Six kaolin samples from the Lower Tertiary Huber Formation near Wrens, Georgia were analyzed using transmission electron microscopy (TEM), electron diffraction (ED), powder X-ray diffraction (XRD), chemical analysis, and magnetic susceptibility to characterize the Ti-bearing phases. Selected samples were treated with 5 M NaOH to remove kaolinite and concentrate the Ti-bearing phases for additional analysis. TiO2 content in the bulk fraction ranges from 1.2 to 5.4 wt. %. There are at least three Ti-bearing phases, including anatase, rutile, and a poorly defined nanocrystalline form. Anatase is most abundant and is commonly found with {010} faces in association with kaolinite edge and basal faces. The nanocrystalline form occurs at 0–1 wt. %, and rutile occurs in trace amounts. Bulk XRD analysis correlates well with the bulk TiO2 chemical measurements. Average anatase unit-cell parameters are a = 0.37908 ± 0.0002 nm and c = 0.951 ± 0.001 nm. These parameters indicate an approximate chemical formula of Fe3+0.05Ti4+0.95O1.95(OH)0.05.

The distribution of TiO2 content as a function of depth may be useful to obtain original grain-size variations associated with relative sea-level changes responsible for the deposition of the Huber Formation. Evidence for original depositional sediment properties can be seen in the occurrence of pseudomorphic replacement of micas and fecal pellets by kaolinite. Additional evidence for post-depositional changes includes the sub-micrometer euhedral character and low Fe content of the anatase (relative to soil-derived anatase). These observations for the Huber Formation are consistent with a previously published theory for kaolin genesis that includes biomineralization of originally coarser-grained aluminosilicates into a kaolinite-rich ore body.

The growing use of nano titanium dioxide (TiO2) in consumer and agricultural products has accelerated its introduction into terrestrial environments, where its impact has not been documented extensively. TiO2 toxicity arises primarily from its ability to photochemically generate reactive oxygen species (ROS), including hydrogen peroxide (H2O2). While common ligands in soil porewaters can either hinder or enhance the degradation of organic contaminants by TiO2, their effects on ROS production by TiO2 have not been understood clearly. The objective of this study was to assess the effect of phosphate (P) and nitrate on UV-irradiated anatase, nano-TiO2. Accordingly, H2O2-generation kinetics experiments were conducted in UV-irradiated TiO2 under environmentally relevant concentrations of the ligands (0, 50, 100, and 250 μM) and pH values (4.00 ± 0.02 and 8.00 ± 0.02) from 0–100 min. Under all conditions, H2O2 grew logarithmically and reached between 5.38 and 22.98 μM after 100 min. At pH 4.00 ± 0.02, H2O2 production was suppressed by P but not by nitrate. Conversely, at pH 8.00 ± 0.02, nitrate did not affect H2O2 concentration while P increased it. Non-specific, minimal adsorption of nitrate prevented interference with the photoreactivity of TiO2. Due to the pH-dependent behavior of suspended TiO2 and H2O2 degradation rates, specific adsorption of P on TiO2 impeded its ability to produce H2O2 photochemically at pH 4.00 ± 0.02 but amplified it at pH 8.00 ± 0.02.

As a photocatalyst with good prospects, TiO2 has the shortcomings of easy agglomeration and no catalytic performance under visible light. The purpose of the present study was to help solve these problems by employing muscovite as a carrier for N-doped TiO2 in a nanocomposite. The nanocomposites were prepared by a liquid precipitation-grinding method using muscovite as the matrix and urea as the nitrogen source. The crystal structures, chemical bonding, and micromorphology of the nanocomposites were analyzed by X-ray diffraction, infrared absorption spectrometry, and field emission scanning electron microscopy, respectively. Visible and ultraviolet (UV-Vis) light absorption of the nanocomposites was analyzed by solid ultraviolet diffuse reflectance spectroscopy. The photocatalytic effect of the nanocomposites was studied based on the degradation of rhodamine B (RhB) solution. The photocatalytic degradation product of RhB was detected by high-performance liquid chromatography-mass spectrometry, revealing that N-doping inhibits the growth of TiO2 nanoparticles. The photocatalytic performance of N-TiO2/muscovite composite nanomaterials decreased with increasing heat-treatment temperature. N-doped TiO2/muscovite nanocomposites that were heated at 400°C showed the best photocatalytic performance under visible-light illumination with an RhB degradation of 97%.

The aim of the present study was to synthesize a photocatalyst on the basis of TiO2 with kaolin as the support material. Properties such as layered structure and a suitable particle size of kaolin could be beneficial in the production of a high-quality and relatively cheap photocatalyst on an industrial scale. Homogeneous hydrolysis with urea as a precipitation agent and kaolin as support material was used to obtain a kaolin surface covered with TiO2. Samples were characterized by means of X-ray powder diffraction, infrared and Raman spectroscopy, high-resolution transmission electron microscopy, Brunauer-Emmett-Teller surface area, and Barrett-Joyner-Halenda porosity determination. Photocatalytic activity was assessed by a Reactive Black 5 azo dye discoloration in a water suspension and by acetone decomposition on a thin layer of sample in a gas phase. The characterization confirmed that the well crystallized TiO2 was distributed effectively over the whole surface of a kaolin substrate, and photocatalytic tests revealed that the active surface layer of titania particles on kaolin performed well, suggesting that kaolin acts as a suitable support.

Reduced graphene oxide supported titanium dioxide (GO/TiO2) heterojunction composites as highly active photocatalysts were synthesized via simple ultrasonic mixing and hydrothermal reaction using TiCl3 and GO as precursors. Their structure and morphology were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, Raman spectra, UV-vis spectroscopy, and thermogravimetic analysis. The GO/TiO2 heterojunction composites were used to degrade methyl orange (MO). The adsorption and photocatalytic degradation rate of the prepared GO/TiO2 composites increased by nearly three times compared with that of pristine TiO2 or GO, which reached up 90%, to degrade MO after 4 h, which provides a simple method to obtain photocatalytic materials.

A novel and highly efficient Ag3VO4/C3N4/reduced TiO2 microsphere composite was obtained through a hydrothermal and depositional process. The microstructure, individual components with different proportions, and optical properties of the ternary nanocomposites were intensively studied. The prepared ternary composites exhibited superior photocatalytic performance of degradation of methylene blue compared with single component and S1 (C3N4/reduced TiO2) binary composites, demonstrating that the introduction of Ag3VO4 into g-C3N4/r-TiO2 can effectively improve the photocatalytic activity. Recycling experiments confirmed that the nanocomposites exhibited superior cycle performance. The enhanced capability could be attributed to a synergetic effect including the formation of heterojunction, large surface area, improved light absorption, matched energy band structure, and the improved separation efficiency of photogenerated charges coming from dual Z-scheme structure. Particularly, the introduction of Ag3VO4 makes the dual Z-scheme charge transfer pathway completed with improved separation efficiency and stronger redox ability of photogenerated electrons and holes. The work provides a promising method to develop a new dual Z-scheme photocatalytic system to remove environmental pollutant.

Since the introduction of laser-assisted atom probe, analysis of nonconductive materials by atom probe tomography (APT) has become more routine. To obtain high-quality data, a number of acquisition variables needs to be optimized for the material of interest, and for the specific question being addressed. Here, the rutile (TiO2) reference material ‘Windmill Hill Quartzite,’ used for secondary ion mass spectrometry U–Pb dating and laser-ablation inductively coupled plasma mass spectrometry, was analyzed by laser-assisted APT to constrain optimal running conditions. Changes in acquisition parameters such as laser energy and detection rate are evaluated in terms of their effect on background noise, ionization state, hit-multiplicity, and thermal tails. Higher laser energy results in the formation of more complex molecular ions and affects the ionization charge state. At lower energies, background noise and hit-multiplicity increase, but thermal tails shorten. There are also correlations between the acquisition voltage and several of these metrics, which remain to be fully understood. The results observed when varying the acquisition parameters will be discussed in detail in the context of utilizing APT analysis of rutile within geology.

In equines, Cr2O3 is widely accepted as an indigestible marker, but there are health concerns regarding the carcinogenic properties of Cr2O3. Recently, TiO2 has been suggested to be an alternative digestibility marker in equines. However, a comparison between Cr2O3 and TiO2 has not been made in equines. Six Welsh pony geldings (initial BW: 254±3 kg; 7 years of age) fed chopped alfalfa hay were used to evaluate the use of TiO2 (Ti) and Cr2O3 (Cr) as markers for calculating apparent digestibility and to investigate the effect of frequency of marker administration on the measurement of digestibility values. Diets contained 4.65 kg dry matter (DM) chopped alfalfa hay supplemented with minerals, vitamins, TiO2 (3.3 g Ti/day) and Cr2O3 (3.2 g Cr/day). Ponies were dosed with either 3.3 g Ti and 3.2 g Cr once daily (DF1) or with 1.65 g Ti and 1.60 g Cr twice daily (DF2). After adaptation to the diets and procedures for 14 days, voluntary voided faeces were collected quantitatively over 7 days and analysed for moisture, ash, Ti and Cr. Apparent total tract DM digestibility (DMD) and organic matter digestibility (OMD) were calculated using the total faecal collection (TFC) and marker method (Ti and Cr). The overall mean cumulative faecal recovery of Cr and Ti (as % of intake) were 102.0% and 96.6%, respectively. Mean daily faecal recoveries of Cr as well as of Ti were not different (P=0.323; P=0.808, respectively) between treatments. Overall daily faecal recovery of Cr differed (P=0.019) from 100% when the marker was dosed once daily, whereas overall daily faecal recovery was similar to 100% for both administration frequencies when Ti was used as a marker. For both markers, the coefficient of variation of the mean faecal marker recovery between horses was lower when the markers were administrated twice per day. Across treatments, cumulative DMD and OMD estimated with Ti were similar (P=0.345; P=0.418, respectively) compared with those values determined by TFC method. When Cr was used, the calculated cumulative DMD tended (P=0.097) to be greater compared with those estimated with TFC, and cumulative OMD values were overestimated (P=0.013). Orally supplemented Ti recovery in the faeces of ponies fed chopped alfalfa hay with Ti administered once or twice daily was close to 100%, making it the preferred marker for digestibility trials in equines.

In recent years it has become apparent that the novel properties of nanomaterials may predispose them to a hitherto unknown potential for toxicity. A number of recent toxicological studies of nanomaterials exist, but these appear to be fragmented and often contradictory. Such discrepancies may be, at least in part, due to poor description of the nanomaterial or incomplete characterization, including failure to recognise impurities, surface modifications or other important physicochemical aspects of the nanomaterial. Herew em ake a casef or the importance of good quality, well-characterized nanomaterials for future toxicological studies, combined with reliable synthesis protocols, and we present our efforts to generate such materials. The model system for which we present results is TiO2 nanoparticles, currently used in a variety of commercial products.

The present study investigated the removal of methylene blue (MB) and orange II (OII) dyes from synthetic wastewater by means of adsorption and photocatalysis using natural kaolins. ForMB adsorption, the raw kaolinite-rich samples showed the greatest adsorption capacity, with rapid uptake (90% after 20 min). The experimental results were fitted better using the Langmuir isotherm model parameters compared to the Freundlich model, suggesting that the adsorption corresponds to monolayer coverage of MB molecules over the kaolinite surface. For OII, neither the Langmuir nor the Freundlich model gave reliable results, because the adsorption of anionic dye molecules by the clayey particles is not favoured.

Mixtures of kaolinite/Degussa TiO2 were also prepared, and their photocatalytic properties under UVlight exposure were investigated. Decolourization of MB solutions was observed, even in a mixture with low TiO2 content. This is related to the combined effect of adsorption and photocatalysis and, unlike the pure clay samples, the efficiency of such mixtures against OII was only slightly weaker (80–94%).

For TiO2-impregnated clays, with the kaolinite layers separated by sol-gel TiO2 particles, the MB removal was slow and effective only after >24 h due to the complexity of the bonding of MB molecules. On the other hand, the removal performance against OII solutions was very efficient (nearly 100%) within only 2 h. This excellent performance was attributed to morphological changes in clay particles.

In this study, the cross-section of electron-selective titanium oxide (TiO2) contacts for n-type crystalline silicon solar cells were investigated by transmission electron microscopy. It was revealed that the excellent cell efficiency of 21.6% obtained on n-type cells, featuring SiO2/TiO2/Al rear contacts and after forming gas annealing (FGA) at 350°C, is due to strong surface passivation of SiO2/TiO2 stack as well as low contact resistivity at the Si/SiO2/TiO2 heterojunction. This can be attributed to the transformation of amorphous TiO2 to a conducting TiO2−x phase. Conversely, the low efficiency (9.8%) obtained on cells featuring an a-Si:H/TiO2/Al rear contact is due to severe degradation of passivation of the a-Si:H upon FGA.

Recently, solution combustion synthetic approach has emerged as a potential route to synthesize a wide range of catalytic oxides. Nano TiO2 was synthesized by solution combustion methods using glycine, urea, and oxalyldihydrazide as fuels. X-ray diffraction and field emission scanning electron microscopy analyses revealed the structural and morphological differences of TiO2 synthesized with different fuels. The oxidizer to fuel ratio from lean to rich conditions also played a crucial role in determining the polymorphic percentage concentration in the synthesized TiO2 powders. However, diffuse reflectance spectroscopy and photoluminescence spectroscopy studies did not show any significant differences in the electronic properties of the synthesized TiO2. As the polymorphic composite phases synergistically influence the catalytic performances, photodegradation of methylene blue (MB) and photo hydrogen production were studied with the synthesized catalysts. The synergistic role crucially depended on the specific reaction. The presence of different TiO2 polymorphs due to difference in fuels during combustion controlled the photocatalytic efficiency of the catalysts toward MB degradation and hydrogen production.

Two novel porphyrins (5,10,15,20-tetra(3-(carboethoxymethyleneoxy)phenyl)porphyrin, H2TEPp and 5,10,15,20-tetra(3-(carboxymethyleneoxy)phenyl)porphyrin, H2TCPp) and their copper(II) porphyrins (CuTEPp, CuTCPp) were synthesized. With these porphyrins, four new porphyrin-sensitized TiO2 nanorod composites (H2TEPp/TiO2, H2TCPp/TiO2, CuTEPp/TiO2, and CuTCPp/TiO2) were prepared and characterized by methods of XRD, SEM, TEM, FT-IR, UV-vis DRS, nitrogen adsorption–desorption and fluorescence spectra. Besides, the photocatalytic activity and stability of the composites were assessed in the degradation of 4-nitrophenol (4-NP). The results indicate that the morphologies and structures of these composites are less influenced by the loaded porphyrins or copper porphyrins compared with the nanorods TiO2 (anatase). The porphyrin or copper porphyrin molecules are confirmed to bond on the surface of TiO2 through carboxyl group, which is beneficial to the electron transfer between porphyrin and TiO2. All composites exhibit enhanced photoactivities compared with the bare TiO2 nanorods. The possible reason is that the recombination of photoproduced electron–hole has been controlled effectively in these composites, which can be seen from their decreased fluorescence emission. The stability results of composites show that they still hold considerable photocatalytic activities after six cycling experiments.

In this study, in situ electrical biasing was combined with transmission electron microscopy (TEM) in order to study the formation and evolution of Wadsley defects and Magnéli phases during electrical biasing and resistive switching in titanium dioxide (TiO2). Resistive switching devices were fabricated from single-crystal rutile TiO2 substrates through focused ion beam milling and lift-out techniques. Defect evolution and phase transformations in rutile TiO2 were monitored by diffraction contrast imaging inside the TEM during electrical biasing. Reversible bipolar resistive switching behavior was observed in these single-crystal TiO2 devices. Biased induced reduction reactions created increased oxygen vacancy concentrations to such an extent that shear faults (Wadsley defects) and oxygen-deficient phases (Magnéli phases) formed over large volumes within the TiO2 TEM specimen. Nevertheless, the observed reversible formation/dissociation of Wadsley defects does not appear to correlate to resistive switching phenomena at these length scales. These defect zones were found to reversibly reconfigure in a manner consistent with charged oxygen vacancy migration responding to the applied bias polarity.

The aim of this research study is to produce high-quality TiO2 nanotube arrays using porous alumina templates. The templates are fabricated through anodizing bulk aluminum foils which can be utilized for the production of thick alumina templates. To produce the nanotube arrays, the alumina template pores are filled with the precursor sol by applying a DC electric field. Then, the deposited nanotubes are heat treated at 320 °C for 2 h and, subsequently, sintered for 2 h at 400 and 750 °C to obtain nanotubes with pure anatase and rutile phases, respectively, as confirmed by x-ray diffraction data. Scanning and transmission electron microscopy (SEM and TEM) investigations show that the nanotubes have been deposited in the channels of the nanoporous alumina template. Also, SEM investigations show the existence of a vast area of TiO2 nanotube arrays when we use semiconductor alumina templates.

TiO2 has attracted tremendous research interest for photocatalytic water splitting, solar hydrogen generation, environmental pollution removal, dye-sensitized solar cells, lithium-ion batteries, supercapacitors, and field emission. Microwave absorption materials (MAMs) play important roles in many military (e.g., the stealth coating on the B-2 bomber) and civil (e.g., telecommunications, noise reduction, information security, signal, and data protection) applications. However, TiO2 is not a good MAM due to its poor absorption in the microwave region. Here, we report that via hydrogenation excellent and tunable microwave absorption is achieved with hydrogenated TiO2 nanocrystals. After hydrogenation, 4.3x and 103x improvements have been obtained in storing and dissipating the electric energy of the microwave electromagnetic field. Their permittivity values are higher than those of the current carbonaceous MAMs. Instead of relying on the dipole rotation or ferromagnetic resonance mechanisms for traditional MAMs, the hydrogenated TiO2 nanocrystals work as good MAMs based on a newly proposed collective-movement-of-interfacial-dipole (CMID) mechanism. Although there is still no direct physical evidence of the interface effects of the CMID mechanism, the CMID as a hypothesis at this point successfully explained the origin of the enhanced microwave absorption of the hydrogenated TiO2 nanoparticles. This study thus may open new applications for TiO2 nanocrystals and also stimulate new approaches for new MAM development.

Aluminum metal matrix hybrid composites were synthesized through powder metallurgy route from ball milled powders to yield the compositions: Al + 0% TiO2, Al + 2.5% TiO2, Al + 2.5% TiO2 + 2% Gr, and Al + 2.5% TiO2 + 4% Gr. The densification and deformation properties of sintered Al–TiO2–Gr composites during cold upsetting were investigated experimentally. The powder preforms are compacted using suitable punch and die in 40 kN hydraulic press and the initial percentage theoretical density was maintained as 85%. Sintering was done in an electric muffle furnace at the temperature of 590 °C for a period of 3 h. The sintered preforms were subjected to incremental compressive loading of 10 kN until cracks were found at the free surface. The true axial stress (σz), true hoop stress (σθ), true hydrostatic stress (σm), and true effective stress (σeff) were calculated for all the preforms and all these stresses are correlated with the true axial strain (εz). The densification behaviors of the composites were studied against true axial strain (εz) and lateral strain. Better densification and deformation property were obtained for pure aluminum preforms compared with other composite preforms. Addition of TiO2 to the pure Al and Gr reinforcements increases the strength coefficient of the Al–TiO2 composite.

Properties of gold nanoparticles (AuNPs) are very different from bulk gold, in particular, highly dispersed AuNPs exhibit high catalytic activities on metal oxide supports. Catalytic activities of AuNPs are strongly dependent on: (i) size and morphology; (ii) synthesis methods; (iii) nature of the support; (iv) interaction between AuNPs and the support; and (v) oxidation state of AuNPs in the synthesized catalysts. A goal is to maintain the size and to prohibit aggregation of AuNPs, since aggregations deteriorate catalytic activities. Some strong interactions are therefore required between AuNPs and their supports to prevent the movement of AuNPs. SBA-15 is a promising material for the support of AuNPs since it has ordered two-dimensional hexagonal pore channels, uniform pore size ranging from 5 to 30 nm, narrow pore size distribution, thick amorphous walls ranging from 3 to 6 nm, and high surface area. In this study, SBA-15, TiO2-SBA-15 and TiO2-SBA-15-AuNP nanocomposites were synthesized by the sol-gel method and microstructural characterizations were carried out by both X-ray diffraction analysis and electron microscopy.

The influence of TiO2 addition to LF refining slag on Ti-stabilized stainlesssteel was evaluated using a vacuum induction furnace at 1873 K. The effect ofCaO-SiO2-MgO-Al2O3 basic slags with different TiO2 contents on the titanium loss,aluminum loss and total oxygen content in the steel was studied. It was observed that theoxidation rate of Ti first decreases and then increases with the increase in the contentof TiO2 in slag andreaches the minimum when 8%TiO2 is added to the slag. However, the change in theoxidation rate of Al shows the opposite tendency. The total oxygen in the molten steelremains unchanged with time when 8%TiO2 is added to the slag, and the total oxygen of theothers increases monotonically with time. The activities of TiO2 and Al2O3 from the calculation of the ionand molecule coexistence theory (IMCT) in the initial slag present the same changetendency, and both first increase and then decrease with the gradual increase inTiO2 in the slagand reach the maximum when 8%TiO2 is added to the slag. The results of a kinetic analysisshowed that the rate-determining step of the oxidation of Ti in the steel is the masstransfer on the slag side, and the rate-determining step of the oxidation of Al in thesteel is the mass transfer on the metal side.

Nanosized anatase TiO2 nanosheets with highly exposed reactive {001} facets (∼80%) were prepared via hydrothermal reaction with the addition of hydrofluoric acid and characterized by various techniques including transmission electron microscopy, x-ray diffraction, x-ray photoelectron spectroscopy, and Brunauer–Emmett–Teller. High-quality TiO2 nanosheets films with different thicknesses (∼5–20 μm) were fabricated by doctor blading, and the effect of film thickness on the performance of dye-sensitized solar cells (DSSCs) was investigated by I-V characterization and dark current potential scan. The results show that each parameter of DSSCs performance depends strongly on the thickness of the TiO2 nanosheets films. An optimized DSSCs performance of 8.39% was obtained by the TiO2nanosheets film with a thickness of ∼15 μm.