NMR spectroscopy of continuous lithium-ion exchange between the promising nanosized anatase TiO(2) electrode material and the electrolyte. Our results reveal that the energy barrier to charge transfer across the electrode/electrolyte interface is equal to or greater than the barrier to lithium-ion diffusion through the solid anatase matrix. The composition of the electrolyte and in turn the solid/electrolyte interface (SEI) has a significant effect on the electrolyte/electrode lithium-ion exchange; this suggests potential improvements in the power of batteries by optimizing the electrolyte composition. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Construction of anatase/rutile TiO2 hollow boxes for highly efficient photocatalytic performance

NASA Astrophysics Data System (ADS)

Jia, Changchao; Zhang, Xiao; Yang, Ping

2018-02-01

Hollow TiO2 hierarchical boxes with suitable anatase and rutile ratios were designed for photocatalysis. The unique hierarchical structure was fabricated via a Topotactic synthetic method. CaTiO3 cubes were acted as the sacrificial templates to create TiO2 hollow hierarchical boxes with well-defined phase distribution. The phase composition of the hollow TiO2 hierarchical boxes is similar to that of TiO2 P25 nanoparticles (∼80% anatase, and 20% rutile). Compared with nanaoparticles, TiO2 hollow boxes with hierarchical structures exhibited an excellent performance in the photocatalytic degradation of methylene blue organic pollutant. Quantificationally, the degradation rate of the hollow boxes is higher than that of TiO2 P25 nanoparticles by a factor of 2.7. This is ascribed that hollow structure provide an opportunity for using incident light more efficiently. The surface hierarchical and well-organized porous structures are beneficial to supply more active sites and enough transport channels for reactant molecules. The boxes consist of single crystal anatase and rutile combined well with each other, which gives photon-generated carriers transfer efficiently.

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.

Rietveld analysis of the effect of annealing atmosphere on phase evolution of nanocrystalline TiO2 powders.

PubMed

Salari, M; Rezaee, M; Chidembo, A T; Konstantinov, K; Liu, H K

2012-06-01

The structural evolution of nanocrystalline TiO2 was studied by X-ray diffraction (XRD) and the Rietveld refinement method (RRM). TiO2 powders were prepared by the sol-gel technique. Post annealing of as-synthesized powders in the temperature range from 500 degrees C to 800 degrees C under air and argon atmospheres led to the formation of TiO2 nanoparticles with mean crystallite size in the range of 37-165 nm, based on the Rietveld refinement results. It was found that the phase structure, composition, and crystallite size of the resulting particles were dependent on not only the annealing temperature, but also the annealing atmosphere. Rietveld refinement of the XRD data showed that annealing the powders under argon atmosphere promoted the polymorphic phase transformation from anatase to rutile. Field emission scanning electron microscopy (FESEM) was employed to investigate the morphology and size of the annealed powders.

Self-assembled chromophores within mesoporous nanocrystalline TiO2: towards biomimetic solar cells.

PubMed

Marek, Peter L; Sieger, Hermann; Scherer, Torsten; Hahn, Horst; Balaban, Teodor Silviu

2009-06-01

Artificial light-harvesting antennas consisting of self-assembled chromophores that mimic the natural pigments of photosynthetic bacteria have been inserted into voids induced in porous titania (TiO2, anatase) in order to investigate their suitability for hybrid solar cells. Mesoporous nanocrystalline TiO2 with additional uniform macropores was treated with precursor solutions of the pigment which was then induced to self-assemble within the voids. The chromophores were tailored to combine the self-assembly characteristics of the natural bacteriochlorophylls with the robustness of artificial Zn-porphyrins being stable for prolonged periods even upon heating to over 200 degrees C. They assemble on the TiO2 surface to form nano- to micro-crystalline structures with lengths from tens of nm up to several microm and show a photosensitization effect which is supposed to be dependent on the assembly size. The natural examples of these antennas are found in green sulfur bacteria which are able to use photosynthesis in deep water regions with minute light intensities. The implementation of biomimetic antennas for light harvesting and a better photon management may lead to a rise in efficiency of dye-sensitized solar cells also under low light illumination conditions.

Synthesis of reduced graphene oxide-anatase TiO2 nanocomposite and its improved photo-induced charge transfer properties.

PubMed

Wang, Ping; Zhai, Yueming; Wang, Dejun; Dong, Shaojun

2011-04-01

The construction of reduced graphene oxide or graphene oxide with semiconductor has gained more and more attention due to its unexpected optoelectronic and electronic properties. The synthesis of reduced graphene oxide (RGO) or graphene oxide-semiconductor nanocomposite with well-dispersed decorated particles is still a challenge now. Herein, we demonstrate a facile method for the synthesis of graphene oxide-amorphous TiO(2) and reduced graphene oxide-anatase TiO(2) nanocomposites with well-dispersed particles. The as-synthesized samples were characterized by transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, UV-Vis absorption spectroscopy, Fourier transform infrared spectrometry, and thermogravimetric analysis. The photovoltaic properties of RGO-anatase TiO(2) were also compared with that of similar sized anatase TiO(2) by transient photovoltage technique, and it was interesting to find that the combination of reduced graphene oxide with anatase TiO(2) will significantly increase the photovoltaic response and retard the recombination of electron-hole pairs in the excited anatase TiO(2).

Synthesis and photocatalytic activity of anatase TiO2 nanoparticles for degradation of methyl orange

NASA Astrophysics Data System (ADS)

Singh, Manmeet; Duklan, Neha; Singh, Pritpal; Sharma, Jeewan

2018-05-01

In present study, TiO2 nanoparticles, in anatase form, were successfully synthesized using TiCl4 as precursor. These nanoparticles were synthesized by sol-gel method at room temperature (298 K). As prepared samples were characterized for phase structure, optical absorption and surface properties using X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), Raman spectroscopy and UV-Visible spectroscopy. The synthesized TiO2 nanoparticles sample was compared with one of the most efficient commercial photocatalyst Degussa TiO2 also known as P(25). The effect of phase composition of anatase TiO2 nanoparticles, as compared to P(25), on photocatalytic decomposition of organic dye, methyl orange (MO) was studies under UV light illumination. An enhanced degradation of hazardous dye was observed in the presence of anatase TiO2 nanoparticles as compared to P(25) due to slow recombination rate. Other possible reasons for this enhancement have also been discussed.

GW quasiparticle bandgaps of anatase TiO2 starting from DFT + U.

PubMed

Patrick, Christopher E; Giustino, Feliciano

2012-05-23

We investigate the quasiparticle band structure of anatase TiO(2), a wide gap semiconductor widely employed in photovoltaics and photocatalysis. We obtain GW quasiparticle energies starting from density-functional theory (DFT) calculations including Hubbard U corrections. Using a simple iterative procedure we determine the value of the Hubbard parameter yielding a vanishing quasiparticle correction to the fundamental bandgap of anatase TiO(2). The bandgap (3.3 eV) calculated using this optimal Hubbard parameter is smaller than the value obtained by applying many-body perturbation theory to standard DFT eigenstates and eigenvalues (3.7 eV). We extend our analysis to the rutile polymorph of TiO(2) and reach similar conclusions. Our work highlights the role of the starting non-interacting Hamiltonian in the calculation of GW quasiparticle energies in TiO(2) and suggests an optimal Hubbard parameter for future calculations.

Anomalous compression behavior of ˜12 nm nanocrystalline TiO2

NASA Astrophysics Data System (ADS)

Wang, Qiming; Li, Shourui; Peng, Fang; Lei, Li; Hu, Qiwei; Wang, Pei; Nan, Xiaolong; Liu, Jing; Zhu, Wenjun; He, Duanwei

2017-06-01

When the grain size decreases, there inevitably exists a critical size (dc) where the contribution of surface atoms to the physical properties is competitive with that of the interior atoms, giving rise to a wide variety of new phenomena. The behavior of granular materials near dc is particularly interesting because of the crossover, a continuous transition from one type of mechanism to another. In situ high-pressure x-ray diffraction experiments showed that the compression curve of nanocrystalline anatase TiO2 with grain size near dc reached a platform after about 5%-6% of deformation under hydrostatic compression. Eventually, the unit cell volume of anatase expanded at ˜14-16 GPa. We propose that the anomalous compression behavior is attributed to the formation and thickening of the stiff high density amorphous shell under high pressure, giving rise to a great arching effect at the grain boundary at the nanolevel. This process results in a remarkable difference in stress between inside and outside of the shell, generating the illusions of the hardening and the negative compressibility. This study offers a new insight into the mechanical properties of nanomaterials under extreme conditions.

Water-assisted crystallization of mesoporous anatase TiO2 nanospheres

NASA Astrophysics Data System (ADS)

Li, Na; Zhang, Qiao; Joo, Ji Bong; Lu, Zhenda; Dahl, Michael; Gan, Yang; Yin, Yadong

2016-04-01

We report a facile water-assisted crystallization process for the conversion of amorphous sol-gel derived TiO2 into mesoporous anatase nanostructures with a high surface area and well-controlled porosity and crystallinity. As an alternative to conventional calcination methods, this approach works under very mild conditions and is therefore much desired for broad biological, environmental and catalytic applications.We report a facile water-assisted crystallization process for the conversion of amorphous sol-gel derived TiO2 into mesoporous anatase nanostructures with a high surface area and well-controlled porosity and crystallinity. As an alternative to conventional calcination methods, this approach works under very mild conditions and is therefore much desired for broad biological, environmental and catalytic applications. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr01892k

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.

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

NASA Astrophysics Data System (ADS)

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

2016-02-01

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

Facile synthesis of high-temperature (1000 °C) phase-stable rice-like anatase TiO2 nanocrystals

NASA Astrophysics Data System (ADS)

Lv, Lizhen; Chen, Qirong; Liu, Xiuyun; Wang, Miaomiao; Meng, Xiangfu

2015-05-01

High-temperature phase-stable rice-like anatase TiO2 nanocrystals were synthesized by one-pot solvothermal method using soluble titania xerogel and isopropyl alcohol (IPA) as the precursor and the solvent, respectively. Sample characterization was carried out by powder X-ray diffraction, high-resolution transmission electron microscopy, field emission scanning electron microscope, X-ray photoelectron spectroscopy, and N2 adsorption-desorption isotherms. The results showed that TiO2 nanocrystals had rice-like shapes with an average size of 5 nm in width and 35 nm in length. The BET surface area was 153 m2/g. Unexpectedly, the rice-like TiO2 nanocrystals exhibited high-temperature phase stability, which could remain as pure anatase phase after calcinations at 1000 °C. Growth mechanism investigation revealed that the IPA solvent played a key role in nucleation and growth of rice-like anatase TiO2 nanocrystals. The photodegradation of rhodamine B demonstrated that rice-like anatase TiO2 nanocrystals exhibited enhanced photocatalytic activity under visible light irradiation.

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.

Structural, electronic and optical properties of CO adsorbed on the defective anatase TiO2 (101) surface; a DFT study

NASA Astrophysics Data System (ADS)

Rafique, Muhammad; Shuai, Yong; Hassan, Muhammad

2017-08-01

This paper illustrates the study of stable structural, electronic and optical properties of carbon mono oxide (CO) molecule adsorbed on pure anatase TiO2 (101) surface and CO molecule adsorbed on defective anatase TiO2 (101) surface containing oxygen (O) atom subsurface vacancy using first-principles study calculations based on density functional theory (DFT) method. A foreign molecule CO was added in the interstitial space of anatase TiO2 (101) surface. It was observed that, adsorption of CO molecule is not favorable on pure anatase TiO2 (101) surface, however adsorption process is improved when subsurface contains O atom vacancy defect. In case of anatase TiO2 (101) surface containing subsurface vacancy, adsorption process is exothermic, resulting in stable structures. The adsorption energies calculated for CO molecules adsorbed at O2c site, at defect site and at Ti5c site of anatase surface containing subsurface O vacancy are 0.16 eV (at O2c), 0.32 eV (at defect site) and 0.43 eV (at Ti5c) site. DOS and PDOS plots are calculated for all the structures. Results indicated that CO molecule adsorption introduces surface states at the Fermi energy level (EF) as shown in partial density of states (PDOS) plots. The dielectric matrix and absorption coefficient (α) for defective anatase TiO2 (101) surface, CO adsorbed at O2c site, at defect site and at Ti5C site of anatase TiO2 (101) surface containing O atom subsurface vacancy has been calculated within the random phase approximation (RPA) using VASP (Vienna ab-initio simulation package) code. It was observed that upon CO adsorption at defective anatase surface, real and imaginary dielectric function peaks were shifted towards lower energy level and a small absorption peak was observed at 1.1 eV energy level which is not present in case of defective anatase (101) surface. CO adsorption produces a red shift in the absorption spectrum of anatase TiO2 (101) surface containing subsurface O atom vacancy.

Nd/TiO2 Anatase-Brookite Photocatalysts for Photocatalytic Decomposition of Methanol.

PubMed

Kočí, Kamila; Troppová, Ivana; Reli, Martin; Matějová, Lenka; Edelmannová, Miroslava; Drobná, Helena; Dubnová, Lada; Rokicińska, Anna; Kuśtrowski, Piotr; Čapek, Libor

2018-01-01

Neodymium enriched TiO 2 anatase-brookite powders were prepared by unconventional method via using pressurized hot fluids for TiO 2 crystallization and purification. The photocatalysts were tested in the CH 3 OH photocatalytic decomposition and they were characterized with respect to the textural (nitrogen adsorption), structural (XRD, XPS, and Raman spectroscopies), chemical (XRF), and optical (DR UV-Vis spectroscopy) and photoelectrochemical measurement. All prepared materials were nanocrystalline, had biphasic (anatase- brookite) structure and relatively large specific surface area (125 m 2 .g -1 ). The research work indicates that the doping of neodymium on TiO 2 photocatalysts significantly enhances the efficiency of photocatalytic reaction. The photocatalytic activity increased with increasing portion of hydroxyl oxygen to the total amount of oxygen species. It was ascertained that the optimal amount of 1 wt% Nd in TiO 2 accomplished the increasing of hydrogen production by 70% in comparison with pure TiO 2 . The neodymium doped on the titanium dioxide act as sites with accumulation of electrons. The higher efficiency of photocatalytic process was achieved due to improved electron-hole separation on the modified TiO 2 photocatalysts. This result was confirmed by electrochemical measurements, the most active photocatalysts proved the highest photocurrent responses.

Nd/TiO2 Anatase-Brookite Photocatalysts for Photocatalytic Decomposition of Methanol

PubMed Central

Kočí, Kamila; Troppová, Ivana; Reli, Martin; Matějová, Lenka; Edelmannová, Miroslava; Drobná, Helena; Dubnová, Lada; Rokicińska, Anna; Kuśtrowski, Piotr; Čapek, Libor

2018-01-01

Neodymium enriched TiO2 anatase-brookite powders were prepared by unconventional method via using pressurized hot fluids for TiO2 crystallization and purification. The photocatalysts were tested in the CH3OH photocatalytic decomposition and they were characterized with respect to the textural (nitrogen adsorption), structural (XRD, XPS, and Raman spectroscopies), chemical (XRF), and optical (DR UV-Vis spectroscopy) and photoelectrochemical measurement. All prepared materials were nanocrystalline, had biphasic (anatase- brookite) structure and relatively large specific surface area (125 m2.g−1). The research work indicates that the doping of neodymium on TiO2 photocatalysts significantly enhances the efficiency of photocatalytic reaction. The photocatalytic activity increased with increasing portion of hydroxyl oxygen to the total amount of oxygen species. It was ascertained that the optimal amount of 1 wt% Nd in TiO2 accomplished the increasing of hydrogen production by 70% in comparison with pure TiO2. The neodymium doped on the titanium dioxide act as sites with accumulation of electrons. The higher efficiency of photocatalytic process was achieved due to improved electron-hole separation on the modified TiO2 photocatalysts. This result was confirmed by electrochemical measurements, the most active photocatalysts proved the highest photocurrent responses. PMID:29552558

A reversible phase transition for sodium insertion in anatase TiO 2

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

Li, Wei; Fukunishi, Mika; Morgan, Benjamin J.

Anatase TiO 2 is a potential negative electrode for sodium-ion batteries. The sodium storage mechanism is, however, still under debate, yet its comprehension is required to optimize the electrochemical properties. To clarify the sodium storage mechanism occurring in anatase, we have used both electrochemical and chemical routes from which we obtained similar trends. During the first discharge, an irreversible plateau region is observed which corresponds to the insertion of Na+ within the interstitial sites of anatase and is accompanied by a drastic loss of the long-range order as revealed by X-ray diffraction, high resolution of high angle annular dark-field scanningmore » transmission electron microscope (HAADF-STEM), and pair distribution function (PDF) analysis. Further structural analysis of the total scattering data indicates that the sodiated phase displays a layered-like rhombohedral R3m structure built from the stacking of Ti and Na slabs. Because of the initial 3D network of anatase, the reduced phase shows strong disorder due to cationic intermixing between the Ti and Na slabs and the refined chemical formula is (Na 0.43Ti 0.57) 3a 0.22Na 0.39Ti 0.39) 3bO 2, where refers to vacancy. The presence of high valence Ti ions in the Na layers induces a contraction of the c-parameter as compared to the ordered phase. Upon desodiation, the structure further amorphized and the local structure probed by PDF is shown to be similar to the anatase TiO 2, suggesting that the 3D network is recovered. The reversible sodium insertion/deinsertion is thus attributed to the rhombohedral active phase formed during the first discharge, and an oxidized phase featuring the local structure of anatase. Due to the amorphous nature of the two phases, the potential-composition curves are characterized by a sloping curve. Lastly, a comparison between the intercalation of lithium and sodium into anatase TiO 2 performed by DFT calculations confirmed that, for the sodiated phase, the

A reversible phase transition for sodium insertion in anatase TiO 2

DOE PAGES

Li, Wei; Fukunishi, Mika; Morgan, Benjamin J.; ...

2017-02-07

Anatase TiO 2 is a potential negative electrode for sodium-ion batteries. The sodium storage mechanism is, however, still under debate, yet its comprehension is required to optimize the electrochemical properties. To clarify the sodium storage mechanism occurring in anatase, we have used both electrochemical and chemical routes from which we obtained similar trends. During the first discharge, an irreversible plateau region is observed which corresponds to the insertion of Na+ within the interstitial sites of anatase and is accompanied by a drastic loss of the long-range order as revealed by X-ray diffraction, high resolution of high angle annular dark-field scanningmore » transmission electron microscope (HAADF-STEM), and pair distribution function (PDF) analysis. Further structural analysis of the total scattering data indicates that the sodiated phase displays a layered-like rhombohedral R3m structure built from the stacking of Ti and Na slabs. Because of the initial 3D network of anatase, the reduced phase shows strong disorder due to cationic intermixing between the Ti and Na slabs and the refined chemical formula is (Na 0.43Ti 0.57) 3a 0.22Na 0.39Ti 0.39) 3bO 2, where refers to vacancy. The presence of high valence Ti ions in the Na layers induces a contraction of the c-parameter as compared to the ordered phase. Upon desodiation, the structure further amorphized and the local structure probed by PDF is shown to be similar to the anatase TiO 2, suggesting that the 3D network is recovered. The reversible sodium insertion/deinsertion is thus attributed to the rhombohedral active phase formed during the first discharge, and an oxidized phase featuring the local structure of anatase. Due to the amorphous nature of the two phases, the potential-composition curves are characterized by a sloping curve. Lastly, a comparison between the intercalation of lithium and sodium into anatase TiO 2 performed by DFT calculations confirmed that, for the sodiated phase, the

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.

Characterization of oxygen and titanium diffusion at the anatase TiO2(001) surface

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

Herman, Gregory S.; Zehr, Robert T.; Henderson, Michael A.

2013-06-01

The diffusion of intrinsic defects in a single crystal anatase TiO2(001) film was explored by isotopic labeling and static secondary ion mass spectrometry. Using both 46Ti and 18O as isotopic labels, we show that the anatase surface responds to redox imbalances by diffusion of both Ti and O into the bulk under vacuum reduction and (at least) Ti from the bulk to the surface during oxidation. The diffusion of Ti between the bulk and surface in anatase TiO2(001) closely resembles what was observed in the literature for the rutile TiO2(110) surface, however the latter is not known to have oxygenmore » diffusion between the bulk and surface under typical ultrahigh vacuum conditions. We speculate that the open lattice of the anatase bulk structure may facilitate independent diffusion of both point defects (Ti interstitials and O vacancies) or concerted diffusion of "TiO" subunits. The authors gratefully acknowledge S.A. Chambers of Pacific Northwest National Laboratory (PNNL) for providing the anatase samples. This research was supported by the U.S. Department of Energy (DOE) Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, the Office of Naval Research Contract Number 200CAR262, and the Oregon Nanoscience and Microtechnologies Institute. PNNL is operated for the U.S. DOE by Battelle under Contract Number DE05-AC76RL0 1830. The research was performed in the William R. Wiley Environmental Molecular Sciences Laboratory, a national scientific user facility funded by the U.S. DOE Office of Biological and Environmental Research.« less

Electronic structures of anatase (TiO2)1-x(TaON)x solid solutions: a first-principles study.

PubMed

Dang, Wenqiang; Chen, Hungru; Umezawa, Naoto; Zhang, Junying

2015-07-21

Sensitizing wide band gap photo-functional materials under visible-light irradiation is an important task for efficient solar energy conversion. Although nitrogen doping into anatase TiO2 has been extensively studied for this purpose, it is hard to increase the nitrogen content in anatase TiO2 because of the aliovalent nitrogen substituted for oxygen, leading to the formation of secondary phases or defects that hamper the migration of photoexcited charge carriers. In this paper, electronic structures of (TiO2)1-x(TaON)x (0 ≤ x ≤ 1) solid solutions, in which the stoichiometry is satisfied with the co-substitution of Ti for Ta along with O for N, are investigated within the anatase crystal structure using first-principles calculations. Our computational results show that the solid solutions have substantially narrower band gaps than TiO2, without introducing any localized energy states in the forbidden gap. In addition, in comparison with the pristine TiO2, the solid solution has a direct band gap when the content of TaON exceeds 0.25, which is advantageous to light absorption. The valence band maximum (VBM) of the solid solutions, which is mainly composed of N 2p states hybridized with O 2p, Ti 3d or Ta 5d orbitals, is higher in energy than that of pristine anatase TiO2 consisting of non-bonding O 2p states. On the other hand, incorporating TaON into TiO2 causes the formation of d-d bonding states through π interactions and substantially lowers the conduction band minimum (CBM) because of the shortened distance between some metal atoms. As a result, the anatase (TiO2)1-x(TaON)x is expected to become a promising visible-light absorber. In addition, some atomic configurations are found to possess exceptionally narrow band gaps.

Uniform Gold-Nanoparticle-Decorated {001}-Faceted Anatase TiO2 Nanosheets for Enhanced Solar-Light Photocatalytic Reactions.

PubMed

Shi, Huimin; Zhang, Shi; Zhu, Xupeng; Liu, Yu; Wang, Tao; Jiang, Tian; Zhang, Guanhua; Duan, Huigao

2017-10-25

The {001}-faceted anatase TiO 2 micro-/nanocrystals have been widely investigated for enhancing the photocatalysis and photoelectrochemical performance of TiO 2 nanostructures, but their practical applications still require improved energy conversion efficiency under solar-light and enhanced cycling stability. In this work, we demonstrate the controlled growth of ultrathin {001}-faceted anatase TiO 2 nanosheets on flexible carbon cloth for enhancing the cycling stability, and the solar-light photocatalytic performance of the synthesized TiO 2 nanosheets can be significantly improved by decorating with vapor-phase-deposited uniformly distributed plasmonic gold nanoparticles. The fabricated Au-TiO 2 hybrid system shows an 8-fold solar-light photocatalysis enhancement factor in photodegrading Rhodamine B, a high photocurrent density of 300 μA cm -2 under the illumination of AM 1.5G, and 100% recyclability under a consecutive long-term cycling measurement. Combined with electromagnetic simulations and systematic control experiments, it is believed that the tandem-type separation and transition of plasmon-induced hot electrons from Au nanoparticles to the {001} facet of anatase TiO 2 , and then to the neighboring {101} facet, is responsible for the enhanced solar-light photochemical performance of the hybrid system. The Au-TiO 2 nanosheet system addresses well the problems of the limited solar-light response of anatase TiO 2 and fast recombination of photogenerated electron-hole pairs, representing a promising high-performance recyclable solar-light-responding system for practical photocatalytic reactions.

Microstructure evolution characteristics induced by oxygen vacancy generation in anatase TiO2 based resistive switching devices

NASA Astrophysics Data System (ADS)

Liu, Chen; Gao, Bin; Huang, Peng; Kang, Jinfeng

2017-03-01

In this work, first principle calculations are employed to study the microstructure characteristics of the anatase TiO2 resistive switching material associated with the generation of oxygen vacancy (V o) based nanofilaments during the switching process. The calculations indicate that both the magnéli phase Ti4O7 and V o-defect phase of anatase TiO2 may be formed with the generation of oxygen vacancies during the forming and SET processes. Based on the calculations, a new physical insight is proposed to clarify the microstructure evolution characteristics of the anatase TiO2 resistive switching material and the correlation with resistive switching behaviors. During the forming or SET process, the anatase TiO2 is first excited to a transition state with the generation of oxygen vacancies, then fully relaxes to a stable V o-defect state. This V o-defect state may either recover to the original state with the recombination of the oxygen vacancies, which causes the reversible resistive switching behavior, or further transform to a much more stable state—the magnéli phase Ti4O7, through a phase transition process with the generation of many more oxygen vacancies. The phase transition from V o- defective anatase phase to magnéli phase Ti4O7 causes the failure of the resistive switching due to the significantly reduced possibility of the reversible phase transition from the magnéli phase to the anatase phase, compared with the possibility of the recombination from the V o-defective anatase.

New insight into singlet oxygen generation at surface modified nanocrystalline TiO2--the effect of near-infrared irradiation.

PubMed

Buchalska, Marta; Labuz, Przemysław; Bujak, Łukasz; Szewczyk, Grzegorz; Sarna, Tadeusz; Maćkowski, Sebastian; Macyk, Wojciech

2013-07-14

The generation of singlet oxygen in aqueous colloids of nanocrystalline TiO2 (anatase) modified by organic chelating ligands forming surface Ti(IV) complexes was studied. Detailed studies revealed a plausible and to date unappreciated influence of near-infrared irradiation on singlet oxygen generation at the surface of TiO2. To detect (1)O2, direct and indirect methods have been applied: a photon counting technique enabling time-resolved measurements of (1)O2 phosphorescence, and fluorescence measurements of a product of singlet oxygen interaction with Singlet Oxygen Sensor Green (SOSG). Both methods proved the generation of (1)O2. Nanocrystalline TiO2 modified with salicylic acid appeared to be the most efficient photosensitizer among the tested materials. The measured quantum yield reached the value of 0.012 upon irradiation at 355 nm, while unmodified TiO2 colloids appeared to be substantially less efficient generators of singlet oxygen with the corresponding quantum yield of ca. 0.003. A photocatalytic degradation of 4-chlorophenol, proceeding through oxidation by OH˙, was also monitored. The influence of irradiation conditions (UV, vis, NIR or any combination of these spectral ranges) on the generation of both singlet oxygen and hydroxyl radicals has been tested and discussed. Simultaneous irradiation with visible and NIR light did not accelerate OH˙ formation; however, for TiO2 modified with catechol it influenced (1)O2 generation. Singlet oxygen is presumably formed according to Nosaka's mechanism comprising O2˙(-) oxidation with a strong oxidant (hole, an oxidized ligand); however, the energy transfer from NIR-excited titanium(iii) centers (trapped electrons) plays also a plausible role.

Preparation of anatase TiO2 thin film by low temperature annealing as an electron transport layer in inverted polymer solar cells

NASA Astrophysics Data System (ADS)

Noh, Hongche; Oh, Seong-Geun; Im, Seung Soon

2015-04-01

To prepare the anatase TiO2 thin films on ITO glass, amorphous TiO2 colloidal solution was synthesized through the simple sol-gel method by using titanium (IV) isopropoxide as a precursor. This amorphous TiO2 colloidal solution was spread on ITO glass by spin-coating, then treated at 450 °C to obtain anatase TiO2 film (for device A). For other TiO2 films, amorphous TiO2 colloidal solution was treated through solvothermal process at 180 °C to obtain anatase TiO2 colloidal solution. This anatase TiO2 colloidal solution was spread on ITO glass by spin coating, and then annealed at 200 °C (for device B) and 130 °C (for device C), respectively. The average particle size of amorphous TiO2 colloidal solution was about 1.0 nm and that of anatase TiO2 colloidal solution was 10 nm. The thickness of TiO2 films was about 15 nm for all cases. When inverted polymer solar cells were fabricated by using these TiO2 films as an electron transport layer, the device C showed the highest PCE (2.6%) due to the lack of defect, uniformness and high light absorbance of TiO2 films. The result of this study can be applied for the preparation of inverted polymer solar cell using TiO2 films as a buffer layer at low temperature on plastic substrate by roll-to roll process.

Improved photoelectrical performance of graphene supported highly crystallized anatase TiO2

NASA Astrophysics Data System (ADS)

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

2015-08-01

In this study, titanium oxysulfate (TiOSO4) and graphene were used as titanium source and supporter, respectively, to synthesize anatase TiO2-graphene (TiO2-G) composite. Crystal structure, morphology, and composition of TiO2-G were investigated by X-ray diffraction, scanning electron microscope, transmission electron microscope, and thermogravimetric analysis. Both TiO2-G and blank TiO2 powders exhibit spindle-shaped structure with the long axis along [001]. Compared to unsupported TiO2, TiO2 nanoparticles uniformly formed on graphene surface. When fabricated into dye-sensitized solar cells, photoelectrical conversion efficiency of TiO2-G (2.3 %) was much higher than that of blank TiO2 (0.89 %) prepared at the same conditions. Moreover, high sintering temperature enhanced photoelectrical performance of the composite. When the temperature was increased from 450 to 600 °C, the efficiency was improved from 1.5 to 2.6 %. The findings above demonstrate that TiO2-G has great potential for applications in dye-sensitized solar cells.

Anatase TiO2 single crystals with dominant {0 0 1} facets: Synthesis, shape-control mechanism and photocatalytic activity

NASA Astrophysics Data System (ADS)

Tong, Huifen; Zhou, Yingying; Chang, Gang; Li, Pai; Zhu, Ruizhi; He, Yunbin

2018-06-01

Anatase TiO2 micro-crystals with 51% surface exposing highly active {0 0 1} facets are prepared by hydrothermal synthesis using TiF4 as Ti resource and HF as morphology control agent. In addition, anatase TiO2 single crystals exposing large {0 0 1} crystal facets are facilely synthesized with "green" NaF plus HCl replacing HF for the morphology control. A series of comparative experiments are carried out for separately studying the effects of F- and H+ concentrations on the growth of TiO2 crystals, which have not been understood very much in depth so far. The results indicate that both F- and H+ synergistically affect the synthesis of truncated anatase octahedrons, where F- is preferentially adsorbed on the {0 0 1} facets resulting in lateral growth of these facets and H+ adjusts the growth rate of anatase TiO2 along different orientations by tuning the hydrolysis rate. Based on this information, anatase TiO2 single crystals with small size (1.3 μm) and large exposure of {0 0 1} facets (45%) are successfully prepared under optimal conditions ([H+]/[F-] = 20:1). Photocatalytic activities of the as-prepared products toward methylene blue photo-degradation are further tested. It is revealed that both crystal size and percentage of {0 0 1} facets are decisive for the photocatalytic performance, and the crystals with a small size (1.3 μm) and large exposure of {0 0 1} facets (45%) are catalytically most active. This work has clarified the main factors that control the growth process and morphology of anatase TiO2 single crystals for achieving superior photocatalytic properties.

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.

Photocatalytic self-cleaning TiO2 coatings on carbonatic stones

NASA Astrophysics Data System (ADS)

Bergamonti, Laura; Bondioli, Federica; Alfieri, Ilaria; Lorenzi, Andrea; Mattarozzi, Monica; Predieri, Giovanni; Lottici, Pier Paolo

2016-02-01

A self-cleaning coating based on TiO2 nanoparticles obtained by sol-gel method in an alkaline environment has been tested on different types of carbonatic stones: Botticino, Carrara and Pietra Dorata, frequently used in historic buildings. XRD and Raman measurements confirmed the nanocrystalline nature of titania in anatase form, with 5-10 nm crystal size, and evidenced a small amount of brookite. A fast photocatalytic oxidation by TiO2 coatings of the stained stones with methyl orange and methylene blue under UV lamp irradiation has been assessed. The enhancement of surface wettability due to UV-induced TiO2 hydrophilicity has been evidenced by contact angle measurements. ESEM/EDS showed a surface distribution of the coating fairly homogeneous. The coating does not introduce significant colorimetric changes of the stones and does not alter the water capillarity absorption. Thus, the alkaline nanocrystalline TiO2 is promising for self-cleaning coatings on carbonatic stones.

Clarification of the interaction between Au atoms and the anatase TiO2 (112) surface using density functional theory

NASA Astrophysics Data System (ADS)

Tada, Kohei; Koga, Hiroaki; Okumura, Mitsutaka; Tanaka, Shingo

2018-04-01

A model (112) surface slab of anatase TiO2 (112) was optimized, and the adsorption of Au atoms onto the (112) surface was investigated by first-principles calculations based on DFT (density functional theory) with the generalized gradient approximation (GGA). Furthermore, the results were compared with those of Au/anatase TiO2 (101) system. The (112) surface has a ridge and a groove (zig-zag structure). The Au atoms were strongly adsorbed in the grooves but became unstable as they climbed toward the ridges, and the promotion of electrons in the 5d orbitals to the 6s and 6p orbitals in the absorbed Au atom occurred. At the Au/anatase TiO2 interface, the Au-Ti4+ coordinate bond in the (112) system is stronger than that in the (101) system because the promotion of electrons is greater in the former interaction than the latter. The results suggest that Au/anatase TiO2 catalysts with a higher dispersion of Au nanoparticles could be prepared when the (112) surface is preferentially exposed.

Atomically engineered epitaxial anatase TiO 2 metal-semiconductor field-effect transistors

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

Kim, Brian S. Y.; Minohara, Makoto; Hikita, Yasuyuki

Here, anatase TiO 2 is a promising material for a vast array of electronic, energy, and environmental applications, including photocatalysis, photovoltaics, and sensors. A key requirement for these applications is the ability to modulate its electrical properties without dominant dopant scattering and while maintaining high carrier mobility. Here, we demonstrate the room temperature field-effect modulation of the conducting epitaxial interface between anatase TiO 2 and LaAlO 3 (001), which arises for LaO-terminated LaAlO 3, while the AlO 2-terminated interface is insulating. This approach, together with the metal-semiconductor field-effect transistor geometry, naturally bypasses the gate/channel interface traps, resulting in a highmore » field-effect mobility μ FE of 3.14 cm 2 (V s) –1 approaching 98% of the corresponding Hall mobility μ Hall. Accordingly, the channel conductivity is modulated over 6 orders of magnitude over a gate voltage range of ~4 V.« less

Atomically engineered epitaxial anatase TiO 2 metal-semiconductor field-effect transistors

DOE PAGES

Kim, Brian S. Y.; Minohara, Makoto; Hikita, Yasuyuki; ...

2018-03-26

Here, anatase TiO 2 is a promising material for a vast array of electronic, energy, and environmental applications, including photocatalysis, photovoltaics, and sensors. A key requirement for these applications is the ability to modulate its electrical properties without dominant dopant scattering and while maintaining high carrier mobility. Here, we demonstrate the room temperature field-effect modulation of the conducting epitaxial interface between anatase TiO 2 and LaAlO 3 (001), which arises for LaO-terminated LaAlO 3, while the AlO 2-terminated interface is insulating. This approach, together with the metal-semiconductor field-effect transistor geometry, naturally bypasses the gate/channel interface traps, resulting in a highmore » field-effect mobility μ FE of 3.14 cm 2 (V s) –1 approaching 98% of the corresponding Hall mobility μ Hall. Accordingly, the channel conductivity is modulated over 6 orders of magnitude over a gate voltage range of ~4 V.« less

Atomically engineered epitaxial anatase TiO2 metal-semiconductor field-effect transistors

NASA Astrophysics Data System (ADS)

Kim, Brian S. Y.; Minohara, Makoto; Hikita, Yasuyuki; Bell, Christopher; Hwang, Harold Y.

2018-03-01

Anatase TiO2 is a promising material for a vast array of electronic, energy, and environmental applications, including photocatalysis, photovoltaics, and sensors. A key requirement for these applications is the ability to modulate its electrical properties without dominant dopant scattering and while maintaining high carrier mobility. Here, we demonstrate the room temperature field-effect modulation of the conducting epitaxial interface between anatase TiO2 and LaAlO3 (001), which arises for LaO-terminated LaAlO3, while the AlO2-terminated interface is insulating. This approach, together with the metal-semiconductor field-effect transistor geometry, naturally bypasses the gate/channel interface traps, resulting in a high field-effect mobility μ FE of 3.14 cm2 (V s)-1 approaching 98% of the corresponding Hall mobility μ Hall . Accordingly, the channel conductivity is modulated over 6 orders of magnitude over a gate voltage range of ˜4 V.

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

Synthesis and Photocatalytic Activity of Anatase TiO2 Nanoparticles-coated Carbon Nanotubes

NASA Astrophysics Data System (ADS)

Xie, Yi; Heo, Sung Hwan; Yoo, Seung Hwa; Ali, Ghafar; Cho, Sung Oh

2010-03-01

A simple and straightforward approach to prepare TiO2-coated carbon nanotubes (CNTs) is presented. Anatase TiO2 nanoparticles (NPs) with the average size ~8 nm were coated on CNTs from peroxo titanic acid (PTA) precursor even at low temperature of 100 °C. We demonstrate the effects of CNTs/TiO2 molar ratio on the adsorption capability and photocatalytic efficiency under UV-visible irradiation. The samples showed not only good optical absorption in visible range, but also great adsorption capacity for methyl orange (MO) dye molecules. These properties facilitated the great enhancement of photocatalytic activity of TiO2 NPs-coated CNTs photocatalysts. The TiO2 NPs-coated CNTs exhibited 2.45 times higher photocatalytic activity for MO degradation than that of pure TiO2.

Synthesis and Photocatalytic Activity of Anatase TiO2 Nanoparticles-coated Carbon Nanotubes

PubMed Central

2010-01-01

A simple and straightforward approach to prepare TiO2-coated carbon nanotubes (CNTs) is presented. Anatase TiO2 nanoparticles (NPs) with the average size ~8 nm were coated on CNTs from peroxo titanic acid (PTA) precursor even at low temperature of 100 °C. We demonstrate the effects of CNTs/TiO2 molar ratio on the adsorption capability and photocatalytic efficiency under UV–visible irradiation. The samples showed not only good optical absorption in visible range, but also great adsorption capacity for methyl orange (MO) dye molecules. These properties facilitated the great enhancement of photocatalytic activity of TiO2 NPs-coated CNTs photocatalysts. The TiO2 NPs-coated CNTs exhibited 2.45 times higher photocatalytic activity for MO degradation than that of pure TiO2. PMID:20671780

Synthesis of anatase TiO2 nanoparticles with beta-cyclodextrin as a supramolecular shell.

PubMed

Li, Landong; Sun, Xiaohong; Yang, Yali; Guan, Naijia; Zhang, Fuxiang

2006-11-20

We report a novel, green hydrothermal-synthesis route to well-dispersed anatase TiO2 nanoparticles with particle sizes of 9-16 nm in the presence of beta-CD (beta-cyclodextrin). During the synthesis process, the CD-containing synthesis mixture assembled in both longitudinal and latitudinal directions. Driven by the interaction between molecules, the beta-CDs assembled in the longitudinal direction to form long-chain compounds, whereas in the latitudinal direction, they tended to form regular aggregates through coordination with the Ti species from the hydrolysis of tetrabutyl titanate. In view of the effect of the coordination and the steric hindrance of beta-CDs as a supramolecular shell, homogeneous nuclei and slow growth of TiO2 crystals during the synthesis process was observed, which was responsible for the formation of uniform TiO2 nanoparticles. The low beta-CD dosage and the high product yield (>90%) demonstrated well the potential of this synthesis route in the large-scale industrial production of anatase nanoparticles.

100-Fold Enhancement of Charge Transport in Uniaxially Oriented Mesoporous Anatase TiO 2 Films

DOE PAGES

Li, Ke; Liu, Jie; Sheng, Xia; ...

2017-12-04

Mesoporous semiconductor films are of considerable interest for applications in photoelectrochemical devices, however, despite intensive research till now, their charge transport properties remain significantly lower than their single-crystal counterparts. Herein, we report a novel low-temperature template-free technique for growing high surface area mesoporous anatase TiO2 films with a preferred [001] crystalline-orientation on FTO-coated glass substrate. Compared to mesoporous films that comprised of randomly oriented crystallites, the uniaxial orientation enables a 100-fold increase in the rate of electron transport. The uniaxially oriented mesoporous anatase TiO2 films exhibit should greatly facilitate the development and application of photoelectrochemical and electrochemical devices.

Influence of surfactant and annealing temperature on optical properties of sol-gel derived nano-crystalline TiO2 thin films.

PubMed

Vishwas, M; Sharma, Sudhir Kumar; Rao, K Narasimha; Mohan, S; Gowda, K V Arjuna; Chakradhar, R P S

2010-03-01

Titanium dioxide thin films have been synthesized by sol-gel spin coating technique on glass and silicon substrates with and without surfactant polyethylene glycol (PEG). XRD and SEM results confirm the presence of nano-crystalline (anatase) phase at an annealing temperature of 300 degrees C. The influence of surfactant and annealing temperature on optical properties of TiO(2) thin films has been studied. Optical constants and film thickness were estimated by Swanepoel's (envelope) method and by ellipsometric measurements in the visible spectral range. The optical transmittance and reflectance were found to decrease with an increase in PEG percentage. Refractive index of the films decreased and film thickness increased with the increase in percentage of surfactant. The refractive index of the un-doped TiO(2) films was estimated at different annealing temperatures and it has increased with the increasing annealing temperature. The optical band gap of pure TiO(2) films was estimated by Tauc's method at different annealing temperature. Copyright 2010 Elsevier B.V. All rights reserved.

Removal of nitric oxide by the highly reactive anatase TiO2 (001) surface: a density functional theory study.

PubMed

Zhao, Wenwen; Tian, Feng Hui; Wang, Xiaobin; Zhao, Linghuan; Wang, Yun; Fu, Aiping; Yuan, Shuping; Chu, Tianshu; Xia, Linhua; Yu, Jimmy C; Duan, Yunbo

2014-09-15

In this paper, density functional theory (DFT) calculation was employed to study the adsorption of nitric oxide (NO) on the highly reactive anatase TiO2 (001) surface. For comparison, the adsorption of NO on the (101) surface was also considered. Different from the physical adsorption on the (101) surface, NO molecules are found to chemisorb on the TiO2 (001) surface. The twofold coordinate oxygen atoms (O2c) on the anatase (001) surface are the active sites. Where NO is oxidized into a nitrite species (NO2(-)) trapping efficiently on the surface, with one of the surface Ti5c-O2c bonds adjacent to the adsorption site broken. Our results, therefore, supply a theoretical guidance to remove NO pollutants using highly reactive anatase TiO2 (001) facets. Copyright © 2014 Elsevier Inc. All rights reserved.

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.

Solvothermal synthesis of nanocrystalline TiO 2 in toluene with surfactant

NASA Astrophysics Data System (ADS)

Kim, Chung-Sik; Moon, Byung Kee; Park, Jong-Ho; Choi, Byung-Chun; Seo, Hyo-Jin

2003-10-01

Synthesis of narrow-dispersed nanocrystalline TiO 2 was investigated by surfactant-aided solvothermal synthetic method in toluene solutions. Titanium isopropoxide (TIP) was used as precursor, which was decomposed at high temperature in the surfactant-dissolved solution. After the solution was thermally treated at 250°C for 20 h in an autoclave, low-dispersed TiO 2 nanocrystalline particles with average size of <6 nm were synthesized. When sufficient amount of TIP or surfactant was added in the solution, long dumbbell-shaped nanorods were formed, which may be due to the oriented growth of particles along [0 0 1] axis. Characterization of products was investigated by X-ray diffraction and transmission electron microscopy.

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.

Characterization of Phosphate Species on Hydrated Anatase TiO2 Surfaces.

PubMed

Tielens, Frederik; Gervais, Christel; Deroy, Geraldine; Jaber, Maguy; Stievano, Lorenzo; Coelho Diogo, Cristina; Lambert, Jean-François

2016-02-02

The adsorption/interaction of KH2PO4 with solvated (100) and (101) TiO2 anatase surfaces is investigated using periodic DFT calculations in combination with GIPAW NMR calculations and experimental IR and solid state (17)O, and (31)P NMR spectroscopies. A complete and realistic model has been used to simulate the solvent by individual water molecules. The most stable adsorption configurations are characterized theoretically at the atomic scale, and experimentally supported by NMR and IR spectroscopies. It is shown that H2PO4(-) chemisorbs on the (100) and (101) anatase surfaces, preferentially via a bidentate geometry. Dimer (H3P2O7(-)) and trimer (H4P3O10(-)) adsorption models are confronted with monomer adsorption models, in order to rationalize their occurrence.

The effect of anatase TiO2 surface structure on the behavior of ethanol adsorption and its initial dissociation step: A DFT study

NASA Astrophysics Data System (ADS)

Zhang, Riguang; Liu, Zhixue; Ling, Lixia; Wang, Baojun

2015-10-01

The perfect and defective surfaces of anatase TiO2 including (1 0 1) and (0 0 1) surfaces have been chosen to probe into the effect of anatase TiO2 surface structure on the behavior of ethanol adsorption and initial dissociation step. Here, the results are obtained by density functional theory (DFT) calculation together with the periodic slab model. Our results show that the surface structure of anatase TiO2 can obviously affect the behavior of ethanol adsorption and the catalytic activity of its initial dissociation step; firstly, on the perfect and defective surfaces of anatase (1 0 1), ethanol dominantly exists in the form of molecule adsorption; however, ethanol is the dissociative adsorption on the hydroxylated anatase (0 0 1), and the coexistences of molecular and dissociation adsorption modes on the perfect anatase (0 0 1). On the other hand, the initial dissociation step of ethanol with molecule adsorption prefers to begin with its O-H bond cleavage leading to CH3CH2O and H species rather than the cleavage of its α-C-H, β-C-H, C-C and C-O bonds, namely, the preferable O-H bond cleavage for the initial dissociation step of ethanol is independent of the surface structure of anatase TiO2; however, the corresponding catalytic activity of ethanol initial dissociation step with the O-H bond cleavage on different anatase TiO2 surfaces is in the following order: hydroxylated (0 0 1) > perfect (0 0 1) > defective (1 0 1) > perfect (1 0 1), suggesting that the catalytic activity for the initial dissociation step of ethanol is sensitive to the surface structure of anatase TiO2, and the hydroxylated (0 0 1) is the most favorable surface. Among these surfaces, the most favorable product for the initial dissociation step of ethanol is CH3CH2O species.

Anatase TiO2@C composites with porous structure as an advanced anode material for Na ion batteries

NASA Astrophysics Data System (ADS)

Shi, Xiaodong; Zhang, Zhian; Du, Ke; Lai, Yanqing; Fang, Jing; Li, Jie

2016-10-01

In this paper, we propose a facile strategy to synthesize the porous structure TiO2@C composites through a two-step method, in which the precursor of MIL-125(Ti) was firstly prepared by solvent thermal method and then calcined under inert atmosphere. When employed as anodes for Na ion batteries, TiO2@C composites can exhibit a superior cyclability with a reversible sodium storage capacity of 148 mAh g-1 at the current density 0.5 A g-1 after 500 cycles and an excellent rate performance with a capacity of 88.9 mAh g-1 even the current reached to 2.5 A g-1 due to the dispersion of anatase TiO2 throughout amorphous carbon matrix and the synergistic effect between the anatase TiO2 nanocrystals and carbon matrix, which can availably enhance the electric conductivity and alleviate the volumetric variation of TiO2 during the insertion/extraction process of Na+.

Adsorption and oxidation of oxalic acid on anatase TiO2 (001) surface: A density functional theory study.

PubMed

Sun, Tao; Wang, Yun; Zhang, Haimin; Liu, Porun; Zhao, Huijun

2015-09-15

Anatase TiO2 (001) surfaces have attracted great interest for photo-degradation of organic species recently due to their high reactivity. In this work, adsorption properties and oxidation mechanisms of oxalic acid on the anatase TiO2 (001) surface have been theoretically investigated using the first-principles density functional theory. Various possible adsorption configurations are considered by diversifying the connectivity of carboxylic groups with the surface. It is found that the adsorption of oxalic acid on the anatase (001) surface prefer the dissociative states. A novel double-bidentate configuration has been found due to the structural match between oxalic acid and the (001) surface. More charge is transferred from the adsorbed oxalic acid to the surface with the double-bidentate configuration when comparing with other adsorption structures. Thus, there is a positive correlation relationship between the transferred charge amount and the interfacial bond numbers when oxalic acid adsorbs on the anatase TiO2 (001) surface. The adsorption energies with dispersion corrections have demonstrated that the van der Waals interactions play an important role in the adsorption, especially when adsorbates are close to the surface. Copyright © 2015 Elsevier Inc. All rights reserved.

Density functional theory study of atomic and electronic properties of defects in reduced anatase TiO2 nanocrystals

NASA Astrophysics Data System (ADS)

Morita, Kazuki; Yasuoka, Kenji

2018-03-01

Anatase TiO2 nanocrystals have received considerable attention owing to their promising applications in photocatalysis, photovoltaics, and fuel cells. Although experimental evidence has shown that the performance of nanocrystals can be significantly improved through reduction, the mechanistic basis of this enhancement remains unclear. To shed a light on the chemistry of reduced anatase TiO2 nanocrystals, density functional theory were used to investigate the properties of defects and excess electrons. We demonstrated that oxygen vacancies are stable both on the surface and at the sub-surface of the nanocrystal, while titanium interstitials prefer sub-surface sites. Different defect locations possessed different excess electron structures, which contributed to deep and shallow states in the band gap of the nanocrystals. Furthermore, valence band tailing was observed, resulting in band gap narrowing. The theoretical results presented here deepen our understanding, and show the potential of defects to considerably change the macroscopic properties of anatase TiO2 nanocrystals.

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.

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.

Superior environment resistance of quartz crystal microbalance with anatase TiO2/ZnO nanorod composite films

NASA Astrophysics Data System (ADS)

Qiang, Wei; Wei, Li; Shaodan, Wang; Yu, Bai

2015-08-01

The precise measurement of quartz crystal microbalance (QCM) in the detection and weighing of organic gas molecules is achieved due to excellent superhydrophobicity of a deposited film composite. Photocatalysis is utilized as a method for the self-cleaning of organic molecules on the QCM for extended long-term stability in the precision of the instrument. In this paper, ZnO nanorod array is prepared via in situ methods on the QCM coated with Au film via hydrothermal process. Subsequently, a TiO2/ZnO composite film is synthesized by surface modification with TiO2 via sol-gel methods. Results show the anatase TiO2/ZnO nanorod composite film with a sharp, pencil-like structure exhibiting excellent superhydrophobicity (water contact angle of 155°), non-sticking water properties, and an autonomous cleaning property under UV irradiation. The anatase TiO2/ZnO nanorod composite film facilitates the precise measurement and extended lifetime of the QCM for the detection of organic gas molecules.

Ultraviolet emission enhancement in ZnO thin films modified by nanocrystalline TiO2

NASA Astrophysics Data System (ADS)

Zheng, Gaige; Lu, Xi; Qian, Liming; Xian, Fenglin

2017-05-01

In this study, nanocrystalline TiO2 modified ZnO thin films were prepared by electron beam evaporation. The structural, morphological and optical properties of the samples were analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), UV-visible spectroscopy, fluorescence spectroscopy, respectively. The composition of the films was examined by energy dispersive X-ray spectroscopy (EDX). The photoluminescent spectrum shows that the pure ZnO thin film exhibits an ultraviolet (UV) emission peak and a strong green emission band. Surface analysis indicates that the ZnO thin film contains many oxygen vacancy defects on the surface. After the ZnO thin film is modified by the nanocrystalline TiO2 layer, the UV emission of ZnO is largely enhanced and the green emission is greatly suppressed, which suggests that the surface defects such as oxygen vacancies are passivated by the TiO2 capping layer. As for the UV emission enhancement of the ZnO thin film, the optimized thickness of the TiO2 capping layer is ∼16 nm. When the thickness is larger than 16 nm, the UV emission of the ZnO thin film will decrease because the TiO2 capping layer absorbs most of the excitation energy. The UV emission enhancement in the nanocrystalline TiO2 modified ZnO thin film can be attributed to surface passivation and flat band effect.

Study on defect properties of nanocrystalline TiO2 during phase transition by positron annihilation lifetime

NASA Astrophysics Data System (ADS)

Zheng, F.; Liu, Y.; Liu, Z.; Dai, Y.-Q.; Fang, P.-F.; Wang, S.-J.

2012-08-01

The defect properties of nanocrystalline TiO2 were investigated by positron annihilation lifetime spectroscopy (PALS) and X-ray diffraction (XRD) as a function of annealed temperature that ranged from 300 to 850 °C. Below 500 °C, the measured positron lifetimes of τ1 (200-206 ps) and τ2 (378-402 ps) revealed the existence of mono-vacancy and vacancy-clusters at grain surface and in the micro-void of intergranular region. Between 500 and 750 °C, the phase transition from anatase to rutile was probed by the variations of positron lifetime and XRD pattern. With the increasing temperature from 500 to 850 °C, the positron lifetime τ1, τ2 and its intensity I2 sharply decreased from 200 ps, 378 ps, and 60% to 135 ps, 274 ps, and 33%, respectively. The results clearly indicate that the mono-vacancy or vacancy-clusters at grain surface and micro-voids between the grains were annealed out during the phase transition.

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.

Simple sol-gel process to obtain silica-coated anatase particles with enhanced TiO2-SiO2 interfacial area.

PubMed

Resende, S F; Nunes, E H M; Houmard, M; Vasconcelos, W L

2014-11-01

In this study we prepared silica-titania composites with a low SiO2:TiO2 molar ratio. These materials were prepared using a simple sol-gel route in which a hydrothermal treatment was used to obtain mesoporous anatase particles. Pure titania was also synthetized for comparison purposes. These materials were examined by scanning and transmission electron microscopy (SEM and TEM, respectively), energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), and nitrogen sorption tests. A thin silica coating was formed on the anatase particles. It was observed that the presence of this coating led to samples with an enhanced thermal stability. Indeed, the composites prepared in this work showed an anatase structure and a high specific surface area (SSA), even after their calcination at 800°C. Thus, we believe that the synthetized material present an outstanding SiO2-TiO2 interfacial area associated with a high amount of anatase particles which could improve its photoactive properties. Copyright © 2014 Elsevier Inc. All rights reserved.

a New Method to Prepare the Novel Anatase TiO2

NASA Astrophysics Data System (ADS)

Cui, Guanjun; Xu, Zhanxia; Wang, Yan; Zhang, Min; Yang, Jianjun

In this paper, a kind of novel anatase TiO2 nanoparticle with single-electron-trapped oxygen vacancies was prepared by hydrothermal treated nanotube titanic acid. The morphology, structure, and properties of the products were characterized by transmission electron microscope, X-ray diffraction, electron spin resonance, and photoluminescence. Photocatalytic decolorization of the Methylene Blue solution was carried out in the visible light region and showed a high photocatalytic activity.

Carbon coated anatase TiO2 mesocrystals enabling ultrastable and robust sodium storage

NASA Astrophysics Data System (ADS)

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

2017-08-01

Nanoporous anatase TiO2 mesocrystals with tunable architectures and crystalline phases were successfully fabricated in the presence of the butyl oleate and oleylamine. Especially, the introduced surfactants served as a carbon source, bring a uniform carbon layer (about 2-8 nm) for heightening the electronic conductivity. The carbon coated TiO2 mesocrystals assembled from crystalline tiny subunits have more space sites for sodium-ion storage. When the material was applied as an electrode material in rechargeable sodium-ion batteries, it exhibited a superior capacity of about 90 mA h g-1 at 20 C (1 C = 168 mA g-1) and a highly reversible capacity for 5000 cycles, which is the longest cycle life reported for sodium storage in TiO2 electrodes.

Synthesis and characterization of a mixed phase of anatase TiO2 and TiO2(B) by low pressure chemical vapour deposition (LPCVD) for high photocatalytic activity

NASA Astrophysics Data System (ADS)

Chimupala, Y.; Hyett, G.; Simpson, R.; Brydson, R.

2014-06-01

This project is concerned with enhancing photocatalytic activity by preparing a mixed phase of nano-sized TiO2. TiO2 thin films were synthesized by using Low Pressure Chemical Vapour Deposition (LPCVD). Titanium isopropoxide and N2 gas were used as the precursor and carrier gas respectively. The effects of reaction temperature, carrier gas flow rate and deposited area were studied. TiO2 thin films with nano-sized TiO2 particles were obtained under suitable conditions and SEM, TEM, powder XRD and Raman spectroscopy were employed to characterize the phase and physical appearance of synthesized materials. Preliminary results show that a dual phase (TiO2(B) and anatase) thin film nanopowder was successfully prepared by LPCVD with needle- and polygonal plate-shape crystallites respectively. This thin film deposit produced a preferred orientation of TiO2(B) needles in the [001] direction of average crystallite size 50-80 nm in length and 5-10 nm in width, whilst the crystallite size of anatase polygonal-plates was around 200 nm. The optimal LPCVD condition for preparing this mixed phase of TiO2 was 600°C with a 1 mL/s N2 flow rate.

Three-dimensional assembly structure of anatase TiO2 hollow microspheres with enhanced photocatalytic performance

NASA Astrophysics Data System (ADS)

Tang, Yihao; Zhan, Shuai; Wang, Li; Zhang, Bin; Ding, Minghui

The pure anatase TiO2 hollow microspheres are synthesized by a one-step template-free hydrothermal route. By defining temperature and time limits, we produce TiO2 hollow microspheres with a fluoride-mediated self-transformation. The surface morphology of TiO2 hollow microspheres was studied by SEM. The hollow microspheres have diameters of about 800 nm and are remarkably uniform. The UV-light photocatalytic activity and the stability/multifunction of TiO2 hollow microspheres structure were evaluated by photocatalytic degradation of methylene blue and photocatalytic hydrogen evolution. The excellent photocatalytic activity is attributed to large specific surface area, more active sites, unique hollow structures, and improved light scattering.

Low-Temperature Synthesis of Anatase TiO2 Nanoparticles with Tunable Surface Charges for Enhancing Photocatalytic Activity

PubMed Central

Li, Ye; Qin, Zhenping; Guo, Hongxia; Yang, Hanxiao; Zhang, Guojun; Ji, Shulan; Zeng, Tingying

2014-01-01

In this work, the positively or negatively charged anatase TiO2 nanoparticles were synthesized via a low temperature precipitation-peptization process (LTPPP) in the presence of poly(ethyleneimine) (PEI) and poly(sodium4- styrenesulfonate) (PSS). X-ray diffraction (XRD) pattern and high-resolution transmission electron microscope (HRTEM) confirmed the anatase crystalline phase. The charges of the prepared TiO2, PEI-TiO2 and PSS-TiO2 nanoparticles were investigated by zeta potentials. The results showed that the zeta potentials of PEI-TiO2 nanoparticles can be tuned from +39.47 mV to +95.46 mV, and that of PSS-TiO2 nanoparticles can be adjusted from −56.63 mV to −119.32 mV. In comparison with TiO2, PSS-TiO2 exhibited dramatic adsorption and degradation of dye molecules, while the PEI modified TiO2 nanoparticles showed lower photocatalytic activity. The photocatalytic performances of these charged nanoparticles were elucidated by the results of UV-vis diffuse reflectance spectra (DRS) and the photoluminescence (PL) spectra, which indicated that the PSS-TiO2 nanoparticles showed a lower recombination rate of electron-hole pairs than TiO2 and PEI-TiO2. PMID:25506839

Direct isolation of flavonoids from plants using ultra-small anatase TiO2 nanoparticles

PubMed Central

Kurepa, Jasmina; Nakabayashi, Ryo; Paunesku, Tatjana; Suzuki, Makoto; Saito, Kazuki; Woloschak, Gayle E.; Smalle, Jan A.

2013-01-01

Summary Surface functionalization of nanoparticles has become an important tool for the in vivo delivery of bioactive agents to their target sites. Here we describe the reverse strategy, nanoharvesting, in which nanoparticles are used as a tool to isolate and enrich bioactive compounds from living cells. Anatase TiO2 nanoparticles smaller than 20 nm form strong bonds with molecules carrying enediol and especially catechol groups. We show that these nanoparticles can enter plant cells, conjugate enediol and catechol group-rich flavonoids in situ, and exit plant cells as flavonoid-nanoparticle conjugates. The source plant tissues remain viable after treatment. As predicted by the surface chemistry of anatase TiO2 nanoparticles, the quercetin-based flavonoids were enriched amongst the nanoharvested flavonoid species. Nanoharvesting eliminates the use of organic solvents, allows spectral identification of the isolated compounds, and offers a new avenue for the use of nanomaterials for the coupled isolation and testing of bioactive properties of plant-made compounds. PMID:24147867

Modulation of Crystal Surface and Lattice by Doping: Achieving Ultrafast Metal-Ion Insertion in Anatase TiO2.

PubMed

Wang, Hsin-Yi; Chen, Han-Yi; Hsu, Ying-Ya; Stimming, Ulrich; Chen, Hao Ming; Liu, Bin

2016-10-26

We report that an ultrafast kinetics of reversible metal-ion insertion can be realized in anatase titanium dioxide (TiO 2 ). Niobium ions (Nb 5+ ) were carefully chosen to dope and drive anatase TiO 2 into very thin nanosheets standing perpendicularly onto transparent conductive electrode (TCE) and simultaneously construct TiO 2 with an ion-conducting surface together with expanded ion diffusion channels, which enabled ultrafast metal ions to diffuse across the electrolyte/solid interface and into the bulk of TiO 2 . To demonstrate the superior metal-ion insertion rate, the electrochromic features induced by ion intercalation were examined, which exhibited the best color switching speed of 4.82 s for coloration and 0.91 s for bleaching among all reported nanosized TiO 2 devices. When performed as the anode for the secondary battery, the modified TiO 2 was capable to deliver a highly reversible capacity of 61.2 mAh/g at an ultrahigh specific current rate of 60 C (10.2 A/g). This fast metal-ion insertion behavior was systematically investigated by the well-controlled electrochemical approaches, which quantitatively revealed both the enhanced surface kinetics and bulk ion diffusion rate. Our study could provide a facile methodology to modulate the ion diffusion kinetics for metal oxides.

N-doped hollow urchin-like anatase TiO2@C composite as a novel anode for Li-ion batteries

NASA Astrophysics Data System (ADS)

Xing, Yalan; Wang, Shengbin; Fang, Baizeng; Song, Ge; Wilkinson, David P.; Zhang, Shichao

2018-05-01

N-doped hollow urchin-like anatase TiO2 spheres (HUTSs) with carbon coating (HUTS@C) are prepared through a facile and scalable hydrothermal reaction followed by coating of polypyrrole and carbonization. The HUTS is composed of radially grown anatase nanorods and possesses an enhanced percentage of exposed {001} facets compared with P25 TiO2 nanoparticles. After the carbon coating, the HUTS@C retains the hollow nanostructure although covered with an N-doped carbon layer. As an anode for Li-ion batteries, the HUTS@C delivers a higher capacity of 165.1 mAh g-1 at 1C after 200 cycles and better rate capability (111.7 mAh g-1 at 10C) than the HUTS. Further electrochemical studies reveal that the HUTS@C has a better electrochemical reversibility, lower charge-transfer resistance, and higher Li-ion diffusion coefficient due to its unique nanosctructure including the hollow core, anatase phase of TiO2 microspheres with high exposed {001} facets and the N-doped carbon layer, which facilitates mass transport and enhances electrical conductivity.

Understanding the effect of surface/bulk defects on the photocatalytic activity of TiO2: anatase versus rutile.

PubMed

Yan, Junqing; Wu, Guangjun; Guan, Naijia; Li, Landong; Li, Zhuoxin; Cao, Xingzhong

2013-07-14

The sole effect of surface/bulk defects of TiO2 samples on their photocatalytic activity was investigated. Nano-sized anatase and rutile TiO2 were prepared by hydrothermal method and their surface/bulk defects were adjusted simply by calcination at different temperatures, i.e. 400-700 °C. High temperature calcinations induced the growth of crystalline sizes and a decrease in the surface areas, while the crystalline phase and the exposed facets were kept unchanged during calcination, as indicated by the characterization results from XRD, Raman, nitrogen adsorption-desorption, TEM and UV-Vis spectra. The existence of surface/bulk defects in calcined TiO2 samples was confirmed by photoluminescence and XPS spectra, and the surface/bulk defect ratio was quantitatively analyzed according to positron annihilation results. The photocatalytic activity of calcined TiO2 samples was evaluated in the photocatalytic reforming of methanol and the photocatalytic oxidation of α-phenethyl alcohol. Based on the characterization and catalytic results, a direct correlation between the surface specific photocatalytic activity and the surface/bulk defect density ratio could be drawn for both anatase TiO2 and rutile TiO2. The surface defects of TiO2, i.e. oxygen vacancy clusters, could promote the separation of electron-hole pairs under irradiation, and therefore, enhance the activity during photocatalytic reaction.

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.

Nanocrystalline Anatase Titania Supported Vanadia Catalysts: Facet-dependent Structure of Vanadia

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

Li, Wei-Zhen; Gao, Feng; Li, Yan

2015-07-09

Titania supported vanadia, a classic heterogeneous catalyst for redox reactions, typically has nonhomogeneous vanadia species on various titania facets, making it challenging not only to determine and quantify each species but also to decouple their catalytic contributions. We prepared truncated tetragonal bipyramidal (TiO2-TTB) and rod-like (TiO2-Rod) anatase titania with only {101} and {001} facets at ratios of about 80:20 and 93:7, respectively, and used them as supports of sub-monolayer vanadia. The structure and redox properties of supported vanadia were determined by XRD, TEM, XPS, EPR, Raman, FTIR and TPR, etc. It was found that vanadia preferentially occupy TiO2 {001} facetsmore » and form isolated O=V4+(O-Ti)2 species, and with further increase in vanadia surface coverage, isolated O=V5+(O-Ti)3 and oligomerized O=V5+(O-M)3 (M = Ti or V) species form on TiO2 {101} facets. The discovery on support facet-dependent structure of vanadia on anatase titania is expected to enable the elucidation of structure-function correlations on high surface area TiO2 supported vanadia catalysts. This work was supported by U. S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Biosciences and Geosciences. The research was performed in the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOE Office of Biological and Environmental Research, and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated for DOE by Battelle.« less

Mechanism of H adatoms improving the O2 reduction reaction on the Zn-modified anatase TiO2 (101) surface studied by first principles calculation.

PubMed

Liu, Liangliang; Li, Chongyang; Jiang, Man; Li, Xiaodong; Huang, Xiaowei; Wang, Zhu; Jia, Yu

2018-06-05

First principles calculations were performed to cast insight into the mechanism of the improvement of O2 reduction reaction (ORR) activity by Zn and H interstitials on the anatase TiO2 (101) surface. For the Zn-modified anatase TiO2 (101) surface, both surface and subsurface Zn interstitials could contribute to O2 adsorption and dissociation, but the dissociation barriers of O2 molecules are still too high, which limits the ORR activity. After a H adatom is introduced onto the Zn-modified anatase TiO2 (101) surface, the highest energy barriers are greatly reduced compared with those of the Zn-modified surface. Meanwhile, it is observed that the dissociation barriers decrease almost linearly with the increase of the charge difference of adsorption O2 between initial and transition state configurations. Specifically, subsurface Zn and surface H interstitials facilitate O2 dissociation and subsequent oxidation reactions, and further frequency analysis shows that these dissociation processes are frequent even at the room temperature of 300 K. In a word, this work provides a theoretical support to design a high ORR activity catalyst of the TiO2 nanocrystal comparable to precious Pt catalysts.

Synthesis of uniform layered protonated titanate hierarchical spheres and their transformation to anatase TiO2 for lithium-ion batteries.

PubMed

Wu, Hao Bin; Lou, Xiong Wen David; Hng, Huey Hoon

2012-02-13

Layered protonated titanates (LPTs), a class of interesting inorganic layered materials, have been widely studied because of their many unique properties and their use as precursors to many important TiO(2)-based functional materials. In this work, we have developed a facile solvothermal method to synthesize hierarchical spheres (HSs) assembled from ultrathin LPT nanosheets. These LPT hierarchical spheres possess a porous structure with a large specific surface area and high stability. Importantly, the size and morphology of the LPT hierarchical spheres are easily tunable by varying the synthesis conditions. These LPT HSs can be easily converted to anatase TiO(2) HSs without significant structural alteration. Depending on the calcination atmosphere of air or N(2), pure anatase TiO(2) HSs or carbon-supported TiO(2) HSs, respectively, can be obtained. Remarkably, both types of TiO(2) HSs manifest excellent cyclability and rate capability when evaluated as anode materials for high-power lithium-ion batteries. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Graphene-Wrapped Anatase TiO2 Nanofibers as High-Rate and Long-Cycle-Life Anode Material for Sodium Ion Batteries

PubMed Central

Yeo, Yeolmae; Jung, Ji-Won; Park, Kyusung; Kim, Il-Doo

2015-01-01

Anatase TiO2 has been suggested as a potential sodium anode material, but the low electrical conductivity of TiO2 often limits the rate capability, resulting in poor electrochemical properties. To address this limitation, we propose graphene-wrapped anatase TiO2 nanofibers (rGO@TiO2 NFs) through an effective wrapping of reduced graphene oxide (rGO) sheets on electrospun TiO2 NFs. To provide strong electrostatic interaction between the graphene oxide (GO) sheets and the TiO2 NFs, poly(allylamine hydrochloride) (PAH) was used to induce a positively charged TiO2 surface by the immobilization of the -NH3+ group and to promote bonding with the negatively charged carboxylic acid (-COO−) and hydroxyl (-O−) groups on the GO. A sodium anode electrode using rGO@TiO2 NFs exhibited a significantly improved initial capacity of 217 mAh g−1, high capacity retention (85% after 200 cycles at 0.2C), and a high average Coulombic efficiency (99.7% from the second cycle to the 200th cycle), even at a 5C rate, compared to those of pristine TiO2 NFs. The improved electrochemical performances stem from highly conductive properties of the reduced GO which is effectively anchored to the TiO2 NFs. PMID:26355340

The Electronic Structure and Optical Properties of Anatase TiO2 with Rare Earth Metal Dopants from First-Principles Calculations

PubMed Central

Xie, Kefeng; Jia, Qiangqiang; Wang, Yizhe; Zhang, Wenxue; Xu, Jingcheng

2018-01-01

The electronic and optical properties of the rare earth metal atom-doped anatase TiO2 have been investigated systematically via density functional theory calculations. The results show that TiO2 doped by Ce or Pr is the optimal choice because of its small band gap and strong optical absorption. Rare earth metal atom doping induces several impurity states that tune the location of valence and conduction bands and an obvious lattice distortion that should reduce the probability of electron–hole recombination. This effect of band change originates from the 4f electrons of the rare earth metal atoms, which leads to an improved visible light absorption. This finding indicates that the electronic structure of anatase TiO2 is tuned by the introduction of impurity atoms. PMID:29364161

Volume versus surface-mediated recombination in anatase TiO2 nanoparticles

NASA Astrophysics Data System (ADS)

Cavigli, Lucia; Bogani, Franco; Vinattieri, Anna; Faso, Valentina; Baldi, Giovanni

2009-09-01

We present an experimental study of the radiative recombination dynamics in size-controlled anatase TiO2 nanoparticles in the range 20-130 nm. From time-integrated photoluminescence spectra and picosecond time-resolved experiments as a function of the nanoparticle size, excitation density, and temperature, we show that photoluminescence comes out from a bulk and a surface radiative recombination. The spectral shift and the different time dynamics provide a clear distinction between them. Moreover, the intrinsic nature of the emission is also proven, providing a quantitative evaluation of volume and surface contributions.

ZrO2-modified mesoporous nanocrystalline TiO2-xNx as efficient visible light photocatalysts.

PubMed

Wang, Xinchen; Yu, Jimmy C; Chen, Yilin; Wu, Ling; Fu, Xianzhi

2006-04-01

Mesoporous nanocrystalline TiO2-xNx and TiO2-xNx/ZrO2 visible-light photocatalysts have been prepared by a sol-gel method. The photocatalysts were characterized by XRD, N2 adsorption-desorption, TEM, XPS, UV/Vis, and IR spectroscopy. The photocatalytic activity of the samples was evaluated by the decomposition of ethylene in air under visible light (lambda > 450 nm) illumination. Results revealed that nitrogen was doped into the lattice of TiO2 by the thermal treatment of NH3-adsorbed TiO2 hydrous gels, converting the TiO2 into a visible-light responsive catalyst. The introduction of ZrO2 into TiO2-xNx considerably inhibits the undesirable crystal growth during calcination. Consequently, the ZrO2-modified TiO2-xNx displays higher porosity, higher specific surface area, and an improved thermal stability over the corresponding unmodified TiO2-xNx samples.

Enhanced dye-sensitized solar cells performance using anatase TiO2 mesocrystals with the Wulff construction of nearly 100% exposed {101} facets as effective light scattering layer.

PubMed

Zhou, Yu; Wang, Xinyu; Wang, Hai; Song, Yeping; Fang, Liang; Ye, Naiqing; Wang, Linjiang

2014-03-28

Anatase TiO2 mesocrystals with a Wulff construction of nearly 100% exposed {101} facets were successfully synthesized by a facile, green solvothermal method. Their morphology, and crystal structure are characterized by powder X-ray diffraction (XRD), Field emission scanning electron microscopy (FESEM) and high-resolution transmission electron microscopy (HRTEM). Accordingly, a possible growth mechanism of anatase TiO2 mesocrystals is elucidated in this work. The as-prepared single anatase TiO2 mesocrystal's mean center diameter is about 500 nm, and the length is about 1 μm. They exhibit high light adsorbance, high reflectance and low transmittance in the visible region due to the unique nearly 100% exposed {101} facets. When utilized as the scattering layer in dye-sensitized solar cells (DSSCs), such mesocrystals effectively enhanced light harvesting and led to an increase of the photocurrent of the DSSCs. As a result, by using an anatase TiO2 mesocrystal film as a scattering overlayer of a compact commercial P25 TiO2 nanoparticle film, the double layered DSSCs show a power conversion efficiency of 7.23%, indicating a great improvement compared to the DSSCs based on a P25 film (5.39%) and anatase TiO2 mesocrystal films, respectively. The synergetic effect of P25 and the mesocrystals as well as the latters unique feature of a Wulff construction of nearly 100% exposed (101) facets are probably responsible for the enhanced photoelectrical performance. In particular, we explore the possibility of the low surface area and exposed {101} facets as an efficient light scattering layer of DSSCs. Our work suggests that anatase TiO2 mesocrystals with the Wulff construction is a promising candidate as a superior scattering material for high-performance DSSCs.

Preparation of (Fe, N)-doped TiO2 powders and their antibacterial activities under visible light irradiation.

PubMed

He, Rong-Liang; Wei, Yi; Cao, Wen-Bin

2009-02-01

Yellowish (Fe, N)-doped nanocrystalline TiO2 powders have been prepared using TiOSO4, CO(NH2)2, Fe(NO3)3.9H2O and CN3H5.HCl as precursors by hydrothermal method. The as-synthesized powders were anatase in phase and the grain size was about 10 nm according to the TEM photos. The ratio of Fe/Ti is 2.2 at% and N/O is 0.8 at% respectively. TiO2 powders were mixed with organic silicon and acrylic syrup to test their antibacterial performance by the colony counting method. The results show that the sterilization ratio of E. coli by the heat-treated (Fe, N)-doped nanocrystalline TiO2 powders is reached up to 94.5% while that of the powders without any heat treatment is 91.1% by 8 hours-400 lux-Visible-light irradiation with humidity of 55% RH.

Fabrication of NIR-responsive NaYF4:Yb,Tm/anatase TiO2 composite aerogel

NASA Astrophysics Data System (ADS)

Li, Fu-Chih; Kitamoto, Yoshitaka

2018-01-01

3-dimensional interconnected network structure of TiO2 aerogel has attracted considerable attention to solve environmental issues due to an advanced oxidation process which uses abundant sunlight for the complete minimization of toxic pollutants. The TiO2 aerogel with high specific surface area, large pores, and low density has a potential to be used as photocatalyst for air and water purification. Nonetheless, due to the larger band gap, TiO2 semiconductor photocatalysts possess high oxidizing properties under UV light only which occupies 5% of solar energy. To expand the absorption spectrum of TiO2 aerogel under solar irradiation, the NaYF4:Yb,Tm nanoparticles (NPs) are introduced into the TiO2 aerogel matrix structure. The morphology and crystal structure of the composite aerogel are investigated by transmission electron microscopy and X-ray diffraction, respectively. The particle size of NaYF4:Yb,Tm NPs is approximately 40 nm and the crystallite size of TiO2 is around 10 nm. In addition, the NaYF4:Yb,Tm NPs are enclosed by anatase phase of TiO2 aerogel. The NaYF4:Yb,Tm NPs which exist in the TiO2 aerogel has a capability of transferring NIR light to UV region.

Reversible magnesium and aluminium ions insertion in cation-deficient anatase TiO2

NASA Astrophysics Data System (ADS)

Koketsu, Toshinari; Ma, Jiwei; Morgan, Benjamin J.; Body, Monique; Legein, Christophe; Dachraoui, Walid; Giannini, Mattia; Demortière, Arnaud; Salanne, Mathieu; Dardoize, François; Groult, Henri; Borkiewicz, Olaf J.; Chapman, Karena W.; Strasser, Peter; Dambournet, Damien

2017-11-01

In contrast to monovalent lithium or sodium ions, the reversible insertion of multivalent ions such as Mg2+ and Al3+ into electrode materials remains an elusive goal. Here, we demonstrate a new strategy to achieve reversible Mg2+ and Al3+ insertion in anatase TiO2, achieved through aliovalent doping, to introduce a large number of titanium vacancies that act as intercalation sites. We present a broad range of experimental and theoretical characterizations that show a preferential insertion of multivalent ions into titanium vacancies, allowing a much greater capacity to be obtained compared to pure TiO2. This result highlights the possibility to use the chemistry of defects to unlock the electrochemical activity of known materials, providing a new strategy for the chemical design of materials for practical multivalent batteries.

First-principles study on codoping effect to enhance photocatalytic activity of anatase TiO2

NASA Astrophysics Data System (ADS)

Bai, Yujie; Zhang, Qinfang; Zheng, Fubao; Yang, Yun; Meng, Qiangqiang; Zhu, Lei; Wang, Baolin

2017-03-01

Codopant is an effective approach to modify the bandgap and band edge positions of transition metal oxide. Here, the electronic structures as well as the optical properties of pristine, mono-doped (N/P/Sb) and codoped (Sb, N/P) anatase TiO2 have been systematically investigated based on density functional theory calculations. It is found that mono-doped TiO2 exhibits either unoccupied or partially occupied intermediate state within the energy gap, which promotes the recombination of electron-hole pairs. However, the presence of (Sb, N/P) codopant not only effectively reduces the width of bandgap by introducing delocalized occupied intermediate states, but also adjusts the band edge alignment to enhance the hydrogen evolution activity of TiO2. Moreover, the optical absorption spectrum for (Sb, N/P) codoped TiO2, which is favored under oxygen-rich condition, demonstrates the improvement of its visible light absorption. These findings will promote the potential application of (Sb, N/P) codoped TiO2 photocatalysis for water splitting under visible light irradiation.

Rheological and volumetric properties of TiO2-ethylene glycol nanofluids

PubMed Central

2013-01-01

Homogeneous stable suspensions obtained by dispersing dry TiO2 nanoparticles in pure ethylene glycol were prepared and studied. Two types of nanocrystalline structure were analyzed, namely anatase and rutile phases, which have been characterized by scanning electron microscopy. The rheological behavior was determined for both nanofluids at nanoparticle mass concentrations up to 25%, including flow curves and frequency-dependent storage and loss moduli, using a cone-plate rotational rheometer. The effect of temperature over these flow curve tests at the highest concentration was also analyzed from 283.15 to 323.15 K. Furthermore, the influence of temperature, pressure, nanocrystalline structure, and concentration on the volumetric properties, including densities and isobaric thermal expansivities, were also analyzed. PMID:23763850

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

Reversible magnesium and aluminium ions insertion in cation-deficient anatase TiO 2

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

Koketsu, Toshinari; Ma, Jiwei; Morgan, Benjamin J.

In contrast to monovalent lithium or sodium ions, the reversible insertion of multivalent ions such as Mg 2+ and Al 3+ into electrode materials remains an elusive goal. In this work, we demonstrate a new strategy to achieve reversible Mg 2+ and Al 3+ insertion in anatase TiO 2, achieved through aliovalent doping, to introduce a large number of titanium vacancies that act as intercalation sites. We present a broad range of experimental and theoretical characterizations that show a preferential insertion of multivalent ions into titanium vacancies, allowing a much greater capacity to be obtained compared to pure TiO 2.more » In conclusion, this result highlights the possibility to use the chemistry of defects to unlock the electrochemical activity of known materials providing a new strategy for the chemical design of materials for practical multivalent batteries.« less

Reversible magnesium and aluminium ions insertion in cation-deficient anatase TiO 2

DOE PAGES

Koketsu, Toshinari; Ma, Jiwei; Morgan, Benjamin J.; ...

2017-09-18

In contrast to monovalent lithium or sodium ions, the reversible insertion of multivalent ions such as Mg 2+ and Al 3+ into electrode materials remains an elusive goal. In this work, we demonstrate a new strategy to achieve reversible Mg 2+ and Al 3+ insertion in anatase TiO 2, achieved through aliovalent doping, to introduce a large number of titanium vacancies that act as intercalation sites. We present a broad range of experimental and theoretical characterizations that show a preferential insertion of multivalent ions into titanium vacancies, allowing a much greater capacity to be obtained compared to pure TiO 2.more » In conclusion, this result highlights the possibility to use the chemistry of defects to unlock the electrochemical activity of known materials providing a new strategy for the chemical design of materials for practical multivalent batteries.« less

Structural and morphological characterization of anatase TiO 2 coating on χ-Alumina scale fiber fabricated by sol-gel dip-coating method

NASA Astrophysics Data System (ADS)

Nguyen, Hue Thi; Miao, Lei; Tanemura, Sakae; Tanemura, Masaki; Toh, Shoichi; Kaneko, Kenji; Kawasaki, Masahiro

2004-10-01

Anatase TiO 2 coatings 0.4 μm thick have been successfully fabricated by sol-gel dip-coating process on χ-Al 2O 3 fibers 100 μm by 10 cm long with a surface fish-scale. This was achieved by adjustment of the sol-gel parameters such as molar ratio of the precursors in TiO 2-sols, dip-coating time, drying duration in air, heating processes and number of cyclical repetitions of the process. Two samples were prepared using two sols containing different molar ratios of precursors. XRD, TEM, EDS and SEM characterization confirmed: (1) the similarity of the growth of anatase-TiO 2 from two sols under the optimal sol-gel parameters, (2) that the coatings are composed of aggregated crystallites of 10-25 nm in diameter, (3) the good compositional uniformity of Ti in the fabricated anatase-TiO 2 crystallites, (4) a surface covering ratio of anatase-TiO 2 around the fiber of at least 90%, and (5) that there is a good adherence of the fabricated anatase-TiO 2 layer on alumina fiber as evidenced by the lack of cracking and peeling off traces around the boundary between the coating and the fiber.

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.

Al13-pillared anatase TiO2 as a cathode for a lithium battery

NASA Astrophysics Data System (ADS)

Sun, X. D.; Ma, C. L.; Wang, Y. D.; Li, H. D.

2004-11-01

Al13-pillared anatase TiO2 is used as a cathode of a lithium battery for the first time. First, a layered titanium dioxide with cationic surfactant ions of cetyltrimethylammonium (CTA+) in the interlayers is synthesized by self-assembly. Then, pillared TiO2 is obtained by exchange of polyoxo cations of aluminium, [Al13O4(OH)24(H2O)12]7+, with CTA+ and subsequent calcination at 300 °C for 1 h in the air. Powder x-ray diffraction (XRD), transmission electron microscopy (TEM) and surface area (BET) methods are used to characterize the layered and pillared forms of titanium dioxide. A lithium battery with the Al13-pillared TiO2 as the cathode and Li metal foil as the anode is studied within the 1-2.2 V voltage range. The specific capacity of the closed button cell (size 2025) that is delivered on the initial discharge reached 191.4 mA h g-1 at the rate of 25 mA g-1. The cell shows good cycling performance over 50 cycles.

CO 2 Adsorption on Anatase TiO 2 (101) Surfaces in the Presence of Subnanometer Ag/Pt Clusters: Implications for CO 2 Photoreduction

DOE PAGES

Yang, Chi-Ta; Wood, Brandon C.; Bhethanabotla, Venkat R.; ...

2014-10-20

We show how CO 2 adsorption on perfect and reduced anatase TiO 2 (101) surfaces can be substantially modified by the presence of surface Ag and Pt octamer clusters, using density functional theory calculations. Furthermore, we found that adsorption was affected even at sites where the adsorbate was not in direct contact with the octamer, which we attributed to charge donation to CO 2 from the Ag/Pt-modified surface, as well as an electrostatic competition between attractive (Ti–O) and repulsive (Ti–C) interactions. Additionally, TiO 2-supported Pt octamers offer key advantages that could be leveraged for CO 2 photoreduction, including providing additionalmore » stable adsorption sites for bent CO 2 species and facilitating charge transfer to aid in CO 2– anion formation. Electronic structure analysis suggests these factors arise primarily from the hybridization of the bonding molecular orbitals of CO 2 with d orbitals of the Pt atoms. Our results show that, for adsorption on TiO 2-supported Pt octamers, the O–C–O bending and C–O asymmetric stretching frequencies can be used as reliable indicators of the presence of the CO 2– anion intermediate as well as to distinguish unique adsorption geometries or sites. Finally, we suggest a possible pathway for subsequent CO 2 dissociation to CO at the surface of a reduced anatase TiO 2 (101)-supported Pt octamer, which has a computed energy barrier of 1.01 eV.« less

Cellulose Tailored Anatase TiO2 Nanospindles in Three-Dimensional Graphene Composites for High-Performance Supercapacitors.

PubMed

Ding, Yangbin; Bai, Wei; Sun, Jinhua; Wu, Yu; Memon, Mushtaque A; Wang, Chao; Liu, Chengbin; Huang, Yong; Geng, Jianxin

2016-05-18

The morphologies of transition metal oxides have decisive impact on the performance of their applications. Here, we report a new and facile strategy for in situ preparation of anatase TiO2 nanospindles in three-dimensional reduced graphene oxide (RGO) structure (3D TiO2@RGO) using cellulose as both an intermediate agent eliminating the negative effect of graphene oxide (GO) on the growth of TiO2 crystals and as a structure-directing agent for the shape-controlled synthesis of TiO2 crystals. High-resolution transmission electron microscopy and X-ray diffractometer analysis indicated that the spindle shape of TiO2 crystals was formed through the restriction of the growth of high energy {010} facets due to preferential adsorption of cellulose on these facets. Because of the 3D structure of the composite, the large aspect ratio of the TiO2 nanospindles, and the exposed high-energy {010} facets of the TiO2 crystals, the 3D TiO2@RGO(Ce 1.7) exhibited excellent capacitive performance as an electrode material for supercapacitors, with a high specific capacitance (ca. 397 F g(-1)), a high energy density (55.7 Wh kg(-1)), and a high power density (1327 W kg(-1)) on the basis of the masses of RGO and TiO2. These levels of capacitive performance far exceed those of previously reported TiO2-based composites.

Photodecomposition of volatile organic compounds using TiO2 nanoparticles.

PubMed

Jwo, Ching-Song; Chang, Ho; Kao, Mu-Jnug; Lin, Chi-Hsiang

2007-06-01

This study examined the photodecomposition of volatile organic compounds (VOCs) using TiO2 catalyst fabricated by the Submerged Arc Nanoparticle Synthesis System (SANSS). TiO2 catalyst was employed to decompose volatile organic compounds and compare with Degussa-P25 TiO2 in terms of decomposition efficiency. In the electric discharge manufacturing process, a Ti bar, applied as the electrode, was melted and vaporized under high temperature. The vaporized Ti powders were then rapidly quenched under low-temperature and low-pressure conditions in deionized water, thus nucleating and forming nanocrystalline powders uniformly dispersed in the base solvent. The average diameter of the TiO2 nanoparticles was 20 nm. X-ray diffraction analysis confirmed that the nanoparticles in the deionized water were Anatase type TiO2. It was found that gaseous toluene exposed to UV irradiation produced intermediates that were even harder to decompose. After 60-min photocomposition, Degussa-P25 TiO2 reduced the concentration of gaseous toluene to 8.18% while the concentration after decomposition by SANSS TiO2 catalyst dropped to 0.35%. Under UV irradiation at 253.7 +/- 184.9 nm, TiO2 prepared by SANSS can produce strong chemical debonding energy, thus showing great efficiency, superior to that of Degussa-P25 TiO2, in decomposing gaseous toluene and its intermediates.

Characterization and properties of TiO2-SnO2 nanocomposites, obtained by hydrolysis method

NASA Astrophysics Data System (ADS)

Kutuzova, Anastasiya S.; Dontsova, Tetiana A.

2018-04-01

The paper deals with the process of TiO2-SnO2 nanocomposites synthesis utilizing simple hydrolysis method with further calcination for photocatalytic applications. The obtained nanopowders contain 100, 90, 75, 65 and 25 wt% of TiO2. The synthesized nanocomposite samples were analyzed by X-ray diffraction method, scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy and N2 adsorption-desorption method. The correlation between structure and morphology of the obtained nanocrystalline composite powders and their sorption and photocatalytic activity towards methylene blue degradation was established. It was found that the presence of SnO2 in the nanocomposites stabilizes the anatase phase of TiO2. Furthermore, sorption and photocatalytic properties of the obtained composites are significantly influenced not only by specific surface area, but also by pore size distribution and mesopore volume of the samples. In our opinion, the results obtained in this study have shown that the TiO2-SnO2 composites with SnO2 content that does not exceed 10% are promising for photocatalytic applications.

Preparation of nanocrystalline TiN coated cubic boron nitride powders by a sol-gel process.

PubMed

Park, Hee S; Umer, M Adeel; Ryu, Ho J; Hong, Soon H

2011-01-01

Cubic boron nitride (cBN) particles coated with 20 wt% nanocrystalline TiN were prepared by coating the surface of cBN particles with TiO2, followed by nitridation with NH3 gas at 900 degrees C. Coating of TiO2 on cBN powders was accomplished by a sol-gel process from a solution of titanium (IV) isopropoxide and anhydrous ethanol. An amorphous TiO(x) layer of 50 nm thickness was homogenously formed on the surface of the cBN particles by the sol-gel process. The amorphous layer was then crystallized to an anatase TiO2 phase through calcination in air at 400 degrees C. The crystallized TiO2 layer was 50 nm in thickness, and the size of TiO2 particles comprising the layer was nearly 10 nm. The TiO2 on cBN surfaces was completely converted into nanocrystalline TiN of uniform particles 20 nm in size on cBN particles by nitridation under flowing NH3 gas.

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.

Anatase TiO2 as a Cheap and Sustainable Buffering Filler for Silicon Nanoparticles in Lithium-Ion Battery Anodes.

PubMed

Maroni, Fabio; Carbonari, Gilberto; Croce, Fausto; Tossici, Roberto; Nobili, Francesco

2017-12-08

The design of effective supporting matrices to efficiently cycle Si nanoparticles is often difficult to achieve and requires complex preparation strategies. In this work, we present a simple synthesis of low-cost and environmentally benign aAnatase TiO 2 nanoparticles as buffering filler for Si nanoparticles (Si@TiO 2 ). The average anatase TiO 2 crystallite size was approximately 5 nm. A complete structural, morphological, and electrochemical characterization was performed. Electrochemical test results show very good specific capacity values of up to 1000 mAh g -1 and cycling at several specific currents, ranging from 500 to 2000 mA g -1 , demonstrating a very good tolerance to high cycling rates. Postmortem morphological analysis shows very good electrode integrity after 100 cycles at 500 mA g -1 specific current. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Anatase TiO2 ultrathin nanobelts derived from room-temperature-synthesized titanates for fast and safe lithium storage

PubMed Central

Wen, Wei; Wu, Jin-ming; Jiang, Yin-zhu; Yu, Sheng-lan; Bai, Jun-qiang; Cao, Min-hua; Cui, Jie

2015-01-01

Lithium-ion batteries (LIBs) are promising energy storage devices for portable electronics, electric vehicles, and power-grid applications. It is highly desirable yet challenging to develop a simple and scalable method for constructions of sustainable materials for fast and safe LIBs. Herein, we exploit a novel and scalable route to synthesize ultrathin nanobelts of anatase TiO2, which is resource abundant and is eligible for safe anodes in LIBs. The achieved ultrathin nanobelts demonstrate outstanding performances for lithium storage because of the unique nanoarchitecture and appropriate composition. Unlike conventional alkali-hydrothermal approaches to hydrogen titanates, the present room temperature alkaline-free wet chemistry strategy guarantees the ultrathin thickness for the resultant titanate nanobelts. The anatase TiO2 ultrathin nanobelts were achieved simply by a subsequent calcination in air. The synthesis route is convenient for metal decoration and also for fabricating thin films of one/three dimensional arrays on various substrates at low temperatures, in absence of any seed layers. PMID:26133276

Band edge movement and structural modifications in transition metal doped TiO2 nanocrystals for the application of DSSC

NASA Astrophysics Data System (ADS)

Patle, L. B.; Huse, V. R.; Chaudhari, A. L.

2017-10-01

Nanocrystalline undoped and transition metal ion doped (TM:Cu2+, Mn2+ and Fe3+) TiO2 nanoparticles, with 1 mol% were synthesized by a simple and cost effective modified co-precipitation method at room temperature and were successfully used as photoanode for dye sensitized solar cell (DSSC). The effect of transition metal ions into TiO2 nano crystalline powder has been systematically investigated using x-ray diffraction (XRD), UV-Vis spectroscope, scanning electron microscope (SEM), transmission electron microscope (TEM) and energy dispersive x-ray spectroscopy (EDX). The results of XRD confirm nanocrystalline anatase tetragonal structure of prepared undoped and TM doped TiO2 semiconductor. The influence of doping on band edge movement has been estimated using UV-visible spectroscopy. The SEM results indicate that microscopic effect of doping on morphology of the TiO2. The peaks of EDX signify incorporation of transition metal cations into TiO2 lattice. The effect of doping on flat band potential was estimated using interpolation on Mott-Schottky plot. The performances of DSSCs of undoped and doped TiO2 photoelectrodes were investigated under light illumination. In comparison with undoped and (Cu2+, Fe3+) doped TiO2 photoanodes we found that incorporation of Mn2+ into TiO2 exhibits improvement in photoconversion efficiency (η). There is increase in photoconversion efficiency of DSSCs with Mn2+ doped TiO2 by 6% as compared to that of undoped TiO2 photoanode.

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.

High Substitution Rate in TiO 2 Anatase Nanoparticles with Cationic Vacancies for Fast Lithium Storage

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

Li, Wei; Corradini, Dario; Body, Monique

2015-06-24

Doping is generally used to tune and enhance the properties of metal oxides. However, their chemical composition cannot be readily modified beyond low dopant amounts without disrupting the crystalline atomic structure. In the case of anatase TiO 2, we introduce a new solution-based chemical route allowing the composition to be significantly modified, substituting the divalent O 2- anions by monovalent F- and OH- anions resulting in the formation of cationic Ti 4+ vacancies (square) whose concentration can be controlled by the reaction temperature. The resulting polyanionic anatase has the general composition Ti 1-x-y square x+yO 2-4(x+y)F 4x(OH) 4y, reaching vacancymore » concentrations of up to 22%, i.e., Ti 0.78 square 0.22O 1.12F 0.4(OH) 0.48. Solid-state F-19 NMR spectroscopy reveals that fluoride ions can accommodate up to three different environments, depending on Ti and vacancies (i.e. Ti 3-F, Ti- 2 square 1-F, and Ti- 1 square 2-F), with a preferential location close to vacancies. DFT calculations further confirm the fluoride/vacancy ordering. When its characteristics were evaluated as an electrode for reversible Li-ion storage, the material shows a modified lithium reaction mechanism, which has been rationalized by the occurrence of cationic vacancies acting as additional lithium hosting sites within the anatase framework. Finally, the material shows a fast discharging/charging behavior, compared to TiO 2, highlighting the benefits of the structural modifications and paving the way for the design of advanced electrode materials, based on a defect mediated mechanism.« less

Photocatalytic Oxidation of Propylene on Pd-Loaded Anatase TiO2 Nanotubes Under Visible Light Irradiation

NASA Astrophysics Data System (ADS)

Li, Chen; Zong, Lanlan; Li, Qiuye; Zhang, Jiwei; Yang, Jianjun; Jin, Zhensheng

2016-05-01

TiO2 nanotubes attract much attention because of their high photoelectron-chemical and photocatalytic efficiency. But their large band gap leads to a low absorption of the solar light and limits the practical application. How to obtain TiO2 nanotubes without any dopant and possessing visible light response is a big challenge nowadays. Orthorhombic titanic acid nanotubes (TAN) are a special precursor of TiO2, which possess large Brunauer-Emmett-Teller (BET) surface areas and strong ion exchange and adsorption capacity. TAN can transform to a novel TiO2 with a large amount of single-electron-trapped oxygen vacancies (SETOV) during calcination, while their nanotubular structure would be destroyed, and a BET surface area would decrease remarkably. And interestingly, SETOV can lead to a visible light response for this kind of TiO2. Herein, glucose was penetrated into TAN by the vacuum inhalation method, and TAN would dehydrate to anatase TiO2, and glucose would undergo thermolysis completely in the calcination process. As a result, the pure TiO2 nanotubes with visible light response and large BET surface areas were obtained. For further improving the photocatalytic activity, Pd nanoparticles were loaded as the foreign electron traps on TiO2 nanotubes and the photocatalytic oxidation efficiency of propylene was as high as 71 % under visible light irradiation, and the photostability of the catalyst kept over 90 % after 4 cyclic tests.

Chemical dynamics of the first proton-coupled electron transfer of water oxidation on TiO2 anatase.

PubMed

Chen, Jia; Li, Ye-Fei; Sit, Patrick; Selloni, Annabella

2013-12-18

Titanium dioxide (TiO2) is a prototype, water-splitting (photo)catalyst, but its performance is limited by the large overpotential for the oxygen evolution reaction (OER). We report here a first-principles density functional theory study of the chemical dynamics of the first proton-coupled electron transfer (PCET), which is considered responsible for the large OER overpotential on TiO2. We use a periodic model of the TiO2/water interface that includes a slab of anatase TiO2 and explicit water molecules, sample the solvent configurations by first principles molecular dynamics, and determine the energy profiles of the two electronic states involved in the electron transfer (ET) by hybrid functional calculations. Our results suggest that the first PCET is sequential, with the ET following the proton transfer. The ET occurs via an inner sphere process, which is facilitated by a state in which one electronic hole is shared by the two oxygen ions involved in the transfer.

The Back Scattering Micro-Raman Spectroscopy of Different Crystalline Phases of TiO2 Nanoparticles Produced by Sol-Gel Technique

NASA Astrophysics Data System (ADS)

Malekfar, R.; Mihanyar, S.; Mozaffari, M.

2007-09-01

TiO2 is known to be one of the best photocatalysts among the semiconductors. In order to improve its photocatalytic features, it is necessary to be able to control factors such as the mean particle size, nanocrystalline system, grain shapes and diffraction. Nanocrystalline TiO2 sample powders were produced using H2O2 and Ti(OBu)4 as precursor materials and their above features were then characterized by using XRD, Raman spectroscopy and SEM. The grain size was calculated using the Debye Scherrer formula for anatase phase, 15 nm, which is in agreement with the value obtained by SEM imaging. Ti(OBu)4 was added dropwise to a very ice-cold solution of H2O2 under intensive stirring. This immediately yielded a red solution which was shortly followed by a strong exothermic reaction due to the unstable nature of the reaction at this stage. This process also involved rigorous giving off of H2O2, O2, and butyl alcohol. A yellow transparent peroxo-polytitanic (PPT) acid gel was thus prepared. This gel was then heated at 150 °C for 5 hours and was transformed into amorphous TiO2. The produced yellow powder was heated at 250 °C, 350 °C and 450 °C for one hour with a ramping up speed of 5 °C/min heating rate. It was later calcined at 550 °C, 750 °C and 950 °C for 30 minutes. By investigating the Raman spectra typically shown in figure 1 and also XRD patterns, it was confirmed that the anatase phase nanocrystalline powder, which is well known for its application as photocatalysts, was produced at the first three lower treatment temperatures mentioned above.

Facile synthesis of carbon-mediated porous nanocrystallite anatase TiO2 for improved sodium insertion capabilities as an anode for sodium-ion batteries

NASA Astrophysics Data System (ADS)

Wu, Feng; Luo, Rui; Xie, Man; Li, Li; Zhang, Xiaoxiao; Zhao, Luzi; Zhou, Jiahui; Wang, KangKang; Chen, Renjie

2017-09-01

Porous carbon-mediated nanocrystallite anatase TiO2 composites are synthesized successfully via a simple dilatory hydrolysis-calcination method. The structural and morphological characterizations reveal that carbon-mediated TiO2 with a carbon content of 9.9 wt % (C2-TiO2) shows a combination of mesoporous and macroporous structures with a pore volume of 0.20 cm3 g-1 and surface area of 40.3 m2 g-1. Notably, C2-TiO2 delivered enhanced electrochemical performances of a high charge capacity of 259 mA h g-1 at 0.1 C and a high rate performance of 110 mA h g-1 after 150 cycles, even at 1 C. A significant decrease is also observed in the electrochemical impedance of the carbon-mediated samples, which explains superior electrochemical performance. Compared with the bare anatase TiO2 (B-TiO2), improved sodium storage capabilities of carbon-mediated samples are attributed to the participation of carbon to form a symbiotic structure with TiO2, which not only increases pore volume of the samples but serves as highly conductive network to provide a Na+ diffusion path during the insertion/de-insertion of sodium ions. All of these encouraging results suggest that carbon-mediated TiO2 has a great potential for improving sodium insertion capabilities with a facile and low-cost synthesis process.

A first principle simulation of competitive adsorption of SF6 decomposition components on nitrogen-doped anatase TiO2 (101) surface

NASA Astrophysics Data System (ADS)

Dong, Xingchen; Zhang, Xiaoxing; Cui, Hao; Zhang, Jun

2017-11-01

Gas insulated switchgear has been widely used in modern electric systems due to its significantly excellent performances such as compact structure and low land occupation as well as the security stability. However, inside defects caused during manufacture process can lead to partial discharge which might develop into serious insulation failure. Online monitoring method on basis of gas sensors is considered a promising way of detecting partial discharge for alarm ahead of time. Research has found that TiO2 nanotubes sensors show good response to SO2, SOF2, SO2F2, the decomposition components as a result of partial discharge. In order to investigate the gas-sensing mechanism of nitrogen-doped TiO2 prepared via plasma treatment methods to SO2, SOF2, and SO2F2, the adsorption structures of both three gas molecules and anatase TiO2 (101) surface were built, and DFT calculations were then carried out for calculation and analysis of adsorption parameters. Adsorption property comparison of anatase TiO2 (101) surface after nitrogen doping with Au doping and without doping shows that nitrogen doping can obviously enhance the adsorption energy for SO2 and SOF2 adsorption and no charge transfer for SO2F2 adsorption, further explaining the adsorption mechanism and doping influence of different doping elements.

Benign Synthesis of Black Microspheres of Anatase TiO2 with Paramagnetic Oxygen Vacancies through NH3 Treatment.

PubMed

Maqbool, Qysar; Srivastava, Aasheesh

2017-10-09

Coloured TiO 2 is coveted for its ability to extract energy from the visible region of electromagnetic spectrum. Here a facile synthesis of black anatase titania microspheres (B-TiO 2 ) through a two-step process is reported. In the first step, amorphous white TiO 2 microspheres (W-TiO 2 ) are obtained by hydrolysing titanium tetraisopropoxide by ammonia vapours in ethanol. In the second step, the W-TiO 2 is thermally annealed at 500 °C to obtain B-TiO 2 . The diffuse reflectance analysis showed that B-TiO 2 absorbs across visible spectrum with absorption extending well into NIR region. Raman scattering together with EPR analysis showed compelling evidence of the existence of oxygen deficiency within the crystal in B-TiO 2 that induces black colouration in the sample. The defects present in the black anatase sample were confirmed to be single-electron-trapped (or paramagnetic) oxygen vacancies (V o ⋅) by XPS and EPR studies. The magnetic susceptibility studies showed existence of antiferromagnetic interactions between these unpaired electron spins. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Acid-assisted hydrothermal synthesis of nanocrystalline TiO2 from titanate nanotubes: influence of acids on the photodegradation of gaseous toluene.

PubMed

Chen, Kunyang; Zhu, Lizhong; Yang, Kun

2015-01-01

In order to efficiently remove volatile organic compounds (VOCs) from indoor air, one-dimensional titanate nanotubes (TiNTs) were hydrothermally treated to prepare TiO2 nanocrystals with different crystalline phases, shapes and sizes. The influences of various acids such as CH3COOH, HNO3, HCl, HF and H2SO4 used in the treatment were separately compared to optimize the performance of the TiO2 nanocrystals. Compared with the strong and corrosive inorganic acids, CH3COOH was not only safer and more environmentally friendly, but also more efficient in promoting the photocatalytic activity of the obtained TiO2. It was observed that the anatase TiO2 synthesized in 15 mol/L CH3COOH solution exhibited the highest photodegradation rate of gaseous toluene (94%), exceeding that of P25 (44%) by a factor of more than two. The improved photocatalytic activity was attributed to the small crystallite size and surface modification by CH3COOH. The influence of relative humidity (20%-80%) on the performance of TiO2 nanocrystals was also studied. The anatase TiO2 synthesized in 15 mol/L CH3COOH solution was more tolerant to moisture than the other TiO2 nanocrystals and P25. Copyright © 2014. Published by Elsevier B.V.

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.

High pressure synthesis of amorphous TiO2 nanotubes

NASA Astrophysics Data System (ADS)

Li, Quanjun; Liu, Ran; Wang, Tianyi; Xu, Ke; Dong, Qing; Liu, Bo; Liu, Jing; Liu, Bingbing

2015-09-01

Amorphous TiO2 nanotubes with diameters of 8-10 nm and length of several nanometers were synthesized by high pressure treatment of anatase TiO2 nanotubes. The structural phase transitions of anatase TiO2 nanotubes were investigated by using in-situ high-pressure synchrotron X-ray diffraction (XRD) method. The starting anatase structure is stable up to ˜20GPa, and transforms into a high-density amorphous (HDA) form at higher pressure. Pressure-modified high- to low-density transition was observed in the amorphous form upon decompression. The pressure-induced amorphization and polyamorphism are in good agreement with the previous results in ultrafine TiO2 nanoparticles and nanoribbons. The relationship between the LDA form and α-PbO2 phase was revealed by high-resolution transmission electron microscopy (HRTEM) study. In addition, the bulk modulus (B0 = 158 GPa) of the anatase TiO2 nanotubes is smaller than those of the corresponding bulks and nanoparticles (180-240 GPa). We suggest that the unique open-ended nanotube morphology and nanosize play important roles in the high pressure phase transition of TiO2 nanotubes.

Er3+ -doped anatase TiO2 nanocrystals: crystal-field levels, excited-state dynamics, upconversion, and defect luminescence.

PubMed

Luo, Wenqin; Fu, Chengyu; Li, Renfu; Liu, Yongsheng; Zhu, Haomiao; Chen, Xueyuan

2011-11-04

A comprehensive survey of electronic structure and optical properties of rare-earth ions embedded in semiconductor nanocrystals (NCs) is of vital importance for their potential applications in areas as diverse as luminescent bioprobes, lighting, and displays. Er3+ -doped anatase TiO2 NCs, synthesized via a facile sol-gel solvothermal method, exhibit intense and well-resolved intra-4f emissions of Er3+ . Crystal-field (CF) spectra of Er3+ in TiO2 NCs are systematically studied by means of high-resolution emission and excitation spectra at 10-300 K. The CF analysis of Er3+ assuming a site symmetry of C(2v) yields a small root-mean-square deviation of 25.1 cm(-1) and reveals the relatively large CF strength (549 cm(-1) ) of Er3+, thus verifying the rationality of the C(2v) symmetry assignment of Er3+ in anatase TiO2 NCs. Based on a simplified thermalization model for the temperature-dependent photoluminescence (PL) dynamics from (4) S(3/2) , the intrinsic radiative luminescence lifetimes of (4) S(3/2) and (2) H(11/2) are experimentally determined to be 3.70 and 1.73 μs, respectively. Green and red upconversion (UC) luminescence of Er3+ can be achieved upon laser excitation at 974.5 nm. The UC intensity of Er3+ in Yb/Er-codoped NCs is found to be about five times higher than that of Er-singly-doped counterparts as a result of efficient Yb3+ sensitization and energy transfer upconversion (ETU) evidenced by its distinct UC luminescence dynamics. Furthermore, the origin of defect luminescence is revealed based on the temperature-dependent PL spectra upon excitation above the TiO2 bandgap at 325 nm. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Association of anatase (TiO2) and microbes: unusual fossilization effect or a potential biosignature?

USGS Publications Warehouse

Glamoclija, Mihaela; Andrew Steele,; Marc Fries,; Juergen Schieber,; Voytek, Mary A.; Charles S. Cockell,

2015-01-01

We combined microbial paleontology and molecular biology methods to study the Eyreville B drill core from the 35.3-Ma-old Chesapeake Bay impact structure,Virginia, USA. The investigated sample is a pyrite vein collected from the 1353.81-1353.89 m depth interval, located within a section of biotite granite. The granite is a pre-impact rock that was disrupted by the impact event. A search for inorganic (mineral) biosignatures revealed the presence of micron-size rod morphologies of anatase (TiO2) embedded in chlorite coatings on pyrite grains. Neither the Acridine Orange microbial probe nor deoxyribonucleic acid (DNA) extraction followed by polymerase chain reaction (PCR) amplifi cation showed the presence of DNA or ribonucleic acid (RNA) at the location of anatase rods, implying the absence of viable cells in the investigated area. A Nile Red microbial probe revealed the presence of lipids in the rods. Because most of the lipids are resistant over geologic time spans, they are good biomarkers, and they are an indicator of biogenicity for these possibly 35-Ma-old microbial fossils. The mineral assemblage suggests that rod morphologies are associated with low-temperature (<100 °C) hydrothermal alteration that involved aqueous fl uids. The temporal constraints on the anatase fossils are still uncertain because pre-impact alteration of the granite and postimpact heating may have provided identical conditions for anatase precipitation and microbial preservation.

500 keV Ar2+ ion irradiation induced anatase to brookite phase transformation and ferromagnetism at room temperature in TiO2 thin films

NASA Astrophysics Data System (ADS)

Bharati, B.; Mishra, N. C.; Kanjilal, D.; Rath, Chandana

2018-01-01

In our earlier report, where we have demonstrated ferromagnetic behavior at room temperature (RT) in TiO2 thin films deposited through electron beam evaporation technique followed by annealing either in Ar or O2 atmosphere [Mohanty et al., Journal of Magnetism and Magnetic Materials 355 (2014) 240-245], here we have studied the evolution of structure and magnetic properties after irradiating the TiO2 thin films with 500 keV Ar2+ ions. The pristine film while exhibits anatase phase, the films become amorphous after irradiating at fluence in the range 1 × 1014 to 1 × 1016 ions/cm2. Increasing the fluence up to 5 × 1016 ions/cm2, amorphous to crystalline phase transformation occurs and the structure becomes brookite. Although anatase to rutile phase transformation is usually reported in literatures, anatase to brookite phase transformation is an unusual feature which we have reported here for the first time. Such anatase to brookite phase transformation is accompanied with grain growth without showing any change in film thickness evidenced from Rutherford's Back Scattering (RBS) measurement. From scanning probe micrographs (SPM), roughness is found to be more in amorphous films than in the crystalline ones. Anatase to brookite phase transformation could be realized by considering the importance of intermediate amorphous phase. Because due to amorphous phase, heat deposited by energetic ions are localized as dissipation of heat is less and as a result, the localized region crystallizes in brookite phase followed by grain growth as observed in highest fluence. Further, we have demonstrated ferromagnetic behavior at RT in irradiated films similar to pristine one, irrespective of their phase and crystallinity. Origin for room temperature ferromagnetism (RTFM) is attributed to the presence of oxygen vacancies which is confirmed by carrying out XPS measurement.

Nanostructured microtubes based on TiO2 doped by Zr and Hf oxides with the anatase structure

NASA Astrophysics Data System (ADS)

Zheleznov, VV; Voit, EI; Sushkov, YV; Sarin, SA; Kuryavyi, VG; Opra, DP; Gnedenkov, SV; Sinebryukhov, SL; Sokolov, AA

2016-01-01

The nanostructured microtubes based on TiO2 have been prepared on the carbon fiber template using the sol-gel method. The microtubes consist of nanoparticles of metal oxides: TiO2/ZrO2 and TiO2/HfO2. The dependence of microtubes morphology and nanoparticles structure on the synthesis conditions has been studied using the methods of SEM, SAXS, and Raman spectroscopy. It has been demonstrated that at the stoichiometric ratio of up to 0.04 for Zr/Ti and up to 0.06 for Hf/Ti microtubes consist of uniform nanoparticles with the anatase structure. Along with further increase of the dopants content in the microtubes composition, nanoparticles acquire the core-shell structure. It has been suggested that nanoparticles have a core composed of the solid solutions Ti1-xZrxO2 or Ti1-xHfxO2 and a shell consisting of zirconium or hafnium titanate. The fabricated Zr- and Hf-doped TiO2 materials were investigated in view of their possible use as anode materials for Li-ion batteries. Charge- discharge measurements showed that the doped samples manifested significantly higher reversibility in comparison with the undoped TiO2. The method opens new prospects in synthesis of nanostructured materials for Li-ion batteries application.

Structure of a Water Monolayer on the Anatase TiO2(101) Surface

NASA Astrophysics Data System (ADS)

Patrick, Christopher E.; Giustino, Feliciano

2014-07-01

Titanium dioxide (TiO2) plays a central role in the study of artificial photosynthesis, owing to its ability to perform photocatalytic water splitting. Despite over four decades of intense research efforts in this area, there is still some debate over the nature of the first water monolayer on the technologically relevant anatase TiO2(101) surface. In this work, we use first-principles calculations to reverse engineer the experimental high-resolution x-ray photoelectron spectra measured for this surface by Walle et al. [J. Phys. Chem. C 115, 9545 (2011)] and find evidence supporting the existence of a mix of dissociated and molecular water in the first monolayer. Using both semilocal and hybrid functional calculations, we revise the current understanding of the adsorption energetics by showing that the energetic cost of water dissociation is reduced via the formation of a hydrogen-bonded hydroxyl-water complex. We also show that such a complex can provide an explanation of an unusual superstructure observed in high-resolution scanning tunneling microscopy experiments.

New anatase-type Til-2xNbxAlxO2 solid solution nanoparticles: direct formation, phase stability, and photocatalytic performance.

PubMed

Hirano, Masanori; Ito, Takaharu

2006-12-01

New anatase-type titania solid solutions co-doped with niobium and aluminum (Til-2xNbxAIlxO2 (X = 0 -0.20)) were synthesized as nanoparticles from precursor solutions of TiOSO4, NbCl5, and Al(NO3)3 under mild hydrothermal conditions at 180 degrees C for 5 h using the hydrolysis of urea. The lattice parameters a0 and c0 of anatase slightly and gradually increased, when the content of niobium and aluminum increased from X = 0 to 0.20. The crystallite size of anatase increased from 12 to 28 nm with increasing the value of X from 0 to 0.20. Their photocatalytic activity and adsorptivity were evaluated separately by the measurement of the concentration of methylene blue (MB) remained in the solution in the dark or under UV-light irradiation. The adsorptivity of TiO2 was improved by the formation of anatase-type Til-2xNbxAlxO2 solid solutions. The photocatalytic activity of anatase-type Til-2xNbxAlxO2 solid solutions was superior to that of commercially available anatase-type pure TiO2 (ST-01) and anatase-type pure TiO2 hydrothermally prepared. The new anatase phase of Til-2xNbxAlxO2 (X = 0-0.20) solid solutions existed stably up to 850 0C during heat treatment in air. In comparison with hydrothermal pure TiO2, the starting temperature of anatase-to-rutile phase transformation was delayed by the formation of Ti1-2xNbxAlxO, (X = 0-0.20) solid solutions, although its completing temperature was accelerated.

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

Graphene quantum dots to enhance the photocatalytic hydrogen evolution efficiency of anatase TiO2 with exposed {001} facet.

PubMed

Yu, Shan; Zhong, Yun-Qian; Yu, Bao-Quan; Cai, Shi-Yi; Wu, Li-Zhu; Zhou, Ying

2016-07-27

Hydrogen evolution through photocatalysis is promising with respect to the environmental problems and challenges of energy shortage that we encounter today. In this paper, we have combined graphene quantum dots (GQDs) and {001} faceted anatase TiO2 (with an exposed percentage of 65-75%) together for effective photocatalytic hydrogen evolution. A series of characterizations including X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, Fourier-transform infrared spectroscopy and UV-visible absorption spectroscopy have been carried out to study the structure of the as-prepared GQDs/{001}TiO2 composite. It turns out that GQDs could be effectively decorated on {001}TiO2 sheet without changing its intrinsic structure. With an optimum loading amount of GQDs (0.5 wt% to {001}TiO2), GQDs/{001}TiO2 exhibits a hydrogen evolution efficiency 8 times higher than that of bare {001}TiO2, which is a significantly more obvious improvement than many other photocatalytic systems relevant to GQDs and TiO2 hybrids. In addition, GQDs/{001}TiO2 could stand long-term photocatalytic experiments. Photocurrent tests show that such an improvement of the photocatalytic efficiency over GQDs/{001}TiO2 may originate from a higher charge separation efficiency. The present study could offer reference for the construction of photocatalytic hydrogen evolution systems with low cost and long term stability.

Density functional theory study on the metal-support interaction between a Au9 cluster and an anatase TiO2(001) surface.

PubMed

Jiang, Zong-You; Zhao, Zong-Yan

2017-08-23

Noble metals supported on TiO 2 surfaces have shown extraordinary photocatalytic properties in many important processes such as hydrogenation, water splitting, degradation of hazards, and so on. Using density functional theory calculations, this work has systematically investigated the microstructure and electronic structure of three different Au 9 isomers loaded on anatase TiO 2 (001) surface. The calculated results show that the interaction between the Au 9 cluster and the TiO 2 support is closely related to the adsorption site and the stability of the Au 9 cluster in the gas phase. The adsorption energy of the 2D configuration is larger than that of the 3D configuration of the Au 9 cluster, owing to the stronger interactions between more adsorption sites. The stable adsorption site for Au 9 clusters deposited on the anatase TiO 2 (001) surface tends to be the O 2c -O 2c hollow site. The presentation of the MIGS of the Au 9 cluster, the disappearance of surface states of the TiO 2 (001) surface, and the shifting of the Fermi level from the top of the valence band to the bottom of the conduction band suggest strong interactions between the Au 9 clusters and the TiO 2 (001) surface. Importantly, the electron transfer from the Au 9 clusters to the TiO 2 support occurs mainly through Au-O 2c interactions, which are mainly localized at the contact layer of the Au 9 clusters. These conclusions are useful to understand various physical and chemical properties of noble metal clusters loaded onto an oxide surface, and helpful to design novel metal/semiconductor functional composite materials and devices.

Mechanism of room temperature oxygen sensor based on nanocrystalline TiO2 film

NASA Astrophysics Data System (ADS)

Bakri, A. S.; Sahdan, M. Z.; Nafarizal, N.; Abdullah, S. A.; Said, N. D. M.; Raship, N. A.; Sari, Y.

2018-04-01

A titanium dioxide (TiO2) thin film is proposed as the active layer for the detection of oxygen gas. The sensor is fabricated on silicon wafer using sol-gel dip coating technique with a constant withdrawal speed. The field emission scanning electron microscope image reveals that the film has a uniform structure while the x-ray diffraction analysis indicates that the film is anatase phase with tetragonal lattice structure. The film exhibit the highest intensity peak at (101) plane. The surface roughness measurement shows that the film has low surface roughness with small grain size. The electrical studies revealed that the resistivity is about 4.02 x 10-3 Ω.cm and the thickness of TiO2 film is 127.44 nm. The gas sensor measurement showed that the sensor response of the film is about 4.21% at room temperature.

Theoretical study on the magnetic moments formation in Ta-doped anatase TiO2

NASA Astrophysics Data System (ADS)

Bupu, A.; Majidi, M. A.; Rusydi, A.

2017-04-01

We present a theoretical study on Ti-vacancy induced ferromagnetism in Ta-doped anatase TiO2. Experimental study of Ti1-x Ta x O2 thin film has shown that Ti-vacancies (assisted by Ta doping) induce the formation of localized magnetic moment around it, then, the observed ferromagnetism is caused by the alignment of localized magnetic moments through Ruderman-Kittel-Kasuya-Yosida (RKKY) interaction. In this study, we focus on the formation of the localized magnetic moments in this system. We hypothesize that on a unit cell, Ti-vacancy has caused four electrons from the surrounding oxygen atoms to become unpaired. These unpaired electrons then arrange themselves into a configuration with a non-zero net magnetic moment. To examine our hypothesis, we construct a Hamiltonian of the four unpaired electrons, incorporating the Coulomb intra- and inter-orbital interactions, in matrix form. Using a set of chosen parameter values, we diagonalize the Hamiltonian to get the eigenstates and eigenvalues, then, with the resulting eigenstates, we calculate the magnetic moment, μ, by obtaining the expectation value of the square of total spin operator. Our calculation results show that in the ground state, provided that the ratio of parameters satisfies some criterion, μ ≈ 4μ B , corresponding to the four electron spins being almost perfectly aligned, can be achieved. Further, as long as we keep the Coulomb intra-orbital interaction between 0.5 and 1 eV, we find that μ ≈ 4μ B is robust up to far above room temperature. Our results demonstrate that Ti vacancies in anatase TiO2 can form very stable localized magnetic moments.

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.

Association of anatase (TiO2) and microbes: Unusual fossilization effect or a potential biosignature?

USGS Publications Warehouse

Glamoclija, M.; Steele, A.; Fries, M.; Schieber, J.; Voytek, M.A.; Cockell, C.S.

2009-01-01

We combined microbial paleontology and molecular biology methods to study the Eyreville B drill core from the 35.3-Ma-old Chesapeake Bay impact structure, Virginia, USA. The investigated sample is a pyrite vein collected from the 1353.81- 1353.89 m depth interval, located within a section of biotite granite. The granite is a pre-impact rock that was disrupted by the impact event. A search for inorganic (mineral) biosignatures revealed the presence of micron-size rod morphologies of anatase (TiO2) embedded in chlorite coatings on pyrite grains. Neither the Acridine Orange microbial probe nor deoxyribonucleic acid (DNA) extraction followed by polymerase chain reaction (PCR) amplifi cation showed the presence of DNA or ribonucleic acid (RNA) at the location of anatase rods, implying the absence of viable cells in the investigated area. A Nile Red microbial probe revealed the presence of lipids in the rods. Because most of the lipids are resistant over geologic time spans, they are good biomarkers, and they are an indicator of biogenicity for these possibly 35-Ma-old microbial fossils. The mineral assemblage suggests that rod morphologies are associated with low-temperature (<100 ??C) hydrothermal alteration that involved aqueous fluids. The temporal constraints on the anatase fossils are still uncertain because pre-impact alteration of the granite and postimpact heating may have provided identical conditions for anatase precipitation and microbial preservation. ?? 2009 The Geological Society of America.

Basic molten salt process-A new route for synthesis of nanocrystalline Li 4Ti 5O 12-TiO 2 anode material for Li-ion batteries using eutectic mixture of LiNO 3-LiOH-Li 2O 2

NASA Astrophysics Data System (ADS)

Rahman, M. M.; Wang, Jia-Zhao; Hassan, Mohd Faiz; Chou, Shulei; Wexler, David; Liu, Hua-Kun

A nanocrystalline Li 4Ti 5O 12-TiO 2 duplex phase has been synthesized by a simple basic molten salt process (BMSP) using an eutectic mixture of LiNO 3-LiOH-Li 2O 2 at 400-500 °C. The microstructure and morphology of the Li 4Ti 5O 12-TiO 2 product are characterized by means of X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and transmission electron microscopy (TEM). The sample prepared by heat-treating at 300 °C for 3 h (S-1) reveals dense agglomerates of ultra-fine nanocrystalline Li 4Ti 5O 12; with heat treatment at 400 °C for 3 h (S-2), there is a duplex crystallite size (fine < 10 nm, and coarse > 20 nm) of Li 4Ti 5O 12-TiO 2; at 500 °C for 3 h (S-3), a much coarser and less-dense distribution of lithium titanate (crystallite size ∼15-30 nm) is observed. According to the results of electrochemical testing, the S-2 sample shows initial discharge capacities of 193 mAh g -1 at 0.2 C, 168 mAh g -1 at 0.5 C, 146 mAh g -1 at 1 C, 135 mAh g -1 at 2 C, and 117 mAh g -1 at 5 C. After 100 cycles, the discharge capacity is 138 mAh g -1 at 1 C with a capacity retention of 95%. The S-2 sample yields the best electrochemical performance in terms of charge-discharge capacity and rate capability compared with other samples. Its superior electrochemical performance can be mainly attributed to the duplex crystallite structure, composed of fine (<10 nm) and coarse (>20) nm nanoparticles, where lithium ions can be stored within the grain boundary interfaces between the spinel Li 4Ti 5O 12 and the anatase TiO 2.

Ultra-Sensitive Humidity Sensor Based on Optical Properties of Graphene Oxide and Nano-Anatase TiO2.

PubMed

Ghadiry, Mahdiar; Gholami, Mehrdad; Lai, C K; Ahmad, Harith; Chong, W Y

2016-01-01

Generally, in a waveguide-based humidity sensors, increasing the relative humidity (RH) causes the cladding refractive index (RI) to increase due to cladding water absorption. However, if graphene oxide (GO) is used, a reverse phenomenon is seen due to a gap increase in graphene layers. In this paper, this interesting property is applied in order to fabricate differential humidity sensor using the difference between RI of reduced GO (rGO) and nano-anatase TiO2 in a chip. First, a new approach is proposed to prepare high quality nano-anatase TiO2 in solution form making the fabrication process simple and straightforward. Then, the resulted solutions (TiO2 and GO) are effortlessly drop casted and reduced on SU8 two channels waveguide and extensively examined against several humid conditions. Investigating the sensitivity and performance (response time) of the device, reveals a great linearity in a wide range of RH (35% to 98%) and a variation of more than 30 dB in transmitted optical power with a response time of only ~0.7 sec. The effect of coating concentration and UV treatment are studied on the performance and repeatability of the sensor and the attributed mechanisms explained. In addition, we report that using the current approach, devices with high sensitivity and very low response time of only 0.3 sec can be fabricated. Also, the proposed device was comprehensively compared with other state of the art proposed sensors in the literature and the results were promising. Since high sensitivity ~0.47dB/%RH and high dynamic performances were demonstrated, this sensor is a proper choice for biomedical applications.

Ultra-Sensitive Humidity Sensor Based on Optical Properties of Graphene Oxide and Nano-Anatase TiO2

PubMed Central

Ghadiry, Mahdiar; Gholami, Mehrdad; Lai, C. K.; Ahmad, Harith; Chong, W. Y.

2016-01-01

Generally, in a waveguide-based humidity sensors, increasing the relative humidity (RH) causes the cladding refractive index (RI) to increase due to cladding water absorption. However, if graphene oxide (GO) is used, a reverse phenomenon is seen due to a gap increase in graphene layers. In this paper, this interesting property is applied in order to fabricate differential humidity sensor using the difference between RI of reduced GO (rGO) and nano-anatase TiO2 in a chip. First, a new approach is proposed to prepare high quality nano-anatase TiO2 in solution form making the fabrication process simple and straightforward. Then, the resulted solutions (TiO2 and GO) are effortlessly drop casted and reduced on SU8 two channels waveguide and extensively examined against several humid conditions. Investigating the sensitivity and performance (response time) of the device, reveals a great linearity in a wide range of RH (35% to 98%) and a variation of more than 30 dB in transmitted optical power with a response time of only ~0.7 sec. The effect of coating concentration and UV treatment are studied on the performance and repeatability of the sensor and the attributed mechanisms explained. In addition, we report that using the current approach, devices with high sensitivity and very low response time of only 0.3 sec can be fabricated. Also, the proposed device was comprehensively compared with other state of the art proposed sensors in the literature and the results were promising. Since high sensitivity ~0.47dB/%RH and high dynamic performances were demonstrated, this sensor is a proper choice for biomedical applications. PMID:27101247

Quantitative Analysis of the Morphology of {101} and {001} Faceted Anatase TiO 2 Nanocrystals and Its Implication on Photocatalytic Activity

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

Liu, Jue; Olds, Daniel; Peng, Rui

The atomistic structure and morphology (shape and size) of nanomaterials have strong influences on their physical and chemical properties. However, many characterization techniques focus exclusively on one length-scale regime or another when developing quantitative morphology/structural models. In this article, we demonstrate that powder X-ray diffraction and neutron pair distribution function (PDF) can be used to obtain accurate average morphology and atomistic structure of {001} and {101} faceted anatase TiO 2 nanocrystals based on differential evolution refinements using Debye scattering equation calculations. It is also demonstrated that the morphology polydispersity of TiO 2 nanocrystals can be effectively obtained from the diffractionmore » data via a numerical refinement routine. The morphology refinement results are in good agreement with those from transmission electron microscopy and the modeling of small angle neutron scattering data. This method is successfully used to quantify the facet-specified photocatalytic hydrogen evolution activity of anatase TiO 2 nanocrystals with different {001} to {101} ratios. It is found that the sample with an intermediate amount of both {001} and {101} facets shows the best photocatalytic hydrogen evolution reaction (HER) activity. It is expected that the simultaneous structure and morphology refinement technique can be generally used to study the relationship between morphology and functionality of nanomaterials.« less

Facile decoration of TiO2 nanoparticles on graphene for solar degradation of organic dye

NASA Astrophysics Data System (ADS)

Salem, Shiva; Salem, Amin; Rezaei, Mostafa

2016-11-01

The reduced graphene oxide is interesting material for the synthesis of TiO2-based photocatalyst. In the present investigation, blackberry fruit, which contains high levels of anthocyanins and other phenolic compounds, was employed as a reducing agent mainly due to its high antioxidant capacity. The nano-crystalline TiO2 was decorated on different amounts of graphene oxide with sol-gel method and then the photocatalytic activity for degradation of cationic dye was evaluated by UV spectroscopy to achieve the optimum content of graphene oxide. The decoration of anatase nanoparticles on prepared reduced graphene oxide was investigated by X-ray diffraction, scanning and transmission electron microscopy techniques. The new composite gives significantly higher activity when is compared to the compositions fabricated by graphene oxide. The compact layer provides a large TiO2-graphene contact area and reduces the electron recombination. The decoration of TiO2 nanoparticles, 5-10 nm, on the graphene oxide reduced by blackberry juice further improves the dye removal. The results imply that the nanoparticle decoration is the key strategy to increase the degradation capacity.

Novel Precursor-Derived Meso-/Macroporous TiO2/SiOC Nanocomposites with Highly Stable Anatase Nanophase Providing Visible Light Photocatalytic Activity and Superior Adsorption of Organic Dyes

PubMed Central

Wasan Awin, Eranezhuth; Lale, Abhijeet; Kumar, Kollamala Chellappan Nair Hari

2018-01-01

Titania (TiO2) is considered to have immense potential as a photocatalyst, the anatase phase in particular. There have been numerous attempts to push the limits of its catalytic activity to higher wavelengths to harness the visible electromagnetic radiation. Most of the investigations till date have been restricted to fine-tuning the bandgap by doping, control of defect chemistry at the surface and several to first principle simulations either with limited success or success at the cost of complexities in processing. Here, we report a simple and elegant way of preparing ceramics through precursor chemistry which involves synthesis of macroporous and mesoporous nanocomposites with in situ formation of TiO2 nanocrystals into a robust and protecting SiOC matrix. The in situ nanoscaled TiO2 is anatase of size 9–10 nm, which is uniformly distributed in an amorphous SiOC matrix forming a new generation of nanocomposites that combine the robustness, structural stability and durability of the SiOC matrix while achieving nanoscaled TiO2 functionalities. The stabilization of the anatase phase even at temperature as high as 1200 °C was evident. With an average pore size of 6.8 nm, surface area of 129 m2/g (BET) and pore volume of 0.22 cm3/g (BET), mesoporosity was achieved in the nanocomposites. The composites exhibited visible light photocatalytic activity, which is attributed to the Ti–O–C/TiC bonds resulting in the reduction of band gap by 0.2 to 0.9 eV. Furthermore, the heterojunction formed between the amorphous SiOC and crystalline TiO2 is also expected to minimize the recombination rate of electron-hole pair, making these novel nanocomposites based on TiO2 extremely active in visible wavelength regime. PMID:29494505

Optimization of macropore evolution towards high photocatalytic activity enhancement in meso/macro porous Anatase TiO2

NASA Astrophysics Data System (ADS)

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

2017-01-01

We report on an optimization strategy for macro pore evolution leading to the design of highly photocatalytic 3D hierarchical meso/macroporous TiO2 via much simpler, faster and cost effective synthesis scheme. Meso/macro porous TiO2 is an excellent candidate material for photocatalytic applications owing to the availability of internal surfaces as active sites for redox reactions. The current research scenario focuses on the design of highly efficient photocatalytic systems as well as rapid, facile and cost effective methods of synthesis and optimization of parameters. The present report is on the gradual evolution of macropores in anatase TiO2 by the effective control of pH of the solvent, reaction time, temperature, solvent ratio and reactant concentration via a facile hydrothermal method in this regard. 3D hierarchical macroporous structures are obtained at pH 7 within a comparatively short reaction time of 5 h and demonstrated to be highly photocatalytic (with rate constant four times that of P25 nanoparticles) through photodegradation of Rhodamine B dye.

Ultrasound with low intensity assisted the synthesis of nanocrystalline TiO2 without calcination.

PubMed

Ghows, Narjes; Entezari, Mohamad H

2010-06-01

A novel method has been developed for the preparation of nano-sized TiO(2) with anatase phase. Nanoparticles with diameter about 6 nm were prepared at a relatively low temperature (75 degrees C) and short time. The synthesis was carried out by the hydrolysis of titanium tetra-isopropoxide (TTIP) in the presence of water, ethanol, and dispersant under ultrasonic irradiation (500 kHz) at low intensity. The results show that variables such as water/ethanol ratio, irradiation time, and temperature have a great influence on the particle size and crystalline phases of TiO(2) nanoparticles. Characterization of the product was carried out by different techniques such as powder X-ray diffraction (XRD), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM) and UV-vis spectroscopy. (c) 2010 Elsevier B.V. All rights reserved.

Adsorption behavior of Zn porphyrins on a (1 0 1) face of anatase TiO2

NASA Astrophysics Data System (ADS)

Zajac, Lukasz; Bodek, Lukasz; Such, Bartosz

2018-06-01

The adsorption behavior of porphyrin molecules on anatase TiO2(1 0 1) has been investigated with scanning tunneling microscopy (STM) in ultra-high vacuum (UHV) at room temperature. At low coverage, the ZnTPP molecules have a tendency to adsorb on the one type of step edges forming molecular chains. Due to relatively high mobility of molecules stable assemblies appear only close to a monolayer coverage. Zn porphyrins in self-assembled molecular domains form a commensurate structure. In-plane rotation of the molecules leads to formation of two domains of different chirality.

Anomalous behavior of B{sub 1g} mode in highly transparent anatase nano-crystalline Nb-doped Titanium Dioxide (NTO) thin films

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

Gautam, Subodh K., E-mail: subodhkgtm@gmail.com, E-mail: fouran@gmail.com; Ojha, S.; Singh, Fouran, E-mail: subodhkgtm@gmail.com, E-mail: fouran@gmail.com

2015-12-15

The effect of Niobium doping and size of crystallites on highly transparent nano-crystalline Niobium doped Titanium Dioxide (NTO) thin films with stable anatase phase are reported. The Nb doping concentration is varied within the solubility limit in TiO{sub 2} lattice. Films were annealed in controlled environment for improving the crystallinity and size of crystallites. Elemental and thickness analysis were carried out using Rutherford backscattering spectrometry and cross sectional field emission scanning electron microscopy. Structural characteristics reveal a substitutional incorporation of Nb{sup +5} in the TiO{sub 2} lattice which inhibits the anatase crystallites growth with increasing the doping percentage. The micro-Ramanmore » (MR) spectra of films with small size crystallites shows stiffening of about 4 cm{sup −1} for the E{sub g(1)} mode and is ascribed to phonon confinement and non-stoichiometry. In contrast, B{sub 1g} mode exhibits a large anomalous softening of 20 cm{sup −1} with asymmetrical broadening; which was not reported for the case of pure TiO{sub 2} crystallites. This anomalous behaviour is explained by contraction of the apical Ti-O bonds at the surface upon substitutional Nb{sup 5+} doping induced reduction of Ti{sup 4+} ions also known as hetero-coordination effect. The proposed hypotheses is manifested through studying the electronic structure and phonon dynamics by performing the near edge x-ray absorption fine structure (NEXAFS) and temperature dependent MR down to liquid nitrogen temperature on pure and 2.5 at.% doped NTO films, respectively.« less

The Influence of Fe2O3 Addition on the Tio2 Structure and Photoactivity Properties

NASA Astrophysics Data System (ADS)

Wahyuningsih, S.; Ramelan, A. H.; Prasetyawati, L.; Saputri, L. N. M. Z.; Ichsan, S.; Kristiawan, Y. R.

2018-03-01

The influence of Fe2O3 addition on the TiO2 structure and photoactivity properties have been studied. The addition of Fe2O3 on the TiO2 done by TiO2-Fe2O3 synthesized with variation of annealing temperature. The result showed that peak of anatase TiO2 at 2θ = 25.35° and Fe2O3 at 2θ = 54.20°. The XRD of TiO2 show annealing temperature at 400°C is anatase phase and the composite with annealing at temperature 150°C, 300°C, 400°C and 500°C is crystalline anatase phase, due to the addition of Fe2O3. Photodegradation of Rhodamin B with TiO2 at 400°C annealing temperature showed optimum degradation 36.2 %, and the composite with annealing at 400°C showed optimum degradation 44.3% for 300 minutes irradiation.

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.

Quantitative Analysis of the Morphology of {101} and {001} Faceted Anatase TiO 2 Nanocrystals and Its Implication on Photocatalytic Activity

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

Liu, Jue; Olds, Daniel; Peng, Rui

The atomistic structure and morphology (shape and size) of nanomaterials have strong influences on their physical and chemical properties. However, many characterization techniques focus exclusively on one length-scale regime or another when developing quantitative morphology/structural models. In this article, we demonstrate that powder X-ray diffraction and neutron pair distribution function (PDF) can be used to obtain accurate average morphology and atomistic structure of {001} and {101} faceted anatase TiO 2 nanocrystals based on differential evolution refinements using Debye scattering equation calculations. It is also demonstrated that the morphology polydispersity of TiO 2 nanocrystals can be effectively obtained from the diffractionmore » data via a numerical refinement routine. The morphology refinement results are in good agreement with those from transmission electron microscopy and the modeling of small angle neutron scattering data. This method is successfully used to quantify the facet-specified photocatalytic hydrogen evolution activity of anatase TiO 2 nanocrystals with different {001} to {101} ratios. It is found that the sample with an intermediate amount of both {001} and {101} facets shows the best photocatalytic hydrogen evolution reaction (HER) activity. As a result, it is expected that the simultaneous structure and morphology refinement technique can be generally used to study the relationship between morphology and functionality of nanomaterials.« less

Quantitative Analysis of the Morphology of {101} and {001} Faceted Anatase TiO 2 Nanocrystals and Its Implication on Photocatalytic Activity

DOE PAGES

Liu, Jue; Olds, Daniel; Peng, Rui; ...

2017-06-14

The atomistic structure and morphology (shape and size) of nanomaterials have strong influences on their physical and chemical properties. However, many characterization techniques focus exclusively on one length-scale regime or another when developing quantitative morphology/structural models. In this article, we demonstrate that powder X-ray diffraction and neutron pair distribution function (PDF) can be used to obtain accurate average morphology and atomistic structure of {001} and {101} faceted anatase TiO 2 nanocrystals based on differential evolution refinements using Debye scattering equation calculations. It is also demonstrated that the morphology polydispersity of TiO 2 nanocrystals can be effectively obtained from the diffractionmore » data via a numerical refinement routine. The morphology refinement results are in good agreement with those from transmission electron microscopy and the modeling of small angle neutron scattering data. This method is successfully used to quantify the facet-specified photocatalytic hydrogen evolution activity of anatase TiO 2 nanocrystals with different {001} to {101} ratios. It is found that the sample with an intermediate amount of both {001} and {101} facets shows the best photocatalytic hydrogen evolution reaction (HER) activity. As a result, it is expected that the simultaneous structure and morphology refinement technique can be generally used to study the relationship between morphology and functionality of nanomaterials.« less

NH3 adsorption on anatase-TiO2(101)

NASA Astrophysics Data System (ADS)

Koust, Stig; Adamsen, Kræn C.; Kolsbjerg, Esben Leonhard; Li, Zheshen; Hammer, Bjørk; Wendt, Stefan; Lauritsen, Jeppe V.

2018-03-01

The adsorption of ammonia on anatase TiO2 is of fundamental importance for several catalytic applications of TiO2 and for probing acid-base interactions. Utilizing high-resolution scanning tunneling microscopy (STM), synchrotron X-ray photoelectron spectroscopy, temperature-programmed desorption (TPD), and density functional theory (DFT), we identify the adsorption mode and quantify the adsorption strength on the anatase TiO2(101) surface. It was found that ammonia adsorbs non-dissociatively as NH3 on regular five-fold coordinated titanium surface sites (5f-Ti) with an estimated exothermic adsorption energy of 1.2 eV for an isolated ammonia molecule. For higher adsorbate coverages, the adsorption energy progressively shifts to smaller values, due to repulsive intermolecular interactions. The repulsive adsorbate-adsorbate interactions are quantified using DFT and autocorrelation analysis of STM images, which both showed a repulsive energy of ˜50 meV for nearest neighbor sites and a lowering in binding energy for an ammonia molecule in a full monolayer of 0.28 eV, which is in agreement with TPD spectra.

Quantum chemical elucidation of the mechanism for hydrogenation of TiO2 anatase crystals

NASA Astrophysics Data System (ADS)

Raghunath, P.; Huang, W. F.; Lin, M. C.

2013-04-01

Hydrogenation of TiO2 is relevant to hydrogen storage and water splitting. We have carried out a detailed mechanistic study on TiO2 hydrogenation through H and/or H2 diffusion from the surface into subsurface layers of anatase TiO2 (101) by periodic density functional theory calculations implementing on-site Coulomb interactions (DFT + U). Both H atoms and H2 molecules can migrate from the crystal surface into TiO2 near subsurface layer with 27.8 and 46.2 kcal/mol energy barriers, respectively. The controlling step for the former process is the dissociative adsorption of H2 on the surface which requires 47.8 kcal/mol of energy barrier. Both hydrogen incorporation processes are expected to be equally favorable. The barrier energy for H2 migration from the first layer of the subsurface Osub1 to the 2nd layer of the subsurface oxygen Osub2 requires only 6.6 kcal. The presence of H atoms on the surface and inside the subsurface layer tends to promote both H and H2 penetration into the subsurface layer by reducing their energy barriers, as well as to prevent the escape of the H2 from the cage by increasing its escaping barrier energy. The H2 molecule inside a cage can readily dissociate and form 2HO-species exothermically (ΔH = -31.0 kcal/mol) with only 26.2 kcal/mol barrier. The 2HO-species within the cage may further transform into H2O with a 22.0 kcal/mol barrier and 19.3 kcal/mol exothermicity relative to the caged H2 molecule. H2O formation following the breaking of Ti-O bonds within the cage may result in the formation of O-vacancies and surface disordering as observed experimentally under a high pressure and moderately high temperature condition. According to density of states analysis, the projected density of states of the interstitial H, H2, and H2O appear prominently within the TiO2 band gap; in addition, the former induces a shift of the band gap position notably towards the conduction band. The thermochemistry for formation of the most stable sub

High Infrared Blocking Cellulose Film Based on Amorphous to Anatase Transition of TiO2 via Atomic Layer Deposition.

PubMed

Li, Wenbin; Li, Linfeng; Wu, Xi; Li, Junyu; Jiang, Lang; Yang, Hongjun; Ke, Guizhen; Cao, Genyang; Deng, Bo; Xu, Weilin

2018-06-27

A high IR-blocking cellulose film was designed based on an amorphous to anatase transition of TiO 2 using atomic layer deposition (ALD). This transition was realized at 250 °C, at which the cellulose is thermal stable. Optimized ALD condition of 250 °C and 1200 cycles give us an excellent heat insulator, which could significantly reduce the enclosed space temperature from 59.2 to 51.9 °C after exposure to IR lamp for 5 min.

High-Temperature Stable Anatase Titanium Oxide Nanofibers for Lithium-Ion Battery Anodes.

PubMed

Lee, Sangkyu; Eom, Wonsik; Park, Hun; Han, Tae Hee

2017-08-02

Control of the crystal structure of electrochemically active materials is an important approach to fabricating high-performance electrodes for lithium-ion batteries (LIBs). Here, we report a methodology for controlling the crystal structure of TiO 2 nanofibers by adding aluminum isopropoxide to a common sol-gel precursor solution utilized to create TiO 2 nanofibers. The introduction of aluminum cations impedes the phase transformation of electrospun TiO 2 nanofibers from the anatase to the rutile phase, which inevitably occurs in the typical annealing process utilized for the formation of TiO 2 crystals. As a result, high-temperature stable anatase TiO 2 nanofibers were created in which the crystal structure was well-maintained even at high annealing temperatures of up to 700 °C. Finally, the resulting anatase TiO 2 nanofibers were utilized to prepare LIB anodes, and their electrochemical performance was compared to pristine TiO 2 nanofibers that contain both anatase and rutile phases. Compared to the electrode prepared with pristine TiO 2 nanofibers, the electrode prepared with anatase TiO 2 nanofibers exhibited excellent electrochemical performances such as an initial Coulombic efficiency of 83.9%, a capacity retention of 89.5% after 100 cycles, and a rate capability of 48.5% at a current density of 10 C (1 C = 200 mA g -1 ).

Theoretical prediction of the band offsets at the ZnO/anatase TiO2 and GaN/ZnO heterojunctions using the self-consistent ab initio DFT/GGA-1/2 method.

PubMed

Fang, D Q; Zhang, S L

2016-01-07

The band offsets of the ZnO/anatase TiO2 and GaN/ZnO heterojunctions are calculated using the density functional theory/generalized gradient approximation (DFT/GGA)-1/2 method, which takes into account the self-energy corrections and can give an approximate description to the quasiparticle characteristics of the electronic structure of semiconductors. We present the results of the ionization potential (IP)-based and interfacial offset-based band alignments. In the interfacial offset-based band alignment, to get the natural band offset, we use the surface calculations to estimate the change of reference level due to the interfacial strain. Based on the interface models and GGA-1/2 calculations, we find that the valence band maximum and conduction band minimum of ZnO, respectively, lie 0.64 eV and 0.57 eV above those of anatase TiO2, while lie 0.84 eV and 1.09 eV below those of GaN, which agree well with the experimental data. However, a large discrepancy exists between the IP-based band offset and the calculated natural band offset, the mechanism of which is discussed. Our results clarify band alignment of the ZnO/anatase TiO2 heterojunction and show good agreement with the GW calculations for the GaN/ZnO heterojunction.

Monoclinic β-Li2TiO3 nanocrystalline particles employing novel urea assisted solid state route: Synthesis, characterization and sintering behavior

NASA Astrophysics Data System (ADS)

Tripathi, Biranchi M.; Mohanty, Trupti; Prakash, Deep; Tyagi, A. K.; Sinha, P. K.

2017-07-01

Pure phase monoclinic nano-crystalline Li2TiO3 powder was synthesized by a novel urea assisted solid state synthesis method using readily available and economical precursors. A single phase and well crystalline Li2TiO3 powder has been obtained at slightly lower temperature (600-700 °C) and shorter duration (2 h) as compared to the conventional solid state method. The proposed method has significant advantages in comparison to other viable methods mainly in terms of phase purity, powder properties and sinterability. Analysis of chemical composition using inductively coupled plasma atomic emission spectroscopy (ICP-AES) shows no loss of lithium from Li2TiO3 in the proposed method. The emergence of monoclinic Li2TiO3 phase was confirmed by X-ray diffraction (XRD) pattern of as-synthesized powder. The crystallite size of Li2TiO3 powder was calculated to be in the range of 15-80 nm, which varied as a function of urea composition and temperature. The morphology of as-prepared Li2TiO3 powders was examined by scanning electron microscope (SEM). The effect of urea composition on phase and morphology was investigated so as to delineate the role of urea. Upon sintering at < 1000 °C temperature, the Li2TiO3 powder compact attained about 98% of the theoretical density with fine grained (grain size: 2-3 μm) microstructure. It indicates excellent sinter-ability of Li2TiO3 powder synthesized by the proposed method. The fine grained structure is desirable for better tritium breeding performance of Li2TiO3. Electrochemical impedance spectroscopy at variable temperature showed good electrical properties of Li2TiO3. The proposed method is simple, anticipated to be cost effective and convenient to realise for large scale production of phase pure nanocrystalline and having significantly enhanced sinter-ability Li2TiO3 powder.

Low temperature biosynthesis of Li2O-MgO-P2O5-TiO2 nanocrystalline glass with mesoporous structure exhibiting fast lithium ion conduction.

PubMed

Du, Xiaoyong; He, Wen; Zhang, Xudong; Ma, Jinyun; Wang, Chonghai; Li, Chuanshan; Yue, Yuanzheng

2013-04-01

We demonstrate a biomimetic synthesis methodology that allows us to create Li2O-MgO-P2O5-TiO2 nanocrystalline glass with mesoporous structure at lower temperature. We design a 'nanocrystal-glass' configuration to build a nanoarchitecture by means of yeast cell templates self-assembly followed by the controlled in-situ biomineralization of materials on the cell wall. Electrochemically active nanocrystals are used as the lamellar building blocks of mesopores, and the semiconductive glass phase can act both as the 'glue' between nanocrystals and functionalized component. The Li2O-MgO-P2O5-TiO2 nanocrystalline glass exhibits outstanding thermal stability, high conductivity and wide potential window. This approach could be applied to many other multicomponent glass-ceramics to fabricate mesoporous conducting materials for solid-state lithium batteries. Copyright © 2012 Elsevier B.V. All rights reserved.

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.

Optical, dielectric and morphological studies of sol-gel derived nanocrystalline TiO2 films.

PubMed

Vishwas, M; Sharma, Sudhir Kumar; Narasimha Rao, K; Mohan, S; Gowda, K V Arjuna; Chakradhar, R P S

2009-10-15

Nanocrystalline TiO(2) films have been synthesized on glass and silicon substrates by sol-gel technique. The films have been characterized with optical reflectance/transmittance in the wavelength range 300-1000 nm and the optical constants (n, k) were estimated by using envelope technique as well as spectroscopic ellipsometry. Morphological studies have been carried out using atomic force microscope (AFM). Metal-Oxide-Silicon (MOS) capacitor was fabricated using conducting coating on TiO(2) film deposited on silicon. The C-V measurements show that the film annealed at 300 degrees C has a dielectric constant of 19.80. The high percentage of transmittance, low surface roughness and high dielectric constant suggests that it can be used as an efficient anti-reflection coating on silicon and other optical coating applications and also as a MOS capacitor.

A one-step thermal decomposition method to prepare anatase TiO2 nanosheets with improved adsorption capacities and enhanced photocatalytic activities

NASA Astrophysics Data System (ADS)

Li, Wenting; Shang, Chunli; Li, Xue

2015-12-01

Anatase TiO2 nanosheets (NSs) with high surface area have been prepared via a one-step thermal decomposition of titanium tetraisopropoxide (TTIP) in oleylamine (OM), and their adsorption capacities and photocatalytic activities are investigated by using methylene blue (MB) and methyl orange (MO) as model pollutants. During the synthesis procedure, only one type of surfactant, oleylamine (OM), is used as capping agents and no other solvents are added. Structure and properties of the TiO2 NSs were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), N2 adsorption analysis, UV-vis spectrum, X-ray photoelectron spectroscopy (XPS) and Photoluminescence (PL) methods. The results indicate that the TiO2 NSs possess high surface area up to 378 m2 g-1. The concentration of capping agents is found to be a key factor controlling the morphology and crystalline structure of the product. Adsorption and photodegradation experiments reveal that the prepared TiO2 NSs possess high adsorption capacities of model pollutants MB and high photocatalytic activity, showing that TiO2 NSs can be used as efficient pollutant adsorbents and photocatalytic degradation catalysts of MB in wastewater treatment.

Photocatalytic mechanism of high-activity anatase TiO2 with exposed (001) facets from molecular-atomic scale: HRTEM and Raman studies

NASA Astrophysics Data System (ADS)

Wu, Jun; Shi, Chentian; Zhang, Yupeng; Fu, Qiang; Pan, Chunxu

2017-12-01

Anatase TiO2 with a variant percentage of exposed (001) facets was prepared under hydrothermal processes by adjusting the volume of HF, and the photocatalytic mechanism was studied from atomic-molecular scale by HRTEM and Raman spectroscopy. It was revealed that: 1) From HRTEM observations, the surface of original TiO2 with exposed (001) facets was clean without impurity, and the crystal lattice was clear and completed; however, when mixed with methylene blue (MB) solution, there were many 1 nm molecular absorbed at the surface of TiO2; after the photocatalytic experiment, MB molecules disappeared and the TiO2 lattice image became fuzzy. 2) The broken path of the MB chemical bond was obtained by Raman spectroscopy, i.e., after the irradiation of the light, the vibrational mode of C-N-C disappeared due to the chemical bond breakage, and the groups containing C-N bond and carbon rings were gradually decomposed. Accordingly, we propose that the driving force for breaking the chemical bond and the disappearance of groups is from the surface lattice distortion of TiO2 during photocatalyzation.

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).

A density functional study of the effect of hydrogen on electronic properties and band discontinuity at anatase TiO2/diamond interface

NASA Astrophysics Data System (ADS)

Wu, Kongping; Liao, Meiyong; Sang, Liwen; Liu, Jiangwei; Imura, Masataka; Ye, Haitao; Koide, Yasuo

2018-04-01

Tailoring the electronic states of the dielectric oxide/diamond interface is critical to the development of next generation semiconductor devices like high-power high-frequency field-effect transistors. In this work, we investigate the electronic states of the TiO2/diamond 2 × 1-(100) interface by using first principles total energy calculations. Based on the calculation of the chemical potentials for the TiO2/diamond interface, it is observed that the hetero-interfaces with the C-OTi configuration or with two O vacancies are the most energetically favorable structures under the O-rich condition and under Ti-rich condition, respectively. The band structure and density of states of both TiO2/diamond and TiO2/H-diamond hetero-structures are calculated. It is revealed that there are considerable interface states at the interface of the anatase TiO2/diamond hetero-structure. By introducing H on the diamond surface, the interface states are significantly suppressed. A type-II alignment band structure is disclosed at the interface of the TiO2/diamond hetero-structure. The valence band offset increases from 0.6 to 1.7 eV when H is introduced at the TiO2/diamond interface.

Molecular level energy and electron transfer processes at nanocrystalline titanium dioxide interfaces

NASA Astrophysics Data System (ADS)

Farzad, Fereshteh

This thesis describes photo-induced molecular electron and energy transfer processes occurring at nanocrystalline semiconductor interfaces. The Introductory Chapter provides background and describes how these materials may be useful for solar energy conversion. In Chapter 2, results describing excitation of Ru(deeb)(bpy)2 2+, bis(2,2'-bipyridine)(2,2'-bipyridine-4,4 '-diethylester)ruthenium(II) hexafluorophosphate, bound to nanocrystalline TiO2 thin films, immersed in an acetonitrile bath are presented. The data indicates that light excitation forms predominately long-lived metal-to-ligand charge-transfer, MLCT, excited states under these conditions. Modeling of the data as a function of irradiance has been accomplished assuming parallel unimolecular and bimolecular excited state deactivation processes. The quantum yield for excited state formation depends on the excitation irradiance, consistent with triplet-triplet annihilation processes that occur with k > 1 x 108 s-1. Chapter 3 extends the work described in Chapter 2 to LiClO4 acetonitrile solutions. Li+ addition results in a red shift in the MLCT absorption and photoluminescence, PL, and a concentration dependent quenching of the PL intensity on TiO2. The Li+ induced spectroscopic changes were found to be reversible by varying the electrolyte composition. A second-order kinetic model quantified charge recombination transients. A model is proposed wherein Li+ ion adsorption stabilizes TiO2 acceptor states resulting in energetically more favorable interfacial electron transfer. The photophysical and photoelectrochemical properties of porous nanocrystalline anatase TiO2 electrodes modified with Ru(deeb)(bpy)2 2+, Os(deeb)(bpy)22+, and mixtures of both are described in Chapters 4 and 5. In regenerative solar cells with 0.5 M LiI/0.05 M I2 acetonitrile electrolyte, both compounds efficiently inject electrons into TiO2 producing monochromatic incident photon-to-current efficiencies (IPCE), IPCE (460 nm) = 0.70 + 0

Room temperature one-step synthesis of microarrays of N-doped flower-like anatase TiO2 composed of well-defined multilayer nanoflakes by Ti anodization

NASA Astrophysics Data System (ADS)

Wang, Chenglin; Wang, Mengye; Xie, Kunpeng; Wu, Qi; Sun, Lan; Lin, Zhiqun; Lin, Changjian

2011-07-01

Microarrays of N-doped flower-like TiO2 composed of well-defined multilayer nanoflakes were synthesized at room temperature by electrochemical anodization of Ti in NH4F aqueous solution. The TiO2 flowers were of good anatase crystallinity. The effects of anodizing time, applied voltage and NH4F concentration on the flower-like morphology were systematically examined. It was found that the morphologies of the anodized Ti were related to the anodizing time and NH4F concentration. The size and density of the TiO2 flowers could be tuned by changing the applied voltage. The obtained N-doped flower-like TiO2 microarrays exhibited intense absorption in wavelengths ranging from 320 to 800 nm. Under both UV and visible light irradiation, the photocatalytic activity of the N-doped flower-like TiO2 microarrays in the oxidation of methyl orange showed a significant increase compared with that of commercial P25 TiO2 film.

Room temperature one-step synthesis of microarrays of N-doped flower-like anatase TiO2 composed of well-defined multilayer nanoflakes by Ti anodization.

PubMed

Wang, Chenglin; Wang, Mengye; Xie, Kunpeng; Wu, Qi; Sun, Lan; Lin, Zhiqun; Lin, Changjian

2011-07-29

Microarrays of N-doped flower-like TiO(2) composed of well-defined multilayer nanoflakes were synthesized at room temperature by electrochemical anodization of Ti in NH(4)F aqueous solution. The TiO(2) flowers were of good anatase crystallinity. The effects of anodizing time, applied voltage and NH(4)F concentration on the flower-like morphology were systematically examined. It was found that the morphologies of the anodized Ti were related to the anodizing time and NH(4)F concentration. The size and density of the TiO(2) flowers could be tuned by changing the applied voltage. The obtained N-doped flower-like TiO(2) microarrays exhibited intense absorption in wavelengths ranging from 320 to 800 nm. Under both UV and visible light irradiation, the photocatalytic activity of the N-doped flower-like TiO(2) microarrays in the oxidation of methyl orange showed a significant increase compared with that of commercial P25 TiO(2) film.

The Effect of High N-DOPED Anatase TiO2 on the Band Gap Narrowing and Redshift by First-Principles

NASA Astrophysics Data System (ADS)

Hou, Qingyu; Jin, Yongjun; Ying, Chun; Zhao, Erjun; Zhang, Yue; Dong, Hongying

2012-10-01

Anatase TiO2 supercells were studied by first-principles, in which one was undoped and another three were high N-doping. Partial densities of states, band structure, population and absorption spectrum were calculated. The calculated results indicated that in the condition of TiO2-xNx (x = 0.0625, 0.125, 0.25), the higher the doping concentration is, the shorter will be the lattice parameters parallel to the direction of c-axis. The strength of covalent bond significantly varied. The formation energy increases at first, and then decreases. The doping models become less stable as N-doping concentration increases. Meanwhile, the narrower the band gap is, the more significant will be the redshift, which is in agreement with the experimental results.

SU-G-TeP3-15: Radiation Dose Enhancement by Anatase TiO2NPs

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

Youkhana, E; Geso, M; Feltis, B

2016-06-15

Purpose: This work investigates radiation dose enhancement caused by TiO2 nanoparticles covering entire X-ray energy ranges used in radiation therapy. Methods: Anatase TiO2NPs crystal were synthesised and modified as hydrophilic and hydrophobic to disperse in culture-medium and halocarbons (PRESAGE chemical composition) respectively. TiO2NPs were characterised using TEM, XPS, XRD, TGA and FTIR. Various Concentrations have been utilised for determination of radiation-dose enhancement. This investigation is carried out in two ways; one using PRESAGE dosimeter/phantom and the other is radiobiological and based on in vitro study using two types of cell lines, Human Keratinocyte (HaCaT) and prostate cancer cell lines. Themore » x-ray used are both kilovoltage and megavoltage separately. The prepared PRESAGE dosimeters were scanned using optical CT scanner. Clonogenic and MTS assays were employed for cell cytotoxicity and viability measurements for determination of the levels of dose enhancement. Results: Significant about (50%, 45%) dose enhancement by TiO2-NPs for kV x-rays is measured in both ways (Presage and Cells study). Slightly more is detected with the cells. However, the dose enhancement with megavoltage beams was insignificant using Presage and under same conditions the cells survival curves indicates around 20% which is relatively high. This difference can only be attributed to some biochemical effects. Such as generation of reactive oxygen species (ROS), this can affect the cells while it can’t be detected by Presage. Elevation of hydroxyl radicals (•OH) of many orders is observed with the inclusion of TiO2-NPs in cells-medium. Conclusion: Dose enhancement inflicted by TiO2-NPs is proven to be significant with megavoltage beams and minimal with kV. The high dose enhancements obtained can be attributed to higher levels of ROS generated. Since MV beams are most commonly used, this research proves potential value for more efficient beam delivery. This has

Atomically precise lateral modulation of a two-dimensional electron liquid in anatase TiO 2 thin films

DOE PAGES

Wang, Zhiming; Zhong, Z.; Walker, S. McKeown; ...

2017-03-10

Engineering the electronic band structure of two-dimensional electron liquids (2DELs) confined at the surface or interface of transition metal oxides is key to unlocking their full potential. Here we describe a new approach to tailoring the electronic structure of an oxide surface 2DEL demonstrating the lateral modulation of electronic states with atomic scale precision on an unprecedented length scale comparable to the Fermi wavelength. To this end, we use pulsed laser deposition to grow anatase TiO 2 films terminated by a (1 x 4) in-plane surface reconstruction. Employing photo-stimulated chemical surface doping we induce 2DELs with tunable carrier densities thatmore » are confined within a few TiO 2 layers below the surface. Subsequent in situ angle resolved photoemission experiments demonstrate that the (1 x 4) surface reconstruction provides a periodic lateral perturbation of the electron liquid. Furthermore, this causes strong backfolding of the electronic bands, opening of unidirectional gaps and a saddle point singularity in the density of states near the chemical potential.« less

Photocatalytic Anatase TiO2 Thin Films on Polymer Optical Fiber Using Atmospheric-Pressure Plasma.

PubMed

Baba, Kamal; Bulou, Simon; Choquet, Patrick; Boscher, Nicolas D

2017-04-19

Due to the undeniable industrial advantages of low-temperature atmospheric-pressure plasma processes, such as low cost, low temperature, easy implementation, and in-line process capabilities, they have become the most promising next-generation candidate system for replacing thermal chemical vapor deposition or wet chemical processes for the deposition of functional coatings. In the work detailed in this article, photocatalytic anatase TiO 2 thin films were deposited at a low temperature on polymer optical fibers using an atmospheric-pressure plasma process. This method overcomes the challenge of forming crystalline transition metal oxide coatings on polymer substrates by using a dry and up-scalable method. The careful selection of the plasma source and the titanium precursor, i.e., titanium ethoxide with a short alkoxy group, allowed the deposition of well-adherent, dense, and crystalline TiO 2 coatings at low substrate temperature. Raman and XRD investigations showed that the addition of oxygen to the precursor's carrier gas resulted in a further increase of the film's crystallinity. Furthermore, the films deposited in the presence of oxygen exhibited a better photocatalytic activity toward methylene blue degradation assumedly due to their higher amount of photoactive {101} facets.

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.

Band alignment investigations of heterostructure NiO/TiO2 nanomaterials used as efficient heterojunction earth-abundant metal oxide photocatalysts for hydrogen production.

PubMed

Uddin, Md T; Nicolas, Y; Olivier, C; Jaegermann, W; Rockstroh, N; Junge, H; Toupance, T

2017-07-26

Earth-abundant NiO/anatase TiO 2 heteronanostructures were prepared by a straightforward one-pot sol-gel synthetic route followed by a suitable thermal post-treatment. The resulting 0.1-4 wt% NiO-decorated anatase TiO 2 nanoparticles were characterized by X-ray diffraction, electron microscopy, Raman and UV-visible spectroscopy and N 2 sorption analysis, and showed both nanocrystallinity and mesoporosity. The careful determination of the energy band alignment diagram by a suitable combination of XPS/UPS and absorption spectroscopy data revealed significant band bending at the interface of the p-n NiO/anatase TiO 2 heterojunction nanoparticles. Furthermore, these heterojunction photocatalysts exhibited an improved photocatalytic activity in H 2 production by methanol photoreforming compared to pure anatase TiO 2 and commercial P25. Thus, an average H 2 production rate of 2693 μmol h -1 g -1 was obtained for the heterojunction of a 1 wt% NiO/anatase photocatalyst, which is one of the most efficient NiO/anatase TiO 2 systems ever reported. An enhanced dissociation efficiency of the photogenerated electron-hole pairs resulting from an internal electric field developed at the interface of the NiO/anatase TiO 2 p-n heterojunctions is suggested to be the reason of this enhanced photocatalytic activity.

One-pot synthesis and optical properties of Eu3+-doped nanocrystalline TiO2 and ZrO2

NASA Astrophysics Data System (ADS)

Julián, Beatriz; Corberán, Rosa; Cordoncillo, Eloisa; Escribano, Purificación; Viana, Bruno; Sanchez, Clément

2005-11-01

A simple and versatile one-pot sol-gel synthesis of Eu3+-doped nanocrystalline TiO2 and ZrO2 nanomaterials is reported in this paper. It consists of the controlled crystallization of Eu3+-doped TiO2 or ZrO2 nanoparticles from an initial solution containing the metal alkoxide, the lanthanide precursor, a complexing agent and a non-complexing acid. The main interest is that it could be extended to different lanthanide ions and inorganic metal oxides to prepare other multifunctional nanomaterials. The characterization by XRD, HRTEM and SAED techniques showed that the TiO2 and ZrO2 crystallization takes place at very low temperatures (60 °C) and that the crystallite size can be tailored by modifying the synthetic conditions. The optical properties of the resulting materials were studied by emission spectra and decay measurements. Both Eu3+:TiO2 and Eu3+:ZrO2 samples exhibited long lifetime values after removing organic components (τ = 0.7 and 1.3 ms, respectively), but the Eu3+:ZrO2 system is specially promising for photonic applications since its τ value is longer than some reported for other inorganic or hybrid matrices in which Eu3+ ions are complexed. This behaviour has been explained through an effective dispersion of the lanthanide ions within the ZrO2 nanocrystals.

Photocatalytic antibacterial effects on TiO2-anatase upon UV-A and UV-A/VIS threshold irradiation.

PubMed

Wu, Yanyun; Geis-Gerstorfer, Jürgen; Scheideler, Lutz; Rupp, Frank

2016-01-01

Photocatalysis mediated by the anatase modification of titanium dioxide (TiO2) has shown antibacterial effects in medical applications. The aim of this study was to investigate the possibility of expanding the excitation wavelengths for photocatalytic antibacterial effects from ultraviolet (UV) into the visible light range. After deposition of salivary pellicle and adhesion of Streptococcus gordonii on anatase, different irradiation protocols were applied to induce photocatalysis: ultraviolet A (UV-A) > 320 nm; ultraviolet/visible (UV-A/VIS) light > 380 nm and > 390 nm; and VIS light 400-410 nm. A quartz crystal microbalance with dissipation (QCM-D) tests and microscopic examination were used to observe the photoinduced antibacterial effects. Salivary pellicle could be photocatalytically decomposed under all irradiation protocols. In contrast, effective photocatalytic attack of bacteria could be observed by UV-A as well as by UV-A/VIS at 380 nm < λ < 390 nm only. Wavelengths above 380 nm show promise for in situ therapeutic antifouling applications.

Spectroelectrochemical studies of hole percolation on functionalised nanocrystalline TiO2 films: a comparison of two different ruthenium complexes.

PubMed

Li, Xiaoe; Nazeeruddin, Mohammad K; Thelakkat, Mukundan; Barnes, Piers R F; Vilar, Ramón; Durrant, James R

2011-01-28

We report the application of spectroelectrochemical techniques to compare the hole percolation dynamics of molecular networks of two ruthenium bipyridyl complexes adsorbed onto mesoporous, nanocrystalline TiO(2) films. The percolation dynamics of the ruthenium complex cis-di(thiocyanato)(2,2'-bipyridyl-4,4'-dicarboxylic acid)-(2,2'-bipyridyl-4,4'-tridecyl) ruthenium(II), N621, is compared with those observed for an analogous dye with an additional tri-phenyl amine (TPA) donor moiety, cis-di(thiocyanato)(2,2'-bipyridyl-4,4'-dicarboxylic acid)-(2,2'-bipyridyl-4,4'-bis(vinyltriphenylamine)) ruthenium(II), HW456. The in situ oxidation of these ruthenium complexes adsorbed to the TiO(2) films is monitored by cyclic voltammetry and voltabsorptometry, whilst the dynamics of hole (cation) percolation between adsorbed ruthenium complexes is monitored by potentiometric spectroelectrochemistry and chronoabsorptometry. The hole diffusion coefficient, D(eff), is shown to be dependent on the dye loading on the nanocrystalline TiO(2) film, with a threshold observed at ∼60% monolayer surface coverage for both dyes. The hole diffusion coefficient of HW456 is estimated to be 2.6 × 10(-8) cm(2)/s, 20-fold higher than that obtained for the control N621, attributed to stronger electronic coupling between the TPA moieties of HW456 accelerating the hole percolation dynamics. The presence of mercuric ions, previously shown to bind to the thiocyanates of analogous ruthenium complexes, resulted in a quenching of the hole percolation for N621/TiO(2) films and an enhancement for HW456/TiO(2) films. These results strongly suggest that the hole percolation pathway is along the overlapped neighbouring -NCS groups for the N621 molecules, whereas in HW456 molecules cation percolation proceeds between intermolecular TPA ligands. These results are discussed in the context of their relevance to the process of dye regeneration in dye sensitised solar cells, and to the molecular wiring of wide

Strongly bound excitons in anatase TiO 2 single crystals and nanoparticles

DOE PAGES

Baldini, E.; Chiodo, L.; Dominguez, A.; ...

2017-04-13

Anatase TiO 2 is among the most studied materials for light-energy conversion applications, but the nature of its fundamental charge excitations is still unknown. Yet it is crucial to establish whether light absorption creates uncorrelated electron-hole pairs or bound excitons and, in the latter case, to determine their character. Here, by combining steady-state angle-resolved photoemission spectroscopy and spectroscopic ellipsometry with state-of-the-art ab initio calculations, we demonstrate that the direct optical gap of single crystals is dominated by a strongly bound exciton rising over the continuum of indirect interband transitions. This exciton possesses an intermediate character between the Wannier-Mott and Frenkelmore » regimes and displays a peculiar two-dimensional wavefunction in the three-dimensional lattice. The nature of the higher-energy excitations is also identified. Furthermore, the universal validity of our results is confirmed up to room temperature by observing the same elementary excitations in defect-rich samples (doped single crystals and nanoparticles) via ultrafast two-dimensional deep-ultraviolet spectroscopy.« less

Highly efficient TiO2-based microreactor for photocatalytic applications.

PubMed

Krivec, Matic; Žagar, Kristina; Suhadolnik, Luka; Čeh, Miran; Dražić, Goran

2013-09-25

A photocatalytic, TiO2-based microreactor is designed and fabricated on a metal-titanium foil. The microchannel is mechanically engraved in the substrate foil, and a double-layered TiO2 anatase film is immobilized on its inner walls with a two-step synthesis, which included anodization and a hydrothermal treatment. X-ray diffraction (XRD) and scanning electron microscopy (SEM) confirm the presence of an approximately 10-μm-thick layer of titania nanotubes and anatase nanoparticles. The SEM and transmission electron microscopy (TEM) of the cross sections show a dense interface between the titanium substrate and the TiO2 nanotubes. An additional layer of TiO2-anatase nanoparticles on the top of the film provides a large, photocatalytic surface area. The metal-titanium substrate with a functionalized serpentine channel is sealed with UV-transparent Plexiglas, and four 0.8-mW UV LEDs combined with a power controller on a small printed-circuit board are fixed over the substrate. The photocatalytic activity and the kinetic properties for the degradation of caffeine are provided, and the longer-term stability of the TiO2 film is evaluated. The results show that after 6 months of use and 3600 working cycles the microreactor still exhibits 60% of its initial efficiency.

Magnetic, electronic, optical, and photocatalytic properties of nonmetal- and halogen-doped anatase TiO2 nanotubes

NASA Astrophysics Data System (ADS)

Fadlallah, M. M.

2017-05-01

The structure stability, magnetic, electronic, optical, and photocatalytic properties of nonmetal (B, C, N, P, and S), and halogen (F, Cl, Br, and I)-doped anatase TiO2 nanotubes (TNTs) have been investigated using spin polarized density functional theory. The N- and F-doped TNTs are the most stable among other doped TNTs. It is found that the magnetic moment of doped TNT is the difference between the number of the valence electrons of the dopant and host anion. All dopants decrease the band gap of TNT. The decrease in the band gap of nonmetal (C, N, P, and S)-doped TNTs, in particular N and P, is larger than that of halogen-doped TNTs due to the created states of the nonmetal dopant in the band gap. There is a good agreement between the calculation results and the experimental observations. Even though C-, N-, and P-doped TNTs have the lowest band gap, they cannot be used as a photocatalysis for water splitting. The B-, S-, and I-doped TiO2 nanotubes are of great potential as candidates for water splitting in the visible light range.

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.

Enhanced supercapacitor performances using C-doped porous TiO2 electrodes

NASA Astrophysics Data System (ADS)

Chen, Juanrong; Qiu, Fengxian; Zhang, Ying; Liang, Jianzheng; Zhu, Huijun; Cao, Shunsheng

2015-11-01

Considerable efforts have been paid to develop electrochemical capacitors with energy storage capability in order to meet the demands of multifunctional electronics. Here we report a facile method to fabricate C-doped porous anatase TiO2. This technique involves the preparation of monodisperse cationic polystyrene nanoparticles (CPN), following sequential deposition of tetrabutylorthotitanate (TBT), and directly carbonizing of CPN. Interestingly, during the process of carbonizing CPN, a phase transition of TiO2 will be happened and whist C-doped porous anatase TiO2 is in situ formed. When this porous C-doped TiO2 is used as electrode material to prepare electrochemical capacitor, it manifests a higher capacitance than the commercial P25, effectively broadening it potential for many practical applications.

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

Visible light driven photocatalyst of vanadium (V3+) doped TiO2 synthesized using sonochemical method

NASA Astrophysics Data System (ADS)

Aini, N.; Ningsih, R.; Maulina, D.; Lami’, F. F.; Chasanah, S. N.

2018-03-01

TiO2 has been widely investigated due to its superior photocatalytic activity under ultraviolet irradiation among the photocatalyst materials. In this research, vanadium (V3+) was doped into TiO2 to enhance its light response under visible irradiation for wider application. Vanadium was introduced into TiO2 lattice at various concentration respectively 0.3, 0.5, 0.7 and 0.9% using simple and fast sonochemical method. X-Ray Diffraction data show that vanadium doped TiO2 crystallized in anatase phase with I41amd space group. X-Ray Diffraction pattern shifted to lower value of 2θ due to vanadium dopant. It indicated that V3+ was incorporated into anatase lattice. UV-Vis Diffuse Reflectance Spectra was revealed that the doped TiO2 has lowered reflectance and enhanced absorption coefficient in visible region than undoped TiO2 and commercial anatase TiO2. Band gap energy for undoped and doped TiO2 were respectively 3.22, 3.05, 2.93, 3.03 and 2.40 eV. Therefore vanadium doped TiO2 had potential to be applied under visible light.

Synthesis of nano anatase for titanosilicate ETS-10 synthesis

NASA Astrophysics Data System (ADS)

Shafeque, Shihara

Functionalized textiles present a vast and growing niche in the global textile market at US $400 billion [1, 2]. Engelhard Titanium Silicate 10 (ETS-10), a photocatalytic zeo-type material if coated on textiles, is expected to impart useful properties similar to TiO2, such as stain-resistant, odor repellant, bactericidal and enhanced UV protection [3, 4]. Typically, small ETS-10 crystals of size ˜300-800 nm are synthesized using solid titania (e.g., anatase or P25) sources [5, 6, 7]. However, smaller ETS-10 crystals are required for a uniform surface coating with highly effective surface area. The dissolution of titania particles (i.e., their size) is hypothesized to be important in small ETS-10 crystal formation [5, 6, 7]. Nano anatase was synthesized by modification of two methods: direct precipitation [7] and sol-gel synthesis [3]. Analysis by XRD confirmed that both methods produced nano anatase of crystallite size ˜4-5 nm. However, FE-SEM analysis showed that product from direct precipitation, existed as intergrown spheroidal particles with size ˜1.0 mum. These particles dispersed poorly in deionized water. Therefore, the best nano anatase samples were from sol-gel synthesis in two forms, dry powder and colloidal anatase. ETS-10 synthesis was investigated using two methods adopted from literature [6, 7]. The method of Yoon and co-workers [7], with nano anatase in a molar composition of 5.5TEOS: TiO2: 8.4NaOH: 1.43KF: 350H2O: 2.2H2SO4 produced unknown phase(s) with some ETS-10 and quartz. Using colloidal anatase with molar composition 5.5TEOS:1.0TiO 2:8.4NaOH:1.43KF:400H2O:2.2H2SO4 also produced unknown phase(s). The method of Anderson and co-workers [6] with nano anatase powder in a molar composition of 5.5SiO2: TiO 2: 5.2Na2O: 0.5K2O: 113H2O produced quartz with ETS-10 impurity. When colloidal anatase was used, with molar composition TiO2:5.5SiO2:5.2Na2O:0.5K2O:332H 2O, unreacted anatase and quartz were formed. It was hypothesized that the very low

Role of Adsorbed Water on Charge Carrier Dynamics in Photoexcited TiO2

PubMed Central

2017-01-01

Overall photocatalytic water splitting is one of the most sought after processes for sustainable solar-to-chemical energy conversion. The efficiency of this process strongly depends on charge carrier recombination and interaction with surface adsorbates at different time scales. Here, we investigated how hydration of TiO2 P25 affects dynamics of photogenerated electrons at the millisecond to minute time scale characteristic for chemical reactions. We used rapid scan diffuse-reflectance infrared Fourier transform spectroscopy (DRIFTS). The decay of photogenerated electron absorption was substantially slower in the presence of associated water. For hydrated samples, the charge carrier recombination rates followed an Arrhenius-type behavior in the temperature range of 273–423 K; these became temperature-independent when the material was dehydrated at temperatures above 423 K or cooled below 273 K. A DFT+U analysis revealed that hydrogen bonding with adsorbed water stabilizes surface-trapped holes at anatase TiO2(101) facet and lowers the barriers for hole migration. Hence, hole mobility should be higher in the hydrated material than in the dehydrated system. This demonstrates that adsorbed associated water can efficiently stabilize photogenerated charge carriers in nanocrystalline TiO2 and suppress their recombination at the time scale up to minutes. PMID:28413570

[Study of the phase transformation of TiO2 with in-situ XRD in different gas].

PubMed

Ma, Li-Jing; Guo, Lie-Jin

2011-04-01

TiO2 sample was prepared by sol-gel method from chloride titanium. The phase transformation of the prepared TiO2 sample was studied by in-situ XRD and normal XRD in different gas. The experimental results showed that the phase transformation temperatures of TiO2 were different under in-situ or normal XRD in different kinds of gas. The transformation of amorphous TiO2 to anatase was controlled by kinetics before 500 degrees C. In-situ XRD showed that the growth of anatase was inhibited, but the transformation of anatase to rutile was accelerated under inactive nitrogen in contrast to air. Also better crystal was obtained under hydrogen than in argon. These all showed that external oxygen might accelerate the growth of TiO2, but reduced gas might partly counteract the negative influence of lack of external oxygen. The mechanism of phase transformation of TiO2 was studied by in-situ XRD in order to control the structure in situ.

TiO2 Processed by pressurized hot solvents as a novel photocatalyst for photocatalytic reduction of carbon dioxide

NASA Astrophysics Data System (ADS)

Reli, Martin; Kobielusz, Marcin; Matějová, Lenka; Daniš, Stanislav; Macyk, Wojciech; Obalová, Lucie; Kuśtrowski, Piotr; Rokicińska, Anna; Kočí, Kamila

2017-01-01

Anatase-brookite TiO2 photocatalysts were prepared by the sol-gel process controlled within reverse micelles and processing by pressurized hot solvents-water/methanol/water (TiO2(M)) and water/ethanol/water (TiO2(E)), as an unconventional alternative to common calcination. The main goal of this work was to prepare anatase-brookite mixtures by processing by two different alcohols (methanol and ethanol) and evaluate the influence of the alcohol on the photocatalytic activity. Prepared photocatalysts were characterized by organic elemental analysis, nitrogen physisorption, XRD, UV-vis, photoelectrochemical and spectroelectrochemical measurements and XPS. The prepared photocatalysts efficiency was tested on the photocatalytic reduction of carbon dioxide and compared with commercial TiO2 Evonik P25. Both prepared nanocomposites were more efficient towards methane production but Evonik P25 was the most efficient towards hydrogen generated through water splitting. The higher performance of anatase-brookite mixture towards methane production can be explained by (i) a higher photocatalytic activity of brookite than rutile; (ii) a large surface area of anatase-brookite composites enabling better carbon dioxide adsorption; (iii) the photoinduced electron transfer from the brookite conduction band to the anatase conduction band. On the other hand, a higher production of hydrogen in the presence of Evonik P25 is caused by a better charge separation in anatase-rutile than anatase-brookite phase compositions. TiO2(M) appeared more active than TiO2(E) in the photocatalytic reduction of carbon dioxide due to a lower density of defects created in the crystal lattice.

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.

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%.

An Unusual Strong Visible-Light Absorption Band in Red Anatase TiO2 Photocatalyst Induced by Atomic Hydrogen-Occupied Oxygen Vacancies.

PubMed

Yang, Yongqiang; Yin, Li-Chang; Gong, Yue; Niu, Ping; Wang, Jian-Qiang; Gu, Lin; Chen, Xingqiu; Liu, Gang; Wang, Lianzhou; Cheng, Hui-Ming

2018-02-01

Increasing visible light absorption of classic wide-bandgap photocatalysts like TiO 2 has long been pursued in order to promote solar energy conversion. Modulating the composition and/or stoichiometry of these photocatalysts is essential to narrow their bandgap for a strong visible-light absorption band. However, the bands obtained so far normally suffer from a low absorbance and/or narrow range. Herein, in contrast to the common tail-like absorption band in hydrogen-free oxygen-deficient TiO 2 , an unusual strong absorption band spanning the full spectrum of visible light is achieved in anatase TiO 2 by intentionally introducing atomic hydrogen-mediated oxygen vacancies. Combining experimental characterizations with theoretical calculations reveals the excitation of a new subvalence band associated with atomic hydrogen filled oxygen vacancies as the origin of such band, which subsequently leads to active photo-electrochemical water oxidation under visible light. These findings could provide a powerful way of tailoring wide-bandgap semiconductors to fully capture solar light. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electron-plasmon and electron-phonon satellites in the angle-resolved photoelectron spectra of n -doped anatase TiO2

NASA Astrophysics Data System (ADS)

Caruso, Fabio; Verdi, Carla; Poncé, Samuel; Giustino, Feliciano

2018-04-01

We develop a first-principles approach based on many-body perturbation theory to investigate the effects of the interaction between electrons and carrier plasmons on the electronic properties of highly doped semiconductors and oxides. Through the evaluation of the electron self-energy, we account simultaneously for electron-plasmon and electron-phonon coupling in theoretical calculations of angle-resolved photoemission spectra, electron linewidths, and relaxation times. We apply this methodology to electron-doped anatase TiO2 as an illustrative example. The simulated spectra indicate that electron-plasmon coupling in TiO2 underpins the formation of satellites at energies comparable to those of polaronic spectral features. At variance with phonons, however, the energy of plasmons and their spectral fingerprints depends strongly on the carrier concentration, revealing a complex interplay between plasmon and phonon satellites. The electron-plasmon interaction accounts for approximately 40% of the total electron-boson interaction strength, and it is key to improve the agreement with measured quasiparticle spectra.

Arginine Interactions with Anatase TiO2 (100) Surface and the Perturbation of 49Ti NMR Chemical Shifts - A DFT Investigation: Relevance to Renu-Seeram Bio Solar Cell

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

Koch, Rainer; Lipton, Andrew S.; Filipek, S.

2011-06-01

Density functional theoretical calculations have been utilized to investigate the interaction of the amino acid arginine with the (100) surface of anatase and the reproduction of experimentally measured 49Ti NMR chemical shifts of anatase. Significant binding of arginine through electrostatic interaction and hydrogen bonds of the arginine guanidinium protons to the TiO2 surface oxygen atoms is observed, allowing attachment of proteins to titania surfaces in the construction of bio-sensitized solar cells. GIAO-B3LYP/6-31G(d) NMR calculation of a three-layer model based on the experimental structure of this TiO2 modification gives an excellent reproduction of the experimental value (-927 ppm) within +/- 7more » ppm, however, the change in relative chemical shifts, EFGs and CSA suggest that the effect of the electrostatic arginine binding might be too small for experimental detection.« less

Non-equilibrium nitrogen DC-arc plasma treatment of TiO2 nanopowder.

PubMed

Suzuki, Yoshikazu; Gonzalez-Aguilar, José; Traisnel, Noel; Berger, Marie-Hélène; Repoux, Monique; Fulcheri, Laurent

2009-01-01

Non-equilibrium nitrogen DC-arc plasma treatment of a commercial TiO2 anatase nanopowder was examined to obtain nitrogen-doped TiO2. By using a non-thermal discharge at low current (150 mA) and high voltage (1200 V) using pure N2 gas, light yellowish-gray TiO2 powder was successfully obtained within a short period of 5-10 min. XPS and TEM-EELS studies confirmed the existence of doped nitrogen. Due to the relatively mild conditions (plasma power of 180 W), metastable anatase structure and fine crystallite size of TiO2 (ca. 10 nm) were maintained after the plasma treatment. The in-flight powder treatment system used in this study is promising for various type of powder treatment.

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

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

PubMed Central

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

2016-01-01

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

Structural and optical characterization of electrodeposited CdSe in mesoporous anatase TiO2 for regenerative quantum-dot-sensitized solar cells.

PubMed

Sauvage, Frédéric; Davoisne, Carine; Philippe, Laetitia; Elias, Jamil

2012-10-05

We investigated CdSe-sensitized TiO(2) solar cells by means of electrodeposition under galvanostatic control. The electrodeposition of CdSe within the mesoporous film of TiO(2) gives rise to a uniform, thickness controlled, conformal layer of nanostructured CdSe particles intimately wrapping the anatase TiO(2) nanoparticles. This technique has the advantage of providing not only a fast method for sensitization ( < 5 min) but also being easily scalable to the sensitization of large-area panels. XRD together with SAED analysis highlight that the deposit of CdSe is exclusively constituted of the hexagonal polymorph. In addition, hierarchical growth has also been shown, starting from the formation of a TiO(2)-CdSe core-shell structure followed by the growth of an assembly of CdSe nanoparticles resembling cauliflowers. This assembly exhibits at its core a mosaic texture with crystallites of about 3 nm in size, in contrast to a shell composed of well-crystallized single crystals between 5 and 10 nm in size. Preliminary results on the photovoltaic performance of such a nanostructured composite of TiO(2) and CdSe show 0.8% power conversion efficiency under A.M.1.5 G conditions-100 mW cm(-2) in association with a new regenerative redox couple based on cobalt(+III/+II) polypyridil complex (V(oc ) = 485 mV, J(sc ) = 4.26 mA cm (-2), ff=0.37).

Surface acidity scales: Experimental measurements of Brønsted acidities on anatase TiO2 and comparison with coinage metal surfaces

NASA Astrophysics Data System (ADS)

Silbaugh, Trent L.; Boaventura, Jaime S.; Barteau, Mark A.

2016-08-01

The first quantitative surface acidity scale for Brønsted acids on a solid surface is presented through the use of titration-displacement and equilibrium experiments on anatase TiO2. Surface acidities of species on TiO2 correlated with gas phase acidities, as was previously observed in qualitative studies of Brønsted acid displacement on Ag(110), Cu(110) and Au(111). A 90% compression of the surface acidity scale relative to the gas phase was observed due to compensation from the covalent component of the conjugate base - surface bond. Adsorbed conjugate bases need not be completely anionic for correlations with gas phase acidities to hold. Positive and negative substituent effects, such as substituted fluorine and hydrocarbon sidechain dispersion interactions with the surface, may modify the surface acidity scale, in agreement with previous experimental and theoretical work on Au(111).

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.

Nanoscale effects of silica particle supports on the formation and properties of TiO2 nanocatalysts

NASA Astrophysics Data System (ADS)

Li, Aize; Jin, Yuhui; Muggli, Darrin; Pierce, David T.; Aranwela, Hemantha; Marasinghe, Gaya K.; Knutson, Theodore; Brockman, Greg; Zhao, Julia Xiaojun

2013-06-01

Small TiO2 crystals in the anatase phase are in high demand as photocatalysts. Stable TiO2 crystals in the anatase phase were obtained using a silica nanoparticle as a support. The focus of this study was to investigate the nanoscale effect of the silica support on the formation and properties of small anatase crystals. The experiments were carried out using powder X-ray diffraction, differential thermal analysis, transmission electron microscopy, and energy dispersion spectroscopy. The results showed that the size of the silica support played a crucial role in crystallization of TiO2 and regulation of TiO2 properties, including phase transition, crystal size, thermodynamic property and catalytic activity. A nanoscale curvature model of the spherical silica support was proposed to explain these size effects. Finally, the developed TiO2 catalysts were applied to the oxidation of methanol using a high-throughput photochemical reactor. The size effect of the silica supports on the TiO2 catalytic efficiency was demonstrated using this system.

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.

Theoretical studies of arsenite adsorption and its oxidation mechanism on a perfect TiO 2 anatase (1 0 1) surface

NASA Astrophysics Data System (ADS)

Wei, Zhigang; Zhang, Shaowen; Pan, Zhanchang; Liu, Yue

2011-11-01

There are many areas in the world where the ground water has been contaminated by arsenic. TiO2 is one of the most promising materials that can remove arsenic from groundwater supplies by the adsorption-based processes. The TiO2 surface is capable of photo-catalytic oxidation (PCO) changing the arsenite [As(III)] to arsenate [As(V)] which is more easily absorbed by the surface, increasing the efficiency of the process. In this paper, a density functional theory calculation has been performed to investigate the adsorption of As(III) on a perfect TiO2 anatase (1 0 1) surface. All the As(III) solution species such as H3AsO3, H2AsO3-, HAsO32- and AsO33- are put onto the surface with many different possible attitudes to obtain the adsorption energy. Based on the adsorption energy and the concentration of H3AsO3, H2AsO3-, HAsO32- and AsO33- in an aqueous solution, the bidentate binuclear (BB) adsorption configurations of H2AsO3- on the surface are more favorable at low As(III) concentrations, whereas BB form and monodentate mononuclear (MM) form may coexist at higher concentrations. By calculating H2AsO3- co-adsorption with water and oxygen, we can confirm the deep acceptor character of an adsorbed O2 molecule which implies that surface superoxide (or hydroperoxyl radical) plays an important role during the PCO process of As(III) on TiO2 surface.

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.

Biomolecule-controlled hydrothermal synthesis of C-N-S-tridoped TiO2 nanocrystalline photocatalysts for NO removal under simulated solar light irradiation.

PubMed

Wang, Yawen; Huang, Yu; Ho, Wingkei; Zhang, Lizhi; Zou, Zhigang; Lee, Shuncheng

2009-09-30

In this study, C-N-S-tridoped titanium dioxide (TiO(2)) nanocrystals were synthesized by using a facile hydrothermal method in the presence of a biomolecule l-cysteine. This biomolecule could not only serve as the common source for the carbon, sulfur and nitrogen tridoping, but also could control the final crystal phases and morphology. The resulting materials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), nitrogen adsorption and UV-vis diffuse reflectance spectroscopy. XPS analysis revealed that S was incorporated into the lattice of TiO(2) through substituting oxygen atoms, N might coexist in the forms of N-Ti-O and Ti-O-N in tridoped TiO(2) and most C could form a mixed layer of carbonate species deposited on the surface of TiO(2) nanoparticles. The photocatalytic activities of the samples were tested on the removal of NO at typical indoor air level in a flow system under simulated solar light irradiation. The tridoped TiO(2) samples showed much higher removal efficiency than commercial P25 and the undoped counterpart photocatalyst. The enhanced visible light photocatalytic activity of C-N-S-tridoped TiO(2) nanocrystals was explained on the basis of characterizations. The possible formation process of the monodispersed C-N-S-tridoped anatase TiO(2) nanocrystals was also proposed. This study provides a new method to prepare visible light active TiO(2) photocatalyst.

Enhanced photocatalytic activity of TiO2-C hybrid aerogels for methylene blue degradation

PubMed Central

Shao, Xia; Lu, Wencong; Zhang, Rui; Pan, Feng

2013-01-01

Carbon-based TiO2 composites have many advantages as photocatalysts. However, they suffer from low light efficiency due to the low contrast of TiO2 with carbon. We synthesized a novel type of anatase-type TiO2-C hybrid aerogel by a one-pot sol-gel method, which shows a photocatalytic activity for methylene degradation up to 4.23 times that of P25, a commercial photocatalyst from Degussa Inc. The hybrid aerogels are prepared from TiCl4 and resorcinol–furfural, and have a tunable macropore size from 167 to 996 nm. They are formed of submicrometer particles that consist of interwoven anatase and carbon nanoparticles. The anatase nanoparticles have a size of 8–9 nm and a tunable oxygen vacancy from 7.2 to 18.0%. The extremely high activity is ascribed to the large light absorption caused by macropore scattering and oxygen vacancies in the anatase. These findings may open up a new avenue and stimulate further research to improve photocatalytic performance. PMID:24145581

Enhanced photocatalytic activity of TiO2-C hybrid aerogels for methylene blue degradation

NASA Astrophysics Data System (ADS)

Shao, Xia; Lu, Wencong; Zhang, Rui; Pan, Feng

2013-10-01

Carbon-based TiO2 composites have many advantages as photocatalysts. However, they suffer from low light efficiency due to the low contrast of TiO2 with carbon. We synthesized a novel type of anatase-type TiO2-C hybrid aerogel by a one-pot sol-gel method, which shows a photocatalytic activity for methylene degradation up to 4.23 times that of P25, a commercial photocatalyst from Degussa Inc. The hybrid aerogels are prepared from TiCl4 and resorcinol-furfural, and have a tunable macropore size from 167 to 996 nm. They are formed of submicrometer particles that consist of interwoven anatase and carbon nanoparticles. The anatase nanoparticles have a size of 8-9 nm and a tunable oxygen vacancy from 7.2 to 18.0%. The extremely high activity is ascribed to the large light absorption caused by macropore scattering and oxygen vacancies in the anatase. These findings may open up a new avenue and stimulate further research to improve photocatalytic performance.

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.

Hydrothermal synthesis of TiO2/WO3 compositions and their photocatalytic activity

NASA Astrophysics Data System (ADS)

Pyachin, Sergey A.; Karpovich, Natalia F.; Zaitsev, Alexey V.; Makarevich, Konstantin S.; Burkov, Alexander A.; Ustinov, Alexander Yu.

2016-11-01

Photocatalytic activity, optical properties, thermal stability, phase patterns and morphology of nano-size TiO2/WO3 compositions obtained from organic precursors through hydrothermal synthesis have been studied. It has been shown that doping of anatase nanoparticles with tungsten W+6 results in particle diameter reduction from 35 to 10 nm; decrease in width of the band gap from 3.15 eV to 2.91 eV and increase in temperature of phase transition of anatase to rutile up to 980oC. Catalytic activity of TiO2/WO3 (4 mol.%) composition under photochemical methylene blue (MB) oxidation by simulated solar light exceeds that of undoped anatase (obtained in the same way) 6-fold.

Photoelectrochemical Performance of TiO2/Ti Electrode for Organic Compounds

NASA Astrophysics Data System (ADS)

Maulidiyah, M.; Wijawan, I. B. P.; Wibowo, D.; Aladin, A.; Hamzah, B.; Nurdin, M.

2018-05-01

Photoelectrochemical performance of TiO2/Ti electrode was investigated by using organic compounds. The TiO2/Ti electrode was prepared by anodic oxidation at a potential bias of 25 V for 4 h then calcined for 450 °C to obtain the anatase polymorph. Subsequently, it was characterized by X-Ray Diffraction (XRD) and Scanning Electron Microscope-Energy Dispersive X-ray (SEM-EDX). The XRD pattern showed that TiO2 has anatase phase as confirmed by 2θ peaks at 37.93° 63.00°, and 83.00°. Using SEM-EDX data the TiO2 layer was formed on Ti plate with the composition of Ti (4.5 keV) and O (0.5 keV) elements. Furthermore, the photoelectrochemical sensing on the three organic compounds (ascorbic acid, glucose, and titan yellow) with the electrolyte addition showed that the linearity of TiO2/Ti electrode were 0.937, 0.968, and 0.938, meanwhile without the electrolyte were 0.998, 0.989, and 0.923, respectively.

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

Home-made experiment of Dye-sensitized TiO2 Nanocrystalline Solar Cells and its education evaluation

NASA Astrophysics Data System (ADS)

Tai, M. F.; Shieh, M. C.; Chen, T. W.

2010-03-01

Dyes extracted from some natural fruits including anthocyanins absorb sunlight and effectively activate electrons of anthocyanins. Thus these activated electrons are conducted between TiO2 nanocrystals and form electric potential and current between two electrodes. The dyes can be gotten from the natural fruits, such as blackberries, raspberry, pomegranate seeds and bing cherries. This principle permits making a dye sensitized TiO2 nanocrystallines solar cell (DSSC). All required materials and tools for fabricating a home- made DSSC are easy to obtain around home. The procedures are perfect hands-on experiment as well as demonstration in K-12 schools or home settings. We have designed several protocols for fabricating DSSC and have successfully demonstrated in more than 100 activities with different level students. K-12 Students were able to build their own working DSSC's within 2-3 hours sessions and learned about alternative energy sources. These experiments can inspire students and general public about the modern technology in daily life. Low cost (low than US 3 in Taiwan)and safety are also ensured in our DSSC experiments.

Water dissociation and CO oxidation over Au/anatase catalyst. A DFT-D2 study

NASA Astrophysics Data System (ADS)

Saqlain, Muhammad Adnan; Hussain, Akhtar; Siddiq, Muhammad; Leitão, Alexandre A.

2018-03-01

With the help of DFT-D2 methodology, we have investigated the adsorption of water on clean anatase(001) and Au/anatase(001). In the former case, adsorption energies of H2O differ to small extent computed employing GGA = PW91 and DFT-D2 methods. While the GGA = PW91 predicts that water would desorb close to 650 K on the TiO2 surface, the DFT-D2 predicts that desorption is most likely to occur above 700 K. A comparison of water adsorption on TiO2 and Au/TiO2 surfaces shows that the TiO2 prefers dimer adsorption whereas the Au/TiO2 prefers monomer adsorption. We found that the diffusion of surface hydroxyls on to the Au cluster from the Au/TiO2 periphery is unlikely and it seems that the CO oxidation would occur at the Au/TiO2 boundary. The results show that water dissociation and CO oxidation steps occur easily on Au/TiO2 indicating that this could be good alternative catalyst for water gas shift reaction industry.

Femtosecond time-resolved X-ray absorption spectroscopy of anatase TiO2 nanoparticles using XFEL

PubMed Central

Obara, Yuki; Ito, Hironori; Ito, Terumasa; Kurahashi, Naoya; Thürmer, Stephan; Tanaka, Hiroki; Katayama, Tetsuo; Togashi, Tadashi; Owada, Shigeki; Yamamoto, Yo-ichi; Karashima, Shutaro; Nishitani, Junichi; Yabashi, Makina; Suzuki, Toshinori; Misawa, Kazuhiko

2017-01-01

The charge-carrier dynamics of anatase TiO2 nanoparticles in an aqueous solution were studied by femtosecond time-resolved X-ray absorption spectroscopy using an X-ray free electron laser in combination with a synchronized ultraviolet femtosecond laser (268 nm). Using an arrival time monitor for the X-ray pulses, we obtained a temporal resolution of 170 fs. The transient X-ray absorption spectra revealed an ultrafast Ti K-edge shift and a subsequent growth of a pre-edge structure. The edge shift occurred in ca. 100 fs and is ascribed to reduction of Ti by localization of generated conduction band electrons into shallow traps of self-trapped polarons or deep traps at penta-coordinate Ti sites. Growth of the pre-edge feature and reduction of the above-edge peak intensity occur with similar time constants of 300–400 fs, which we assign to the structural distortion dynamics near the surface. PMID:28713842

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.

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.

Photoassist-phosphorylated TiO2 as a catalyst for direct formation of 5-(hydroxymethyl)furfural from glucose.

PubMed

Hattori, Masashi; Kamata, Keigo; Hara, Michikazu

2017-02-01

Photo-assisted phosphorylation of an anatase TiO 2 catalyst was examined to improve its catalytic performance for the direct production of 5-(hydroxymethyl)furfural (HMF), a versatile chemical platform, from glucose. In phosphorylation based on simple esterification between phosphoric acid and surface OH groups on anatase TiO 2 with water-tolerant Lewis acid sites, the density of phosphates immobilized on TiO 2 is limited to 2 phosphates nm -2 , which limits selective HMF production. Phosphorylation of the TiO 2 surface under fluorescent light irradiation increases the surface phosphate density to 50%, which is higher than the conventional limit, thus preventing the adsorption of hydrophilic glucose molecules on TiO 2 and resulting in a more selective HMF production over photoassist-phosphorylated TiO 2 .

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.

Surface and interface engineering of anatase TiO2 anode for sodium-ion batteries through Al2O3 surface modification and wise electrolyte selection

NASA Astrophysics Data System (ADS)

Li, Tao; Gulzar, Umair; Bai, Xue; Monaco, Simone; Longoni, Gianluca; Prato, Mirko; Marras, Sergio; Dang, Zhiya; Capiglia, Claudio; Proietti Zaccaria, Remo

2018-04-01

In the present study, Al2O3 is utilized for the first time as coating agent on nanostructured anatase TiO2 in order to investigate its effect on sodium-ion batteries performance. Our results show that the Al2O3 coating, introduced by a facile two-step approach, provides beneficial effects to the TiO2-based anodes. However, the coated TiO2 still suffers of capacity fading upon cycling when using 1.0 M of NaClO4 in propylene carbonate (PC) as electrolyte. To address this issue, the influence of different electrolytes (NaClO4 salt in various solvents) is further studied. It is found that the modified TiO2 exhibits significant improvements in cycling performance using binary ethylene carbonate (EC) and PC solvent mixture without the need of the commonly used fluoroethylene carbonate (FEC) additive. Under the best configuration, our battery could deliver a high reversible capacity of 188.1 mAh g-1 at 0.1C after 50 cycles, good rate capability up to 5C, and remarkable long-term cycling stability at 1C rate for 650 cycles. This excellent performance can be ascribed to the synergistic effects of surface and interface engineering enabling the formation of a stable and highly ionic conductive interface layer in EC:PC based electrolyte which combines the native SEI film and an 'artificial' SEI layer of irreversibly formed Na-Al-O.

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.

Morphology-controlled cactus-like branched anatase TiO2 arrays with high light-harvesting efficiency for dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Wu, Wu-Qiang; Rao, Hua-Shang; Feng, Hao-Lin; Guo, Xin-Dong; Su, Cheng-Yong; Kuang, Dai-Bin

2014-08-01

The present work establishes a facile process for one-step hydrothermal growth of vertically aligned anatase cactus-like branched TiO2 (CBT) arrays on a transparent conducting oxide (TCO) substrate. Various CBT morphologies are obtained by adjusting the potassium titanium oxide oxalate (PTO) reactant concentration (from 0.05 M to 0.15 M) and this yields a morphologically-controllable branched TiO2 arrays geometry. The CBT arrays consist of a vertically oriented nanowire (NW) or nanosheet (NS) stem and a host of short nanorod (NR) branches. The hierarchical CBT arrays demonstrate their excellent candidatures as photoanodes, which are capable of exhibiting high light-harvesting efficiency in dye-sensitized solar cells (DSSCs). Consequently, DSSCs based on 7 μm long optimized CBT arrays (0.05 M PTO), which are assembled with high density and high aspect-ratio NR branches, exhibit an impressive power conversion efficiency of 6.43% under AM 1.5G one sun illumination. The high performance can be attributed to the prominent light-harvesting efficiency, resulting from larger surface area and superior light-scattering capability.

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.

One-dimensional TiO2 nanomaterials: preparation and catalytic applications.

PubMed

Wu, Yu; Yu, Jie; Liu, Hong-Mei; Xu, Bo-Qing

2010-10-01

This work reports on the syntheses of one-dimensional (1D) H2Ti3O7 materials (nanotubes, nanowires and their mixtures) by autoclaving anatase titania (Raw-TiO2) in NaOH-containing ethanol-water solutions, followed by washing with acid solution. The synthesized nanosized materials were characterized using XRD, TEM/HRTEM, BET and TG techniques. The autoclaving temperature (120-180 degrees C) and ethanol-to-water ratio (V(EtOH)/V(H2O) = 0/60 approximately 30/30) were shown to be critical to the morphology of H2Ti3O7 product. The obtained H2Ti3O7 nanostructures were calcined at 400-900 degrees C to prepare 1D-TiO2 nanomaterials. H2Ti3O7 nanotubes were converted to anatase nanorods while H2Ti3O7 nanowires to TiO2(B) nanowires after the calcination at 400 degrees C. The calcination at higher temperatures led to gradual decomposition of the wires to rods and phase transformation from TiO2(B) to anatase then to rutile. Photocatalytic degradation of methyl orange was conducted to compare the photocatalytic activity of these 1D materials. These 1D materials were used as new support to prepare Au/TiO2 catalysts for CO oxidation at 0 degrees C and 1,3-butadiene hydrogenation at 120 degrees C. For the CO oxidation reaction, Au particles supported on anatase nanorods derived from the H2Ti3O7 nanotubes (Au/W-180-400) were 1.6 times active that in Au/P25-TiO2, 4 times that in Au/Raw-TiO2, and 8 times that on TiO2(B) nanowires derived from the H2Ti3O7 nanotubes (Au/M-180-400). For the hydrogenation of 1,3-butadiene, however, the activity of Au particles in Au/M-180-400 was 3 times higher than those in Au/W-180-400 but similar to those in Au/P25-TiO2. These results demonstrate that the potential of 1D-TiO2 nanomaterials in catalysis is versatile.

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

Highly Ordered TiO2 Microcones with High Rate Performance for Enhanced Lithium-Ion Storage.

PubMed

Rhee, Oonhee; Lee, Gibaek; Choi, Jinsub

2016-06-15

The perpendicularly oriented anatase TiO2 microcones for Li-ion battery application were synthesized via anodization of a Ti foil in aqueous HF + H3PO4 solution. The TiO2 microcones exhibited a high active surface area with a hollow core depending on applied voltage and reaction time, confirmed by SEM, XRD and TEM with EDS mapping. Li insertion/desertion into TiO2 microcones was evaluated for the first time in half-cell configuration in terms of various current density and long-term cyclability. The electrochemical experiments demonstrated that the as-prepared TiO2 microcones as anode material exhibited 3 times higher capacity as compared with TiO2 nanotubular structures, excellent rate performance (0.054 mAhcm(-2) even at 50 C) and reliable capacity retention during 500 cycles, which was attributed to facile diffusion of Li-ions induced in hollow anatase TiO2 microcones structure with multilayered nanofragment.

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.

The origin of facet selectivity and alignment in anatase TiO 2 nanoparticles in electrolyte solutions: implications for oriented attachment in metal oxides

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

Sushko, M. L.; Rosso, K. M.

Atomic-to-mesoscale simulations were used to reveal the origin of oriented attachment between anatase TiO2 nanoparticles in aqueous HCl solutions. Analysis of the distance and pH dependence of interparticle interactions demonstrates that ion correlation forces are responsible for facet-specific attraction and rotation into lattice co-alignment at long-range. These forces give rise to a metastable solvent separated capture minimum on the disjoining pressure-distance curve, with the barrier to attachment largely due to steric hydration forces from structured intervening solvent.

Zr-doped TiO2 supported on delaminated clay materials for solar photocatalytic treatment of emerging pollutants.

PubMed

Belver, C; Bedia, J; Rodriguez, J J

2017-01-15

Solar light-active Zr-doped TiO 2 nanoparticles were successfully immobilized on delaminated clay materials by a one-step sol-gel route. Fixing the amount of TiO 2 at 65wt.%, this work studies the influence of Zr loading (up to 2%) on the photocatalytic activity of the resulting Zr-doped TiO 2 /clay materials. The structural characterization demonstrates that all samples were formed by a delaminated clay with nanostructured anatase assembled on its surface. The Zr dopant was successfully incorporated into the anatase lattice, resulting in a slight deformation of the anatase crystal and the reduction of the band gap. These materials exhibit high surface area with a disordered mesoporous structure formed by TiO 2 particles (15-20nm) supported on a delaminated clay. They were tested in the solar photodegradation of antipyrine, usually used as an analgesic drug and selected as an example of emerging pollutant. High degradation rates have been obtained at low antipyrine concentrations and high solar irradiation intensities with the Zr-doped TiO 2 /clay catalyst, more effective than the undoped one. This work demonstrates the potential application of the synthesis method for preparing novel and efficient solar-light photocatalysts based on metal-doped anatase and a delaminated clay. Copyright © 2016 Elsevier B.V. All rights reserved.

Enhanced photocatalytic degradation of Amaranth dye on mesoporous anatase TiO2: evidence of C-N, N[double bond, length as m-dash]N bond cleavage and identification of new intermediates.

PubMed

Naik, Amarja P; Salkar, Akshay V; Majik, Mahesh S; Morajkar, Pranay P

2017-07-01

The photocatalytic degradation mechanism of Amaranth, a recalcitrant carcinogenic azo dye, was investigated using mesoporous anatase TiO 2 under sunlight. Mesoporous anatase TiO 2 of a high photocatalytic activity has been synthesized using a sol-gel method and its photocatalytic activity for the degradation of Amaranth dye has been evaluated with respect to Degussa P25. The effect of bi-dentate complexing agents like oxalic acid, ethylene glycol and urea on the surface properties of TiO 2 catalyst has been investigated using TG-DTA, FTIR, HR-TEM, SAED, PXRD, EDS, UV-DRS, PL, BET N 2 adsorption-desorption isotherm studies and BJH analysis. The influence of catalyst properties such as the mesoporous network, pore volume and surface area on the kinetics of degradation of Amaranth as a function of irradiation time under natural sunlight has been monitored using UV-Vis spectroscopy. The highest rate constant value of 0.069 min -1 was obtained for the photocatalytic degradation of Amaranth using TiO 2 synthesized via a urea assisted sol-gel synthesis method. The effect of the reaction conditions such as pH, TiO 2 concentration and Amaranth concentration on the photodegradation rate has been investigated. The enhanced photocatalytic activity of synthesized TiO 2 in comparison with P25 is attributed to the mesoporous nature of the catalyst leading to increased pore diameter, pore volume, surface area and enhanced charge carrier separation efficiency. New intermediates of photocatalytic degradation of Amaranth, namely, sodium-3-hydroxynaphthalene-2,7-disulphonate, 3-hydroxynaphthalene, sodium-4-aminonaphthalenesulphonate and sodium-4-aminobenzenesulphonate have been identified using LC-ESI-MS for the very first time, providing direct evidence for simultaneous bond cleavage pathways (-C-N-) and (-N[double bond, length as m-dash]N-). A new plausible mechanism of TiO 2 catalysed photodegradation of Amaranth along with the comparison of its toxicity to that of its degradation

Hierarchical TiO2/C nanocomposite monoliths with a robust scaffolding architecture, mesopore-macropore network and TiO2-C heterostructure for high-performance lithium ion batteries

NASA Astrophysics Data System (ADS)

Huang, Hai-Bo; Yang, Yue; Chen, Li-Hua; Wang, Yun; Huang, Shao-Zhuan; Tao, Jia-Wei; Ma, Xiao-Ting; Hasan, Tawfique; Li, Yu; Xu, Yan; Su, Bao-Lian

2016-05-01

Engineering hierarchical structures of electrode materials is a powerful strategy for optimizing the electrochemical performance of an anode material for lithium-ion batteries (LIBs). Herein, we report the fabrication of hierarchical TiO2/C nanocomposite monoliths by mediated mineralization and carbonization using bacterial cellulose (BC) as a scaffolding template as well as a carbon source. TiO2/C has a robust scaffolding architecture, a mesopore-macropore network and TiO2-C heterostructure. TiO2/C-500, obtained by calcination at 500 °C in nitrogen, contains an anatase TiO2-C heterostructure with a specific surface area of 66.5 m2 g-1. When evaluated as an anode material at 0.5 C, TiO2/C-500 exhibits a high and reversible lithium storage capacity of 188 mA h g-1, an excellent initial capacity of 283 mA h g-1, a long cycle life with a 94% coulombic efficiency preserved after 200 cycles, and a very low charge transfer resistance. The superior electrochemical performance of TiO2/C-500 is attributed to the synergistic effect of high electrical conductivity, anatase TiO2-C heterostructure, mesopore-macropore network and robust scaffolding architecture. The current material strategy affords a general approach for the design of complex inorganic nanocomposites with structural stability, and tunable and interconnected hierarchical porosity that may lead to the next generation of electrochemical supercapacitors with high energy efficiency and superior power density.Engineering hierarchical structures of electrode materials is a powerful strategy for optimizing the electrochemical performance of an anode material for lithium-ion batteries (LIBs). Herein, we report the fabrication of hierarchical TiO2/C nanocomposite monoliths by mediated mineralization and carbonization using bacterial cellulose (BC) as a scaffolding template as well as a carbon source. TiO2/C has a robust scaffolding architecture, a mesopore-macropore network and TiO2-C heterostructure. TiO2/C-500

TiO2 nanosheets decorated with B4C nanoparticles as photocatalysts for solar fuel production under visible light irradiation

NASA Astrophysics Data System (ADS)

Zhang, Xiaojie; Yang, Jipeng; Cai, Tiancong; Zuo, Guoqiang; Tang, Changqing

2018-06-01

Boron carbide (B4C) nanoparticles-decorated anatase titanium dioxide (TiO2) nanosheets photocatalysts were synthesized by a hydrothermal method in the presence of hydrofluoric acid and characterized by field emission scanning electron microscope, high-resolution transmission electron microscope, UV-vis diffuse reflectance spectra, photoluminescence spectra, etc. With metallic Pt nanoparticles as a co-catalyst, the as-synthesized B4C/TiO2 composites were evaluated using photocatalytic CO2 or H2O reduction to solar fuels such as methane and hydrogen. Under either simulated sunlight or visible light irradiation, coupling p-type B4C with n-type anatase TiO2 significantly improved the photocatalytic performance. Both photoluminescence and transient photocurrent measurements indicated that the interfacial coupling effect between B4C and anatase TiO2 could significantly promote photo-excited charges separations. On the basis of measurements and literatures, a possible mechanism of excited charges transfer at the B4C-anatase TiO2 heterojunction interface during irradiation was deduced.

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.

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.

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.

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.

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.

Well-crystallized mesoporous TiO2 shells for enhanced photocatalytic activity: prepared by carbon coating and silica-protected calcination.

PubMed

Zhang, Zewu; Zhou, Yuming; Zhang, Yiwei; Zhou, Shijian; Shi, Junjun; Kong, Jie; Zhang, Sicheng

2013-04-14

Mesoporous anatase-phase TiO2 hollow shells were successfully fabricated by the solvothermal and calcination process. This method involves preparation of SiO2@TiO2 core-shell colloidal templates, sequential deposition of carbon and then silica layers through solvothermal and sol-gel processes, crystallization of TiO2 by calcination and finally removal of the inner and outer silica to produce hollow anatase TiO2 shells. The prepared samples were characterized by transmission electron microscopy, X-ray diffraction, N2 adsorption-desorption isotherms and UV-vis absorption spectroscopy. The results show that a uniform carbon layer is coated on the core-shell particles through the solvothermal process. The combustion of carbon offers the space for the TiO2 to further grow into large crystal grains, and the outer silica layer serves as a barrier against the excessive growth of anatase TiO2 nanocrystals. Furthermore, the initial crystallization of TiO2 generated in the carbon coating step and the heat generated by the combustion of the carbon layer allow the crystallization of TiO2 at a relatively low temperature without changing the uniform structure. When used as photocatalysts for the oxidation decomposition of Rhodamine B in aqueous solution under UV irradiation, the hollow TiO2 shells showed enhanced catalytic activity. Moreover, the TiO2 hollow shells prepared with optimal crystallinity by this method showed a higher performance than commercial P25 TiO2.

Effects of N precursor on the agglomeration and visible light photocatalytic activity of N-doped TiO2 nanocrystalline powder.

PubMed

Hu, Yulong; Liu, Hongfang; Rao, Qiuhua; Kong, Xiaodong; Sun, Wei; Guo, Xingpeng

2011-04-01

N-doped TiO2 nanocrystalline powders were prepared by the sol-gel method using various N precursors, including triethylamine, hydrazine hydrate, ethylenediamine, ammonium hydroxide, and urea. The samples were characterized by X-ray diffraction, N2 adsorption isotherms, transmission electron microscopy, ultraviolet-visible diffuse reflectance spectroscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The photocatalytic activities of as-prepared samples under irradiation of visible light (lambda > 405 nm) were evaluated by photodecomposition of methyl orange. The alkalinity of N precursor was found to play a key role in the gel process. The N precursor with moderate alkalinity causes TiO2 nanoparticles to be sol-transformed into a loosely agglomerated gel. This transformation facilitates the preparation of an N-doped TiO2 powder with small nanocrystal size, large specific surface area, and high N doping level and results in high visible light photocatalytic activity. The N in TiO2 with N is binding energy at 399-400 eV may be assigned to the N-H species located in interstitial sites of TiO2 lattice which is the active N species responsible for the visible light photocatalytic activity. The N species of N 1s peak at 402 and 405 eV are ineffective to the visible light photocatalytic activity and may inhibit the photocatalytic activity. Moreover, a TiO2 nanoparticle powder with large specific area can be achieved by using urea as a template and then by using ammonium hydroxide to transform the sol into gel.

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.

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.

A new preparation of doped photocatalytic TiO2 anatase nanoparticles: a preliminary study for the removal of pollutants in confined museum areas

NASA Astrophysics Data System (ADS)

Greco, Enrico; Ciliberto, Enrico; Cirino, Antonio M. E.; Capitani, Donatella; Di Tullio, Valeria

2016-05-01

The use of nanotechnology in conservation is a relatively new concept. Usually, classical cleanup methods take into account the use of other chemicals: On the one hand they help the environment destroying pollutants, but on the other hand they often become new pollutants. Among the new oxidation methods called advanced oxidation processes, heterogeneous photocatalysis has appeared an emerging technology with several economic and environmental advantages. A new sol-gel method of synthesis of TiO2 anatase is reported in this work using lithium and cobalt (II) salts. The activation energy of the doped photocatalyst was analyzed by solid-state UV-Vis spectrophotometer. The mobility of Li ions on TiO2 NPs surface was studied by 7Li MAS NMR spectroscopy. Use of doped nanotitania is suggested from authors for the removal of pollutants in confined areas containing goods that must be preserved from decomposition and aging phenomena.

Rational design of anatase TiO2 architecture with hierarchical nanotubes and hollow microspheres for high-performance dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Gu, Jiuwang; Khan, Javid; Chai, Zhisheng; Yuan, Yufei; Yu, Xiang; Liu, Pengyi; Wu, Mingmei; Mai, Wenjie

2016-01-01

Large surface area, sufficient light-harvesting and superior electron transport property are the major factors for an ideal photoanode of dye-sensitized solar cells (DSSCs), which requires rational design of the nanoarchitectures and smart integration of state-of-the-art technologies. In this work, a 3D anatase TiO2 architecture consisting of vertically aligned 1D hierarchical TiO2 nanotubes (NTs) with ultra-dense branches (HTNTs, bottom layer) and 0D hollow TiO2 microspheres with rough surface (HTS, top layer) is first successfully constructed on transparent conductive fluorine-doped tin oxide glass through a series of facile processes. When used as photoanodes, the DSSCs achieve a very large short-current density of 19.46 mA cm-2 and a high overall power conversion efficiency of 8.38%. The remarkable photovoltaic performance is predominantly ascribed to the enhanced charge transport capacity of the NTs (function as the electron highway), the large surface area of the branches (act as the electron branch lines), the pronounced light harvesting efficiency of the HTS (serve as the light scattering centers), and the engineered intimate interfaces between all of them (minimize the recombination effect). Our work demonstrates a possibility of fabricating superior photoanodes for high-performance DSSCs by rational design of nanoarchitectures and smart integration of multi-functional components.

The Electronic Structures and Optical Properties of Alkaline-Earth Metals Doped Anatase TiO2: A Comparative Study of Screened Hybrid Functional and Generalized Gradient Approximation.

PubMed

Ma, Jin-Gang; Zhang, Cai-Rong; Gong, Ji-Jun; Wu, You-Zhi; Kou, Sheng-Zhong; Yang, Hua; Chen, Yu-Hong; Liu, Zi-Jiang; Chen, Hong-Shan

2015-08-24

Alkaline-earth metallic dopant can improve the performance of anatase TiO2 in photocatalysis and solar cells. Aiming to understand doping mechanisms, the dopant formation energies, electronic structures, and optical properties for Be, Mg, Ca, Sr, and Ba doped anatase TiO2 are investigated by using density functional theory calculations with the HSE06 and PBE functionals. By combining our results with those of previous studies, the HSE06 functional provides a better description of electronic structures. The calculated formation energies indicate that the substitution of a lattice Ti with an AEM atom is energetically favorable under O-rich growth conditions. The electronic structures suggest that, AEM dopants shift the valence bands (VBs) to higher energy, and the dopant-state energies for the cases of Ca, Sr, and Ba are quite higher than Fermi levels, while the Be and Mg dopants result into the spin polarized gap states near the top of VBs. The components of VBs and dopant-states support that the AEM dopants are active in inter-band transitions with lower energy excitations. As to optical properties, Ca/Sr/Ba are more effective than Be/Mg to enhance absorbance in visible region, but the Be/Mg are superior to Ca/Sr/Ba for the absorbance improvement in near-IR region.

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

PubMed Central

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

2014-01-01

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

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).

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 nanodimensional TiO2 thin films.

PubMed

Thakurdesai, Madhavi; Mohanty, T; John, J; Rao, T K Gundu; Raychaudhuri, Pratap; Bhattacharyya, V; Kanjilal, D

2008-08-01

Nanodimensional TiO2 has wide application in the field of photocatalysis, photovoltaic and photochromic devices. In present investigation TiO2 thin films deposited by pulsed laser deposition method are irradiated by 100 MeV Ag ion beam to achieve growth of nanophases. The nanostructure evolution is characterized by atomic force microscopy (AFM). The phases of TiO2 formed after irradiation are identified by glancing angle X-ray diffraction and Raman spectroscopy. The particle radius estimated by AFM varies from 10-13 nm. Anatase phase of TiO2 is formed after irradiation. The blue shift observed in UV-VIS absorption spectra indicates the nanostructure formation. The shape and size of nanoparticles formed due to high electronic excitation depend upon thickness of the film.

Recovery TiO2 by leaching process of carbothermic reduced Kalimantan ilmenite

NASA Astrophysics Data System (ADS)

Wahyuningsih, S.; Sari, P. P.; Ramelan, A. H.

2018-05-01

Ilmenite naturally occurred in iron titanate (FeTiO3) minerals. The separation of natural ilmenite into TiO2 and Fe2O3 need to be explored to gain the high purity separation product. A new combination method named of carbothermic reduction, acidic-leaching and complexation by EDTA were proposed for separation TiO2 from Ilmenite. Roasting of ilmenite was carried out at 950 °C for 1 h by the addition of activated carbon with mass ratio of ilmenite : activated carbon =4:3. The carbothermic reduction was carried out to yield a high separation of initial content of ilmenite that will be easily to dissolve within hydrochloric acid solution in leaching process. The composition of ilmenite observed by X-Ray Fluoresences (XRF) changed after the carbothermic reduction process and the dominant content is TiO2 (57.56%). X-Ray Diffraction (XRD) of roasted ilmenite composed of decomposed product of ilmenite i.e. hematite (Fe2O3), TiO2 anatase, TiO2 rutile, and inorganic salt. The leaching of the roasted ilmenite has been done by sulphuric acid solution (6 M) to gain the titanyl sulphate solution. Separation of iron impurities of TiO2 gel from titanyl sulphate (TiOSO4) solution was conducted by complexation method using EDTA as a complexation agent. The characteristic of TiO2 obtained using XRD showed that TiO2 is anatase type and the percentage of TiO2 using XRF showed that TiO2 content of 86,03%.

Anatase phase stability and doping concentration dependent refractivity in codoped transparent conducting TiO2 films

NASA Astrophysics Data System (ADS)

Chen, T. L.; Furubayashi, Y.; Hirose, Y.; Hitosugi, T.; Shimada, T.; Hasegawa, T.

2007-10-01

Nb0.06SnxTi0.94-xO2 (x <= 0.3) thin films were grown by a pulsed-laser deposition method with varying Sn concentration. Through a combinatorial technique, we find that Sn concentration can reach a maximum of about x = 0.3 while maintaining the stable anatase phase and epitaxy. A doping concentration dependence of the refractivity is revealed, in which refractivity reduction at a wavelength of λ = 500 nm is estimated to be 12.4% for Nb0.06Sn0.3 Ti0.64O2 thin film. Sn doping induced band-gap blue shift can be contributed to the mixing of extended Sn 5s orbitals with the conduction band of TiO2. Low resistivity on the order of 10-4 Ω cm at room temperature and high internal transmittance of more than 95% in the visible light region are exhibited for Nb0.06Snx Ti0.94-xO2 thin films (x <= 0.2). Optical and transport analyses demonstrate that doping Sn into Nb0.06 Ti0.94O2 can reduce the refractivity while maintaining low resistivity and high transparency.

Nb and Ta Co-Doped TiO2 Transparent Conductive Thin Films by Magnetron Sputtering: Fabrication, Structure, and Characteristics

NASA Astrophysics Data System (ADS)

Liu, Yang; Peng, Qian; Qiao, Yadong; Yang, Guang

2018-06-01

Nb and Ta co-doped anatase titanium dioxide (NTTO) nanocrystalline thin films were deposited on quartz and Si (100) substrates by RF magnetron sputtering. The influence of RF power on the growth, structure, morphology, and properties of the samples are discussed in detail. X-ray diffraction measurements show that the films are polycrystalline with anatase tetragonal structure, which is further confirmed by Raman spectroscopy analysis. Meanwhile, Raman spectroscopy results indicate that the peak width of E g(1) mode, which is directly correlated to the carrier density, changes obviously with RF power. It is found that the substitution of Nb5+ and Ta5+ at Ti site is significantly improved with the increase of RF power from 150 W to 210 W. For the sample deposited at 210 W, the optical transmittance is above 82% in the visible range and the electrical resistivity is as low as 1.3 × 10-3 Ω cm with carrier density of 1.1 × 1021 cm-3 and Hall mobility of 4.5 cm2 V-1 s-1. The optical and electrical properties of NTTO thin films can be compared to those of Nb or Ta doped anatase TiO2. However, co-doping with Nb and Ta gives a possible platform to complement the limitations of each individual dopant.

Water Adsorption on Clean and Defective Anatase TiO2 (001) Nanotube Surfaces: A Surface Science Approach.

PubMed

Kenmoe, Stephane; Lisovski, Oleg; Piskunov, Sergei; Bocharov, Dmitry; Zhukovskii, Yuri F; Spohr, Eckhard

2018-05-31

We use ab initio molecular dynamics simulations to study the adsorption of thin water films with 1 and 2 ML coverage on anatase TiO 2 (001) nanotubes. The nanotubes are modeled as 2D slabs, which consist of partially constrained and partially relaxed structural motifs from nanotubes. The effect of anion doping on the adsorption is investigated by substituting O atoms with N and S impurities on the nanotube slab surface. Due to strain-induced curvature effects, water adsorbs molecularly on defect-free surfaces via weak bonds on Ti sites and H bonds to surface oxygens. While the introduction of an S atom weakens the interaction of the surface with water, which adsorbs molecularly, the presence of an N impurity renders the surface more reactive to water, with a proton transfer from the water film and the formation of an NH group at the N site. At 2 ML coverage, a further surface-assisted proton transfer takes place in the water film, resulting in the formation of an OH - group and an NH 2 + cationic site on the surface.

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.

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.

Tunability of morphological properties of Nd-doped TiO2 thin films

NASA Astrophysics Data System (ADS)

Rehan, Imran; Sultana, Sabiha; Khan, Nauman; Qamar, Zahid; Rehan, Kamran

2016-11-01

In this work, an endeavor is made toward structural assessment and morphological variation of titanium dioxide (TiO2) thin films when doped with neodymium (Nd). The electron beam deposition technique was employed to fabricate Nd-based TiO2 thin films on n-Type Si substrates. Nd concentration was varied from 0.0 to 2.0 atomic percent (at.%) under identical growth environments. The films were deposited in an oxygen-deficient environment to cause the growth of rutile phases. Energy dispersive x-ray spectroscopy confirmed the presence and variation of Nd dopant in TiO2. X-ray diffraction analysis showed the transformation of amorphous structures of the as-grown samples to anatase polycrystalline after annealing at 500 °C, while atomic force microscopy exposed linearity in grain density in as-grown samples with doping until 1 at.%. Raman spectrums of as-grown and annealed samples revealed the growth of the anatase phase in the annealed samples. Based on these results it can be proposed that Nd doping has pronounced effects on the structural characteristics of TiO2 thin films.

Hydrothermal growth of highly monodispersed TiO2 nanoparticles: Functional properties and dye-sensitized solar cell performance

NASA Astrophysics Data System (ADS)

Navaneethan, M.; Nithiananth, S.; Abinaya, R.; Harish, S.; Archana, J.; Sudha, L.; Ponnusamy, S.; Muthamizhchelvan, C.; Ikeda, H.; Hayakawa, Y.

2017-10-01

Monodispersed anatase TiO2 nanoparticles were synthesized by hydrothermal method using citric acid as a capping agent. The effect of citric acid and the growth time on the formation of TiO2, functional properties and dye-sensitized solar cell performances were investigated. X-ray diffraction pattern (XRD) and Raman spectroscopy results revealed that the TiO2 nanoparticles possess the anatase phase. Transmission electron microscopy (TEM) measurement revealed the formation of spherical nanoparticles with monodispersity in size and morphology. An average size of 14 nm was obtained for the growth period of 15 h. The maximum efficiency (η) of dye-sensitized solar cell was achieved for TiO2 nanoparticles grown for 15 h as 7.66% which was higher than that of commercial P25 TiO2 (5.23%) and uncapped nanoparticles (3.68%).

Ultrasonic spray pyrolysis synthesis of reduced graphene oxide/anatase TiO2 composite and its application in the photocatalytic degradation of methylene blue in water.

PubMed

Park, Jeong-Ann; Yang, Boram; Lee, Joongki; Kim, In Gyeom; Kim, Jae-Hyun; Choi, Jae-Woo; Park, Hee-Deung; Nah, In Wook; Lee, Sang-Hyup

2018-01-01

Reduced graphene oxide (RGO)/anatase TiO 2 composite was prepared using a simple one-step technique-ultrasonic spray pyrolysis-in order to inhibit the aggregation of TiO 2 nanoparticles and to improve the photocatalytic performance for degradation of methylene blue (MB). Different proportions (0-5 wt%) of RGO/TiO 2 composites were characterized by scanning electronic microscopy (SEM), dispersive X-ray spectrometry (EDS), transmission electron microscopy (TEM), Brunauer-Emmett-Teller (BET) surface area, X-ray photoelectron spectroscopy (XPS), X-ray diffractometry (XRD), Raman spectroscopy, UV-vis spectroscopy, and electrochemical impedance spectroscopy (EIS) to verify mechanism. From these analysis, TiO 2 nanoparticles are distributed uniformly on the RGO sheets with crumpled shape during ultrasonic spray pyrolysis and surface area is increasing by increasing portion of RGO. Band gap of RGO 5 /TiO 2 (5 wt% of RGO) composite is 2.72 eV and band gap was reduced by increasing portion of RGO in RGO/TiO 2 composites. The RGO 5 /TiO 2 composite was superior to other lower content of RGO/TiO 2 composites with a rapid transport of charge carriers and an effective charge separation. The highest removal efficiency of MB was obtained at the RGO 5 /TiO 2 composite under UVC irradiation, which coincided with the EIS, and the optimal dose of the composite was determined to be 0.5 g/L. The RGO 5 /TiO 2 composite improve the photocatalytic degradation rate of MB over the TiO 2 due to a retardation of electron-hole recombination. The MB adsorption capacity and photocatalytic degradation efficiency were greatly affected by pH changes and increased with increasing pH due to electrostatic interactions and generation of more hydroxyl radicals. The reusability of RGO 5 /TiO 2 composite was examined during 3 cycles. Copyright © 2017 Elsevier Ltd. All rights reserved.

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.

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.

Oxygen vacancies enabled enhancement of catalytic property of Al reduced anatase TiO2 in the decomposition of high concentration ozone

NASA Astrophysics Data System (ADS)

Ding, Yanhua; Zhang, Xiaolei; Chen, Li; Wang, Xiaorui; Zhang, Na; Liu, Yufeng; Fang, Yongzheng

2017-06-01

The catalytic decomposition of gaseous ozone (O3) is investigated using anatase TiO2 (A-TiO2) and Aluminum-reduced A-TiO2 (ARA-TiO2) at high concentration and high relative humidity (RH) without light illumination. Compared with the pristine A-TiO2, the ARA-TiO2 sample possesses a unique crystalline core-amorphous shell structure. It is proved to be an excellent solar energy ;capture; for solar thermal collectors due to lots of oxygen vacancies. The results indicate that the overall decomposition efficiency of O3 without any light irradiation has been greatly improved from 4.8% on A-TiO2 to 100% on ARA-TiO2 under the RH=100% condition. The ozone conversion over T500/ARA-TiO2 catalyst is still maintained at 95% after a 72 h test under the reaction condition of 18.5 g/m3 ozone initial concentration, and RH=90%. The results can be explained that T500/ARA-TiO2 possesses the largest amorphous contour, the lowest crystallinity, the most surface-active Ti3+/Ti4+couples, and the most oxygen vacancies. This result opens a new door to widen the application of TiO2 in the thermal-catalytic field.

TiO2 Nanostructure Synthesized by Sol-Gel for Dye Sensitized Solar Cells as Renewable Energy Source

NASA Astrophysics Data System (ADS)

Ramelan, A. H.; Wahyuningsih, S.; Saputro, S.; Supriyanto, E.; Hanif, Q. A.

2017-02-01

The use of renewable materials as a constituent of a smart alternative energy such as the use of natural dyes for light harvesting needs to be developed. Synthesis of anatase titanium dioxide (TiO2) and fabrication Dye-Sensitized Solar Cell (DSSC) using dye-based of anthocyanin from purple sweet potato (Ipomoea batatas L.) as a photosensitizer had been done. Synthesis TiO2 through sol-gel process with the addition of triblock copolymer Pluronic F127 template was controlled at pH 3 whereas calcination was carried out at a temperature of 500 °C, 550 °C and 600 °C. The obtained TiO2 were analyzed by XRD, SAA, and SEM. The conclusion is anatase TiO2 obtained until annealing up to 600 °C. Self-assembly Pluronic F127 triblock copolymer capable of restraining the growth of TiO2 crystals. Retention growth of TiO2 mesoporous produces material character that can be used as builders photoanode DSSC with natural sensitizer anthocyanin from purple sweet potatoes. Based on the analysis of X-ray diffraction patterns and surface area analyser, the higher the calcination temperature the greater the size of the anatase crystals is obtained, however, the smaller its surface area. Purple sweet potato anthocyanin’s dyed on to TiO2 was obtained a good enough performance for DSSC’s and gain the optimum performance from DSSC’s system built with mesoporous TiO2 annealed 550 °C using flavylium form anthocyanin.

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.

The Electronic Structures and Optical Properties of Alkaline-Earth Metals Doped Anatase TiO2: A Comparative Study of Screened Hybrid Functional and Generalized Gradient Approximation

PubMed Central

Ma, Jin-Gang; Zhang, Cai-Rong; Gong, Ji-Jun; Wu, You-Zhi; Kou, Sheng-Zhong; Yang, Hua; Chen, Yu-Hong; Liu, Zi-Jiang; Chen, Hong-Shan

2015-01-01

Alkaline-earth metallic dopant can improve the performance of anatase TiO2 in photocatalysis and solar cells. Aiming to understand doping mechanisms, the dopant formation energies, electronic structures, and optical properties for Be, Mg, Ca, Sr, and Ba doped anatase TiO2 are investigated by using density functional theory calculations with the HSE06 and PBE functionals. By combining our results with those of previous studies, the HSE06 functional provides a better description of electronic structures. The calculated formation energies indicate that the substitution of a lattice Ti with an AEM atom is energetically favorable under O-rich growth conditions. The electronic structures suggest that, AEM dopants shift the valence bands (VBs) to higher energy, and the dopant-state energies for the cases of Ca, Sr, and Ba are quite higher than Fermi levels, while the Be and Mg dopants result into the spin polarized gap states near the top of VBs. The components of VBs and dopant-states support that the AEM dopants are active in inter-band transitions with lower energy excitations. As to optical properties, Ca/Sr/Ba are more effective than Be/Mg to enhance absorbance in visible region, but the Be/Mg are superior to Ca/Sr/Ba for the absorbance improvement in near-IR region. PMID:28793520

A facile method to synthesize nitrogen and fluorine co-doped TiO2 nanoparticles by pyrolysis of (NH4)2TiF6

NASA Astrophysics Data System (ADS)

Chen, Daimei; Jiang, Zhongyi; Geng, Jiaqing; Zhu, Juhong; Yang, Dong

2009-02-01

The nitrogen and fluorine co-doped TiO2 (N-F-TiO2) nanoparticles of anatase crystalline structure were prepared by a facile method of (NH4)2TiF6 pyrolysis, and characterized by thermogravimetry-differential thermal analysis (TG-DTA), X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and ultraviolet visible (UV-Vis) spectroscopy etc. With the increase of calcination temperature, (NH4)2TiF6 decomposed into TiOF2 and NH4TiOF3 at first, and then formed anatase-type TiO2 with thin sheet morphology. H3BO3 as oxygen source can promote the formation of anatase TiO2, but decrease the F content in the N-F-TiO2 materials due to the formation of volatile BF3 during the precursor decomposition. The photocatalytic activity of the obtained N-F-TiO2 samples was evaluated by the methylene blue degradation under visible light, and all the samples exhibited much higher photocatalytic activity than P25. Moreover, the merits and disadvantages of this proposed method to prepare doped TiO2 are discussed.

Teflon impregnated anatase TiO2 nanoparticles irradiated by 80 keV Xe+ ions

NASA Astrophysics Data System (ADS)

Khanam, Rizwin; Paul, Nibedita; Kumar, P.; Kanjilal, D.; Ahmed, Gazi A.; Mohanta, Dambarudhar

2014-10-01

We report the effect of 80 keV Xe+ ion irradiation on the morphological and optical responses of TiO2 nanoparticles spread over commercially available polytetrafluoroethylene (PTFE, Teflon). These nanoparticles were synthesized via a convenient, sol-gel approach with titanium isopropoxide as the main precursor. From X-ray diffraction (XRD) studies we found that, the nanoparticles crystallize in anatase phase and with a preferential orientation of crystallites along (1 0 1) plane. Upon irradiation at a fluence of 1.25 × 1017 ions/cm2, the nanoparticle dimension was found to increase from a value of ∼9 nm to ∼20-30 nm. Essentially, particle growth is predicted as a consequence of swelling behavior accompanied by the formation of Xe van der Waal crystals in isolated regions of nano-titania. Evidence of nanoripples was also witnessed on the surface of the irradiated nano-titania. The morphological evolution was assessed both by atomic force and transmission electron microscopies (AFM and TEM) independently. From the UV-Vis optical absorption studies, the estimated optical band gap was found to drop with increasing fluence, while refractive index exhibited a remarkable improvement. Photoluminescence (PL) studies have revealed that, the band edge emission and those due to the self trapped excitons (STE) and other oxygen vacancy related ones were manifested considerably as a result of Xe ion irradiation.

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

Selective defunctionalization by TiO2 of monomeric phenolics from lignin pyrolysis into simple phenols.

PubMed

Mante, Ofei D; Rodriguez, Jose A; Babu, Suresh P

2013-11-01

This study is focused on defunctionalizing monomeric phenolics from lignin into simple phenols for applications such as phenol/formaldehyde resins, epoxidized novolacs, adhesives and binders. Towards this goal, Titanium dioxide (TiO2) was used to selectively remove hydroxyl, methoxy, carbonyl and carboxyl functionalities from the monomeric phenolic compounds from lignin to produce mainly phenol, cresols and xylenols. The results showed that anatase TiO2 was more selective and active compared to rutile TiO2. Catechols were found to be the most reactive phenolics and 4-ethylguaiacol the least reactive with anatase TiO2. An overall conversion of about 87% of the phenolics was achieved at 550°C with a catalyst-to-feed ratio of 5 w/w. Over 97% conversion of phenolics is achievable at moderate temperatures (550°C or ≤ 600°C) and a moderate catalyst-to-feed ratio of 6.5:1. The reactivity of catechols on TiO2 suggests that titania is a promising catalyst in the removal of hydroxyl moiety. Published by Elsevier Ltd.

Effect of sulfate ions on the crystallization and photocatalytic activity of TiO2/diatomite composite photocatalyst

NASA Astrophysics Data System (ADS)

Zhang, Jinjun; Wang, Xiaoyan; Wang, Jimei; Wang, Jing; Ji, Zhijiang

2016-01-01

TiO2 nanoparticles were immobilized on diatomite by hydrolysis-deposition method using titanium tetrachloride as precursor. The effect of sulfate ions on the crystallization and photocatalytic activity of TiO2/diatomite composite photocatalyst was characterized by TG-DSC, XRD, BET surface area, SEM, FT-IR spectroscopy, XPS and UV-vis diffuse reflectance spectra. The results indicate that addition of a small amount of sulfate ions promotes the formation of anatase phase and inhibits the transformation from anatase to rutile. On the other hand, sulfate ions immobilized on the surface of TiO2/diatomite have strong affinity for electrons, capturing the photo-generated electrons, which hinders the recombination of electrons and holes.

When Anatase Nanoparticles Become Bulklike: Properties of Realistic TiO2 Nanoparticles in the 1-6 nm Size Range from All Electron Relativistic Density Functional Theory Based Calculations.

PubMed

Lamiel-Garcia, Oriol; Ko, Kyoung Chul; Lee, Jin Yong; Bromley, Stefan T; Illas, Francesc

2017-04-11

All electron relativistic density functional theory (DFT) based calculations using numerical atom-centered orbitals have been carried out to explore the relative stability, atomic, and electronic structure of a series of stoichiometric TiO 2 anatase nanoparticles explicitly containing up to 1365 atoms as a function of size and morphology. The nanoparticles under scrutiny exhibit octahedral or truncated octahedral structures and span the 1-6 nm diameter size range. Initial structures were obtained using the Wulff construction, thus exhibiting the most stable (101) and (001) anatase surfaces. Final structures were obtained from geometry optimization with full relaxation of all structural parameters using both generalized gradient approximation (GGA) and hybrid density functionals. Results show that, for nanoparticles of a similar size, octahedral and truncated octahedral morphologies have comparable energetic stabilities. The electronic structure properties exhibit a clear trend converging to the bulk values as the size of the nanoparticles increases but with a marked influence of the density functional employed. Our results suggest that electronic structure properties, and hence reactivity, for the largest anatase nanoparticles considered in this study will be similar to those exhibited by even larger mesoscale particles or by bulk systems. Finally, we present compelling evidence that anatase nanoparticles become effectively bulklike when reaching a size of ∼20 nm diameter.

Biphase-Interface Enhanced Sodium Storage and Accelerated Charge Transfer: Flower-Like Anatase/Bronze TiO2/C as an Advanced Anode Material for Na-Ion Batteries.

PubMed

Chu, Chenxiao; Yang, Jing; Zhang, Qianqian; Wang, Nana; Niu, Feier; Xu, Xuena; Yang, Jian; Fan, Weiliu; Qian, Yitai

2017-12-20

Flower-like assembly of ultrathin nanosheets composed of anatase and bronze TiO 2 embedded in carbon is successfully synthesized by a simple solvothermal reaction, followed with a high-temperature annealing. As an anode material in sodium-ion batteries, this composite exhibits outstanding electrochemical performances. It delivers a reversible capacity of 120 mA h g -1 over 6000 cycles at 10 C. Even at 100 C, there is still a capacity of 104 mA h g -1 . Besides carbon matrix and hierarchical structure, abundant interfaces between anatase and bronze greatly enhance the performance by offering additional sites for reversible Na + storage and improving the charge-transfer kinetics. The interface enhancements are confirmed by discharge/charge profiles, rate performances, electrochemical impedance spectra, and first-principle calculations. These results offer a new pathway to upgrade the performances of anode materials in sodium-ion batteries.

Synthesis and structural characteristics of high surface area TiO2 aerogels by ultrasonic-assisted sol-gel method

NASA Astrophysics Data System (ADS)

Qingge, Feng; Huidong, Cai; Haiying, Lin; Siying, Qin; Zheng, Liu; Dachao, Ma; Yuyang, Ye

2018-02-01

TiO2 aerogel is a unique three-dimensional porous nano-particle material with the characteristics of high specific surface area and good light transmittance. In this paper, a novel method involving ultrasonic-assisted sol-gel, solvent exchange, and vacuum drying was successfully developed to synthesis the TiO2 aerogel. The morphology and properties of the prepared TiO2 aerogels were characterized by the Brunauer-Emmett-Teller theory (BET), x-ray diffraction, field-emission scanning electron microscopy, energy dispersive spectroscopy, thermogravimetric analysis-differential thermal analysis, Fourier transform infrared spectroscopy, and Raman spectroscopy. The adsorption and photocatalytic activity of TiO2 aerogels was evaluated by monitoring the degradation of Rhodamine B solution. Our results indicated that: (1) with an optimum ratio of Ti:H2O = 8:1 the BET surface area, average pore diameter, and total pore volume of TiO2 aerogel are enhanced to 563.6 m2 g-1, 3.01 nm, and 0.42 cm3 g-1, respectively; (2) the TiO2 aerogels possessed controllable crystal form depending on the thermal treatments conditions. The crystal face (101) of anatase, complete anatase, mixed state of anatase and rutile, and rutile were obtained by increasing the temperature from 200 °C-300 °C, from 400 °C-500 °C, 600 °C, and from 700 °C-1000 °C, respectively; and (3) the excellent catalytic activity of the as-prepared TiO2 aerogels for the ultraviolet photolytic degradation of Rhodamine B had attributed to the synergistic effect of adsorption and photoactivity.

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.

Rapid heat treatment for anatase conversion of titania nanotube orthopedic surfaces

NASA Astrophysics Data System (ADS)

Bhosle, Sachin M.; Friedrich, Craig R.

2017-10-01

The amorphous to anatase transformation of anodized nanotubular titania surfaces has been studied by x-ray diffraction and transmission electron microscopy (TEM). A more rapid heat treatment for conversion of amorphous to crystalline anatase favorable for orthopedic implant applications was demonstrated. Nanotube titania surfaces were fabricated by electrochemical anodization of Ti6Al4V in an electrolyte containing 0.2 wt% NH4F, 60% ethylene glycol and 40% deionized water. The resulting surfaces were systematically heat treated in air with isochronal and isothermal experiments to study the temperature and time dependent transformation respectively. Energy dispersive spectroscopy shows that the anatase phase transformation of TiO2 in the as-anodized amorphous nanotube layer can be achieved in as little as 5 min at 350 °C in contrast to reports of higher temperature and much longer time. Crystallinity analysis at different temperatures and times yield transformation rate coefficients and activation energy for crystalline anatase coalescence. TEM confirms the (101) TiO2 presence within the nanotubes. These results confirm that for applications where amorphous titania nanotube surfaces are converted to crystalline anatase, a 5 min production flow-through heating process could be used instead of a 3 h batch process, reducing time, cost, and complexity.

Enhanced photovoltaic performance of a quantum dot-sensitized solar cell using a Nb-doped TiO2 electrode.

PubMed

Jiang, Lei; You, Ting; Deng, Wei-Qiao

2013-10-18

In this work Nb-doped anatase TiO2 nanocrystals are used as the photoanode of quantum-dot-sensitized solar cells. A solar cell with CdS/CdSe quantum dots co-sensitized 2.5 mol% Nb-doped anatase TiO2 nanocrystals can achieve a photovoltaic conversion efficiency of 3.3%, which is almost twice as high as the 1.7% obtained by a cell based on undoped TiO2 nanocrystals. The incident photon-to-current conversion efficiency can reach as high as 91%, which is a record for all quantum-dot-sensitized solar cells. Detailed analysis shows that such an enhancement is due to improved lifetime and diffusion length of electrons in the solar cell.

Single-walled carbon nanotube-facilitated dispersion of particulate TiO2 on ZrO2 ceramic membrane filters.

PubMed

Yao, Yuan; Li, Gonghu; Gray, Kimberly A; Lueptow, Richard M

2008-07-15

We report that SWCNTs substantially improve the uniformity and coverage of TiO2 coatings on porous ZrO2 ceramic membrane filters. The ZrO2 filters were dip coated with 100 nm anatase TiO2, TiO2/SWCNT composites, a TiO2+SWCNT mixture, and a TiO2/MWCNT composite at pH 3, 5, and 8. Whereas the TiO2+SWCNT mixture and the TiO2/MWCNT composite promote better coverage and less clumping than TiO2 alone, the TiO2/SWCNT composite forms a complete uniform coating without cracking at pH 5 ( approximately 100% coverage). A combination of chemical and electrostatic effects between TiO2 and SWCNTs forming the composite as well as between the composite and the ZrO2 surface explains these observations.

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.

Solution equilibrium behind the room-temperature synthesis of nanocrystalline titanium dioxide

NASA Astrophysics Data System (ADS)

Seisenbaeva, Gulaim A.; Daniel, Geoffrey; Nedelec, Jean-Marie; Kessler, Vadim G.

2013-03-01

Formation of nanocrystalline and monodisperse TiO2 from a water soluble and stable precursor, ammonium oxo-lactato-titanate, (NH4)8Ti4O4(Lactate)8.4H2O, often referred to as TiBALDH or TALH, is demonstrated to be due to a coordination equilibrium. This compound, individual in the solid state, exists in solution in equilibrium with ammonium tris-lactato-titanate, (NH4)2Ti(Lactate)3 and uniform crystalline TiO2 nanoparticles (anatase) stabilized by surface-capping with lactate ligands. This equilibrium can be shifted towards nano-TiO2via application of a less polar solvent like methanol or ethanol, dilution of the solution, introduction of salts or raising the temperature, and reverted on addition of polar and strongly solvating media such as dimethyl sulfoxide, according to NMR. Aggregation and precipitation of the particles were followed by DLS and could be achieved by a decrease in their surface charge by adsorption of strongly hydrogen-bonding cations, e.g. in solutions of ammonia, ethanolamine or amino acid arginine or by addition of ethanol. The observed equilibrium may be involved in formation of nano-titania on the surface of plant roots exerting chelating organic carboxylate ligands and thus potentially influencing plant interactions.Formation of nanocrystalline and monodisperse TiO2 from a water soluble and stable precursor, ammonium oxo-lactato-titanate, (NH4)8Ti4O4(Lactate)8.4H2O, often referred to as TiBALDH or TALH, is demonstrated to be due to a coordination equilibrium. This compound, individual in the solid state, exists in solution in equilibrium with ammonium tris-lactato-titanate, (NH4)2Ti(Lactate)3 and uniform crystalline TiO2 nanoparticles (anatase) stabilized by surface-capping with lactate ligands. This equilibrium can be shifted towards nano-TiO2via application of a less polar solvent like methanol or ethanol, dilution of the solution, introduction of salts or raising the temperature, and reverted on addition of polar and strongly solvating

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.

A mini-review on rare earth metal-doped TiO2 for photocatalytic remediation of wastewater.

PubMed

Saqib, Najm Us; Adnan, Rohana; Shah, Irfan

2016-08-01

Titanium dioxide (TiO2) has been considered a useful material for the treatment of wastewater due to its non-toxic character, chemical stability and excellent electrical and optical properties which contribute in its wide range of applications, particularly in environmental remediation technology. However, the wide band gap of TiO2 photocatalyst (anatase phase, 3.20 eV) limits its photocatalytic activity to the ultraviolet region of light. Besides that, the electron-hole pair recombination has been found to reduce the efficiency of the photocatalyst. To overcome these problems, tailoring of TiO2 surface with rare earth metals to improve its surface, optical and photocatalytic properties has been investigated by many researchers. The surface modifications with rare earth metals proved to enhance the efficiency of TiO2 photocatalyts by way of reducing the band gap by shifting the working wavelength to the visible region and inhibiting the anatase-to-rutile phase transformations. This review paper summarises the attempts on modification of TiO2 using rare earth metals describing their effect on the photocatalytic activities of the modified TiO2 photocatalyst.

Preparation of Pd-loaded La-doped TiO2 nanotubes and investigation of their photocatalytic activity under visible light

NASA Astrophysics Data System (ADS)

Zong, Lanlan; Li, Qiuye; Zhang, Jiwei; Wang, Xiaodong; Yang, Jianjun

2013-11-01

Orthorhombic titanic acid nanotubes (TAN) have large BET surface area and small-diameter one-dimensional nanotubular morphology, so they can work as a good supporter and a precursor of TiO2. However, in our former research, we found that calcination of TAN to anatase TiO2 would destroy the nanotubular structure and decrease the BET surface area sharply. In this work, we utilized the pillar effect of the foreign nanoparticles (La2O3) to keep the nanotubular morphology of TiO2, and obtained the anatase TiO2 nanotubes with large BET surface area. For improving the photocatalytic activity, Pd nanoparticles were loaded as the electron traps on the surface of La-doped TiO2 by photo-deposition method. The photocatalysts were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, diffuse reflectance spectra, and N2 adsorption-desorption isotherms measurement. Their photocatalytic activities were evaluated by the removal of propylene under visible light irradiation ( λ ≥ 420 nm). The results showed that the photocatalytic activity of Pd-loaded La-doped TiO2 nanotubes improved effectively compared with that of La-doped TiO2 and pure TiO2.

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

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-

Surface properties of anatase TiO2 nanowire films grown from a fluoride-containing solution.

PubMed

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

2013-06-03

Controlling the surface chemistry of nucleating seeds during wet-chemical synthesis allows for the preparation of morphologically well-defined nanostructures. Synthesis conditions play a key role in the surface properties, which directly affect the functional properties of the material. Therefore, it is important to establish post-synthesis treatments to facilitate the optimization of surface properties with respect to a specific application, without losing the morphological peculiarity of the nanostructure. We studied the surface properties of highly crystalline and porous anatase TiO2 nanowire (NW) electrodes, grown by chemical-bath deposition in fluoride-containing solutions, using a combined electrochemical and spectroscopic approach. As-deposited films showed low capacity for catechol adsorption and a poor photoelectrocatalytic activity for water oxidation. Mild thermal annealing at 200 °C resulted in a significant improvement of the electrode photoelectrocatalytic activity, whereas the bulk properties of the NWs (crystal structure, band-gap energy) remained unchanged. Enhancement of the functional properties of the material is discussed on the basis of adsorption capacity and electronic properties. The temperature-induced decrease of recombination centers, along with the concomitant increase of adsorption and reaction sites upon thermal annealing are called to be responsible for such improved performance. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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