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Concept: Rutile

160

The prototypical photocatalyst TiO2 exists in different polymorphs, the most common forms are the anatase- and rutile-crystal structures. Generally, anatase is more active than rutile, but no consensus exists to explain this difference. Here we demonstrate that it is the bulk transport of excitons to the surface that contributes to the difference. Utilizing high -quality epitaxial TiO2 films of the two polymorphs we evaluate the photocatalytic activity as a function of TiO2-film thickness. For anatase the activity increases for films up to ~5 nm thick, while rutile films reach their maximum activity for ~2.5 nm films already. This shows that charge carriers excited deeper in the bulk contribute to surface reactions in anatase than in rutile. Furthermore, we measure surface orientation dependent activity on rutile single crystals. The pronounced orientation-dependent activity can also be correlated to anisotropic bulk charge carrier mobility, suggesting general importance of bulk charge diffusion for explaining photocatalytic anisotropies.

Concepts: Particle physics, Orientation, Titanium dioxide, Rutile, Young's modulus, Photocatalysis, Anatase, Charge carrier

92

Food-grade titanium dioxide (TiO2) containing a nanoscale particle fraction (TiO2-NPs) is approved as a white pigment (E171 in Europe) in common foodstuffs, including confectionary. There are growing concerns that daily oral TiO2-NP intake is associated with an increased risk of chronic intestinal inflammation and carcinogenesis. In rats orally exposed for one week to E171 at human relevant levels, titanium was detected in the immune cells of Peyer’s patches (PP) as observed with the TiO2-NP model NM-105. Dendritic cell frequency increased in PP regardless of the TiO2 treatment, while regulatory T cells involved in dampening inflammatory responses decreased with E171 only, an effect still observed after 100 days of treatment. In all TiO2-treated rats, stimulation of immune cells isolated from PP showed a decrease in Thelper (Th)-1 IFN-γ secretion, while splenic Th1/Th17 inflammatory responses sharply increased. E171 or NM-105 for one week did not initiate intestinal inflammation, while a 100-day E171 treatment promoted colon microinflammation and initiated preneoplastic lesions while also fostering the growth of aberrant crypt foci in a chemically induced carcinogenesis model. These data should be considered for risk assessments of the susceptibility to Th17-driven autoimmune diseases and to colorectal cancer in humans exposed to TiO2 from dietary sources.

Concepts: Immune system, Inflammation, Monocyte, Titanium dioxide, Titanium, Rutile, Pigment, Titanium tetrachloride

28

The synthesis of highly-crystalline porous TiO(2) microspheres is reported using ultrasonic spray pyrolysis (USP) in the presence of colloidal silica as a template. We have exploited the interactions between hot SiO(2) template particles surface and TiO(2) precursor that occur during reaction inside the droplets, to control the physical and chemical properties of the resulting particles. Varying the SiO(2) to titanium precursor molar ratio and the colloidal silica dimension, we obtained porous titania microspheres with tunable morphology, porosity, BET surface area, crystallite size, band-gap, and phase composition. In this regard, we have also observed the preferential formation of anatase vs. rutile with increasing initial surface area of the silica template. The porous TiO(2) microspheres were tested in the photocatalytic degradation of nitrogen oxides (NO(x)) in the gas phase. USP prepared nanostructured titania samples were found to have significantly superior specific activity per surface area compared to a commercial reference sample (P25 by Evonik-Degussa).

Concepts: Oxygen, Chemical reaction, Oxide, Oxides, Titanium dioxide, Titanium, Rutile, Anatase

28

Six representative isotope-labeled samples of titanium dioxide were synthesized: Ti(16)O(2), Ti(17)O(2) and Ti(18)O(2), each in anatase and rutile forms. Their Raman scattering was analyzed at temperatures down to 5 K. Spectral assignment was supported by numerical simulation using DFT calculations. The combination of experimental and theoretical Raman frequencies with the corresponding isotopic shifts allowed us to address various still-open questions about the second-order Raman scattering in rutile, and the analysis of overlapping features in the anatase spectrum.

Concepts: Oxygen, Titanium dioxide, Titanium, Rutile

26

Understanding the kinetics of dye adsorption and desorption on semiconductors is crucial for optimizing the performance of dye-sensitized solar cells (DSSCs). Quartz Crystal Microbalance with Dissipation Monitoring (QCM-D) measures adsorbed mass in real time, allowing determination of binding kinetics. In this work, we characterize adsorption of the common RuBipy dye, “N3,” to the native oxide layer of a planar, sputter-coated titanium surface, simulating the TiO2 substrate of a DSSC. We report adsorption equilibrium constants consistent with prior optical measurements of N3 adsorption. Dye binding and surface integrity were also verified by SEM, EDX, and XPS. We further study desorption of the dye from the native oxide layer on the QCM sensors using tetrabutylammonium hydroxide (TBAOH), a commonly used industrial desorbant. We find that using TBAOH as a desorbant does not fully regenerate the surface, though little ruthenium or nitrogen is observed by XPS after desorption, suggesting that carboxyl moieties of N3 remain bound. We demonstrate the native oxide layer of a titanium sensor as a valid and readily available planar TiO2 morphology to study dye adsorption and desorption, and begin to investigate the mechanism of dye desorption in DSSCs, a system that requires further study.

Concepts: Adsorption, Oxide, Solar cell, Titanium dioxide, Dye-sensitized solar cell, Quartz, Quartz crystal microbalance, Rutile

26

Stable reduced TiO2 rutile nanorods with well-defined facets were prepared by a solvothermal route in the presence of Zn powder. The oxygen vacancy in the TiO2 nanorods, which can be tuned by the amount of Zn, results in a narrow band gap and visible-light photocatalytic activity.

Concepts: Solar cell, Titanium dioxide, Titanium, Rutile, Zinc oxide, Photocatalysis, Anatase, Band gap

26

Glycerol is selectively converted to hydroxyacetaldehyde (HAA) and H2 in aqueous solution on TiO2-based photocatalysts. The product selectivity was verified to be strongly dependent on the facets of TiO2. Rutile with high percentage of {110} facets results in over 90% superior selectivity of HAA, while anatase with {001} or {101} facets gives only 16% and 49% selectivity for HAA, respectively.

Concepts: Concentration, Chemistry, Titanium dioxide, Solutions, Aqueous solution, Rutile, Photocatalysis, Anatase

25

Abstract The production of titanium dioxide nanoparticles (TiO2 NPs) for commercial applications has greatly increased over the last years and consequently the potential risk for human health. There is a growing awareness of the need to understand the behavior and influence these nanoparticles exert on the environment. Bioaccumulation serves as a good integrator to assess chemical exposure in aquatic systems and is dependent on factors, such as the exposure routes, diet and the aqueous medium. We analyzed the experimental bioaccumulation capability of ionic titanium and TiO2 NPs by zebrafish (Danio rerio) eleutheroembryos through bioconcentration factors (BCFs), after 48 or 72 h of exposure. The stability of both chemical forms in an aquatic medium was fully characterized for further bioaccumulation studies. Several stabilizing agents (humic acids, soluble starch, polyethylene glycol, Na4P2O7 and Na2HPO4) for anatase and rutile, the two allotrophs of TiO2 NPs, were evaluated to check the evolution of the aggregation process. Around 60% of TiO2 NPs remained disaggregated under simulated environmental conditions with the addition of 50 mg L(-1) of humic acids. However, the presence of eleutheroembryos in the exposure medium increased TiO2 NPs aggregation in the experimental tests. The BCFs values obtained in all cases were <100, which classifies ionic titanium and TiO2 NPs as non-bioaccumulative substances, under the REACH regulations.

Concepts: Oxide, Titanium dioxide, Titanium, Rutile, Danio kyathit, Anatase, Titanium tetrachloride, Ilmenite

24

Developing cell sensitive indicators on interacting substrates that allows specific cell manipulation by a combination of physical, chemical or mechanical cues is a challenge for current biomaterials. Hence, various fabrication approaches have been created on a variety of substrates to mimic or create cell specific cues. However, to achieve cell specific cues a multistep process or a post-chemical treatment is often necessitated. So, a simple approach without any chemical or biological treatment would go a long way in developing bio-functionalized substrates to effectively modulate cell adhesion and interaction. The present investigation is aimed to study the manipulative activity induced by phase transformed titanium surface. An ultra-short laser is used to fabricate the phase transformed titanium surface where a polymorphic titanium oxide phases with titanium monoxide (TiO), tri-titanium oxide (Ti3O) and titanium dioxide (TiO2) have been synthesized on commercially pure titanium. Control over oxide phase transformed area was demonstrated via a combination of laser scanning time (laser pulse interaction time) and laser pulse widths (laser pulse to pulse separation time). The interaction of phase transformed titanium surface with NIH 3T3 fibroblasts and MC 3T3-E1 osteoblast cells developed a new bio-functionalized platforms on titanium based biomaterials to modulate cell migration and adhesion. The synthesized phase transformed titanium surface on the whole appeared to induce directional cues for cell migration with unique preferential cell adhesion unseen by other fabrication approaches. The precise bio-functionalization controllability exhibited during fabrication offers perceptible edge for developing a variety of smart bio-medical devices, implants and cardiovascular stents where the need in supressing specific cell adhesion and proliferation is of great demand.

Concepts: Ultraviolet, Laser, Oxide, Oxides, Titanium dioxide, Titanium, Rutile, Titanium(II) oxide

16

Water creates special problems for prebiotic chemistry, as it is thermodynamically favorable for amide and phosphodiester bonds to hydrolyze. The availability of alternative solvents with more favorable properties for the formation of prebiotic molecules on the early Earth may have helped bypass this so-called “water paradox”. Formamide (FA) is one such solvent, and can serve as a nucleobase precursor, but it is difficult to envision how FA could have been generated in large quantities or accumulated in terrestrial surface environments. We report here the conversion of aqueous acetonitrile (ACN) via hydrogen cyanide (HCN) as an intermediate into FA by γ-irradiation under conditions mimicking exposure to radioactive minerals. We estimate that a radioactive placer deposit could produce 0.1‒0.8 mol FA km-2 year-1. A uraninite fission zone comparable to the Oklo reactors in Gabon can produce 0.1‒1 mol m-2 year-1, orders of magnitude greater than other scenarios of FA production or delivery for which reaching sizeable concentrations of FA are problematic. Radioactive mineral deposits may be favorable settings for prebiotic compound formation through emergent geologic processes and FA-mediated organic chemistry.

Concepts: Oxygen, Molecule, Chemistry, Mineral, Gold, Geology, Rutile, Hydrogen cyanide