Effect of hydrothermal growth temperature on structural and optical properties of TiO2 nanoparticles

TiO₂ nanoparticles have been prepared by hydrothermal method at different temperatures. The X-ray diffraction results showed that anatase TiO₂ nanoparticles with grain size in the range of 7–27 nm has been obtained. HRTEM images show the formation of TiO₂ nanoparticles with grain size ranging from 7 to 26 nm. The Raman spectra exhibited peaks corresponding to the anatase phase of TiO₂. Optical absorption studies reveal that the absorption edge shifts towards longer wavelength (red shift) with increasing hydrothermal temperature.     

Preparation of anatase TiO2 thin films by vacuum arc plasma evaporation

Anatase titanium dioxide (TiO₂) thin films with high photocatalytic activity have been prepared with deposition rates as high as 16 nm/min by a newly developed vacuum arc plasma evaporation (VAPE) method using sintered TiO₂ pellets as the source material. Highly transparent TiO₂ thin films prepared at substrate temperatures from room temperature to 400 °C exhibited photocatalytic activity, regardless whether oxygen (O₂) gas was introduced during the VAPE deposition. The highest photocatalytic activity and photo-induced hydrophilicity were obtained in anatase TiO₂ thin films prepared at 300 °C, which correlated to the best crystallinity of the films, as evidenced from X-ray diffraction. In addition, a transparent and conductive anatase TiO₂ thin film with a resistivity of 2.6 × 10^− 1 Ω cm was prepared at a substrate temperature of 400 °C without the introduction of O₂ gas.     

An All Low‐Temperature Fabrication of Macroporous,Electrochemically Addressable Anatase Thin Films

Macroporous TiO₂ (anatase) thin films are fabricated by an all low‐temperature process in which substrates are dip‐coated in suspensions of mixed anatase nanoparticles and polystyrene beads, and the templating agents are removed by ultraviolet (UV) irradiation at a temperature below 50 °C. Scanning electron microscopy (SEM) and Raman spectroscopy show that the templating polymer beads are removed by UV irradiation combined with the photocatalytic activity of TiO₂. X‐Ray diffraction reveals that nanoparticle growth is negligible in UV irradiated films, while nanoparticle size increases by almost 10 times in calcined films that are prepared for comparison. The macroporous films are prepared on FTO‐(fluorine‐doped tin oxide) coated glass and ITO (indium tin oxide) coated flexible plastics and thereby used as working electrodes. In both cases, the films are electrochemically addressable, and cyclic voltammetry is consistent with the response of bulk TiO₂ for calcined films and of nanoscale‐TiO₂ for UV‐irradiated films.     

Innovative one-step immobilization of TiO2 on polymer material by the sol–gel method under IL/MW conditions

An innovative one-step immobilization of titanium dioxide (TiO₂) nano-particles on organic polymer (PMMA) substrate at ambient condition is reported in this article. This immobilization can be achieved by the sol–gel method under ionic liquid/microwave heating conditions. In this method, a sol–gel reaction is conducted at specific sites of the polymer surface. These sites are the tiny cavities of the rough surface resulting from the softening and swelling effect of an alcohol, such as isopropyl alcohol, on the polymer surface under microwave irradiation. The roughness of the polymer surface is an important factor for the effective immobilization. In addition, ionic liquid can induce low temperature surface anatase crystallization of immobilized titanium dioxide in a short time. From the field emission scanning electron microscopy and energy dispersive spectroscopy observation, the TiO₂ particles could be effectively immobilized on the PMMA substrate. Raman spectra analysis data showed that the immobilized TiO₂ was anatase phase. The experimental data also shows that the immobilized TiO₂ prepared by this novel method has good immobilization stability and photocatalytic water treatment performance.     

PANI/TiO2 nanocomposite‐based chemiresistive gas sensor for the detection of E. Coli bacteria

In the modern pace of the world, food safety is a major concern. In this work, a simple chemiresistive type gas sensor was fabricated to detect Escherichia Coli (E. coli) bacteria. Polyaniline (PANI) films were deposited on the indium tin oxide substrate by an electrochemical deposition method. TiO₂ nanoparticles were synthesised by facile hydrothermal method. PANI films were modified using hydrothermally prepared TiO₂ nanoparticles by a spin coating method. X‐ray diffraction (XRD), field emission scanning electron microscope (FESEM), Fourier transform infrared (FTIR) and ultraviolet– visible spectrophotometer techniques were used to characterise the PANI/TiO₂ nanocomposites. The peaks obtained in the XRD pattern confirmed the anatase phase of TiO₂ nanoparticles. FESEM analysis showed the nanofibrous structure of the nanocomposite. The FTIR characteristic peaks confirmed the formation of the nanocomposite. The electrical resistance of the sensors was evaluated as a function of the bacterial concentration. The PT2 (TiO₂ coated 5 times on PANI) in comparison with PT1 (TiO₂ coated 3 times on PANI) exhibited good sensitivity to the gas molecules at room temperature. The p‐n junction at PANI/TiO₂ interface improved the physical adsorption of gas molecules. Since no specific antibodies or receptors are used, the sensor has the potential for adaptation to real‐life applications. Thus low cost, real‐time, portable, reusable and sensitive bacteria sensors were fabricated and tested.Inspec keywords: conducting polymers, nanoparticles, nanocomposites, visible spectra, ultraviolet spectra, microorganisms, nanosensors, adsorption, gas sensors, nanofabrication, nanofibres, X‐ray diffraction, titanium compounds, spin coating, field emission scanning electron microscopy, Fourier transform infrared spectra, polymer films, electrodeposition, electrical resistivity, wide band gap semiconductors, biological techniques, nanobiotechnologyOther keywords: simple chemiresistive type gas sensor, polyaniline films, indium tin oxide substrate, electrochemical deposition method, TiO₂ nanoparticles, facile hydrothermal method, PANI films, spin coating method, gas molecules, portable bacteria sensors, reusable bacteria sensors, sensitive bacteria sensors, PANI‐TiO₂ nanocomposite‐based chemiresistive gas sensor, Escherichia Coli bacteria detection, X‐ray diffraction, XRD, field emission scanning electron microscopy, FESEM, Fourier transform infrared spectra, FTIR spectra, ultraviolet‐visible spectra, anatase phase, nanofibrous structure, electrical resistance, bacterial concentration, p‐n junction, physical adsorption, temperature 293.0 K to 298.0 K, TiO₂ , ITO     

Toxicological Aspects of Long‐Term Treatment of Keratinocytes with ZnO and TiO2 Nanoparticles

Sunscreens containing ZnO and TiO₂ nanoparticles (NPs) are increasingly applied to skin over long time periods to reduce the risk of skin cancer. However, long‐term toxicological studies of NPs are very sparse. The in vitro toxicity of ZnO and TiO₂ NPs on keratinocytes over short‐ and long‐term applications is reported. The effects studied are intracellular formation of radicals, alterations in cell morphology, mitochondrial activity, and cell‐cycle distribution. Cellular response depends on the type of NP, concentration, and exposure time. ZnO NPs have more pronounced adverse effects on keratinocytes than TiO₂. TiO₂ has no effect on cell viability up to 100 μg mL^?1, whereas ZnO reduces viability above 15 μg mL^?1 after short‐term exposure. Prolonged exposure to ZnO NPs at 10 μg mL^?1 results in decreased mitochondrial activity, loss of normal cell morphology, and disturbances in cell‐cycle distribution. From this point of view TiO₂ has no harmful effect. More nanotubular intercellular structures are observed in keratinocytes exposed to either type of NP than in untreated cells. This observation may indicate cellular transformation from normal to tumor cells due to NP treatment. Transmission electron microscopy images show NPs in vesicles within the cell cytoplasm, particularly in early and late endosomes and amphisomes. Contrary to insoluble TiO₂, partially soluble ZnO stimulates generation of reactive oxygen species to swamp the cell redox defense system thus initiating the death processes, seen also in cell‐cycle distribution and fluorescence imaging. Long‐term exposure to NPs has adverse effects on human keratinocytes in vitro, which indicates a potential health risk.     

Low‐Temperature In Situ Amino Functionalization of TiO2 Nanoparticles Sharpens Electron Management Achieving over 21% Efficient Planar Perovskite Solar Cells

Titanium oxide (TiO₂) has been commonly used as an electron transport layer (ETL) of regular‐structure perovskite solar cells (PSCs), and so far the reported PSC devices with power conversion efficiencies (PCEs) over 21% are mostly based on mesoporous structures containing an indispensable mesoporous TiO₂ layer. However, a high temperature annealing (over 450 °C) treatment is mandatory, which is incompatible with low‐cost fabrication and flexible devices. Herein, a facile one‐step, low‐temperature, nonhydrolytic approach to in situ synthesizing amino‐functionalized TiO₂ nanoparticles (abbreviated as NH₂‐TiO₂ NPs) is developed by chemical bonding of amino (‐NH₂) groups, via Ti? N bonds, onto the surface of TiO₂ NPs. NH₂‐TiO₂ NPs are then incorporated as an efficient ETL in n‐i‐p planar heterojunction (PHJ) PSCs, affording PCE over 21%. Cs_0.05FA_0.83MA_0.12PbI_2.55Br_0.45 (abbreviated as CsFAMA) PHJ PSC devices based on NH₂‐TiO₂ ETL exhibit the best PCE of 21.33%, which is significantly higher than that of the devices based on the pristine TiO₂ ETL (19.82%) and is close to the record PCE for devices with similar structures and fabrication procedures. Besides, due to the passivation of the surface trap states of perovskite film, the hysteresis of current–voltage response is significantly suppressed, and the ambient stability of devices is improved upon amino functionalization.     

Synthesis of titanium dioxide nanoparticles by reactive DC magnetron sputtering

Nanometer-sized titanium dioxide (TiO₂) particles were prepared on carbon substrates by reactive direct-current magnetron sputtering. By performing measurements with high resolution electron microscopes, the mean nanoparticle diameter and the coverage fraction of the substrate by the nanoparticles (NPs) were measured at 19 nm and 30%, respectively. Moreover, electron diffraction analysis showed that the TiO₂ NPs' crystalline structure on the carbon substrate was a mixture of anatase and rutile. Finally, we provided information on the TiO₂ initial growth stage: crystalline NPs were formed after deposition of amorphous nanoparticles on the substrate and heating.     

Vapor‐Phase Hydrothermal Transformation of HTiOF3 Intermediates into {001} Faceted Anatase Single‐Crystalline Nanosheets

For the first time, a facile, one‐pot hydrofluoric acid vapor‐phase hydrothermal (HF‐VPH) method is demonstrated to directly grow single‐crystalline anatase TiO₂ nanosheets with 98.2% of exposed {001} faceted surfaces on the Ti substrate via a distinctive two‐stage formation mechanism. The first stage produces a new intermediate crystal (orthorhombic HTiOF₃) that is transformed into anatase TiO₂ nanosheets during the second stage. The findings reveal that the HF‐VPH reaction environment is unique and differs remarkably from that of liquid‐phase hydrothermal processes. The uniqueness of the HF‐VPH conditions can be readily used to effectively control the nanostructure growth.     

Multichannel Porous TiO2 Hollow Nanofibers with Rich Oxygen Vacancies and High Grain Boundary Density Enabling Superior Sodium Storage Performance

TiO₂ as an anode for sodium‐ion batteries (NIBs) has attracted much recent attention, but poor cyclability and rate performance remain problematic owing to the intrinsic electronic conductivity and the sluggish diffusivity of Na ions in the TiO₂ matrix. Herein, a simple process is demonstrated to improve the sodium storage performance of TiO₂ by fabricating a 1D, multichannel, porous binary‐phase anatase‐TiO₂–rutile‐TiO₂ composite with oxygen‐deficient and high grain‐boundary density (denoted as a‐TiO_2?x /r‐TiO_2?x ) via electrospinning and subsequent vacuum treatment. The introduction of oxygen vacancies in the TiO₂ matrix enables enhanced intrinsic electronic conductivity and fast sodium‐ion diffusion kinetics. The porous structure offers easy access of the liquid electrolyte and a short transport path of Na⁺ through the pores toward the TiO₂ nanoparticle. Furthermore, the high density of grain boundaries between the anatase TiO₂ and rutile TiO₂ offer more interfaces for a novel interfacial storage. The a‐TiO_2?x /r‐TiO_2?x shows excellent long cycling stability (134 mAh g^?1 at 10 C after 4500 cycles) and superior rate performance (93 mAh g^?1 after 4500 cycles at 20 C) for sodium‐ion batteries. This simple and effective process could serve as a model for the modification of other materials applied in energy storage systems and other fields.     

The study of the effect of external additives on the synthesis of fumed TiO2 with a high content of rutile structure by the novel natural dropping thermal treatment

The effect of external additives on the synthesis of fumed TiO₂ with a high rutile structure content was studied. The focus of this investigation was on the external additive species, agglomerates of the fumed TiO₂ before and after the thermal treatment. The transformation ratio from the anatase to rutile structure of the thermally-treated fumed TiO₂ was investigated as a function of the fumed TiO₂ agglomerate before the thermal treatment. Small agglomerated powders resulted in a decrease of transformation temperature. Two novel results were obtained in this investigation. One was a new fumed TiO₂ with a 100% rutile structure having an excellent dispersibility being successfully synthesized by the thermal treatment of AEROXIDE® TiO₂ P 25 with a small portion of AEROSIL® R 972. The other was the remarkable acceleration of the transformation from the anatase to rutile structure and grain growth/sintering of the thermally-treated fumed TiO₂ observed at a relatively low thermal treatment temperature by the oxidation reaction of calcium stearate as an external additive.     

Foodborne Titanium Dioxide Nanoparticles Induce Stronger Adverse Effects in Obese Mice than Non‐Obese Mice: Gut Microbiota Dysbiosis,Colonic Inflammation,and Proteome Alterations

The recent ban of titanium dioxide (TiO₂) as a food additive (E171) in France intensified the controversy on safety of foodborne‐TiO₂ nanoparticles (NPs). This study determines the biological effects of TiO₂ NPs and TiO₂ (E171) in obese and non‐obese mice. Oral consumption (0.1 wt% in diet for 8 weeks) of TiO₂ (E171, 112 nm) and TiO₂ NPs (33 nm) does not cause severe toxicity in mice, but significantly alters composition of gut microbiota, for example, increased abundance of Firmicutes phylum and decreased abundance of Bacteroidetes phylum and Bifidobacterium and Lactobacillus genera, which are accompanied by decreased cecal levels of short‐chain fatty acids. Both TiO₂ (E171) and TiO₂ NPs increase abundance of pro‐inflammatory immune cells and cytokines in the colonic mucosa, indicating an inflammatory state. Importantly, TiO₂ NPs cause stronger colonic inflammation than TiO₂ (E171), and obese mice are more susceptible to the effects. A microbiota transplant study demonstrates that altered fecal microbiota by TiO₂ NPs directly mediate inflammatory responses in the mouse colon. Furthermore, proteomic analysis shows that TiO₂ NPs cause more alterations in multiple pathways in the liver and colon of obese mice than non‐obese mice. This study provides important information on the health effects of foodborne inorganic nanoparticles.     

Photocatalytic Evidence of the Rutile‐to‐Anatase Electron Transfer in Titania

Layered anatase‐rutile titania thin‐films were synthesized via atmospheric‐pressure chemical vapor deposition and characterized using X‐ray diffraction, Raman spectroscopy and electron microscopy. The interposition of an amorphous TiO₂‐based interlayer allowed direct vapor deposition of anatase on a rutile substrate, which is otherwise hindered by templating. This resourceful approach and the subsequent crystallization of the amorphous layer after annealing of the films allowed investigation on the impact of an efficient interface of the two anatase‐rutile phases in the photodegradation of a model organic pollutant. Clear evidence is presented on the synergy between the two polymorphs and more importantly, on the charge flow across the interface, which, against much conventional understanding, it involves electron transfer from rutile to anatase and is in agreement with a recent theoretical model and electron paramagnetic resonance data. Here, an increasing density of trapped electrons on the anatase surface of the A/R film is confirmed by photoreduction of silver. This observation is attributed to a defect‐free efficient contact between the two phases and the presence of small rutile particles that promote rapid electron transfer at the A‐R interface of the films.     

Rutile Nanorod/Anatase Nanowire Junction Array as Both Sensor and Power Supplier for High‐Performance,Self‐Powered,Wireless UV Photodetector

Self‐powered UV photodetectors based on TiO₂ nanotree arrays have captured much attention in recent years because of their many advantages. In this work, rutile/anatase TiO₂ (R/A‐TiO₂) heterostructured nanotree arrays are fabricated by assembling anatase nanowires as branches on rutile nanorods. External quantum efficiencies as high as 90% are reached at 325 nm. These high quantum efficiencies are related to the higher amount of light harvesting due to the larger surface area, the better separation ability of the photogenerated carriers by the rutile/anatase heterostructure, and the faster electron transport, related to the 1D nanostructure and lattice connection at the interface of the two kinds of TiO₂. Furthermore, a self‐powered wireless UV photodetector is shown with excellent wireless detection performance. Such devices will enable significant advances for next‐generation photodetection and photosensing applications.     

Preparation and photocatalytic activity of anatase TiO2 nanocrystallites with high thermal stability

Anatase TiO₂ nanocrystallites were prepared from TiCl₄ with addition of aqueous ammonia by changing Ti(OH)₄ hydrogel into its corresponding alcogel followed by supercritical drying in ethanol medium. The as-prepared TiO₂ was characterized by XRD, TG and BET. The results show that the prepared anatase TiO₂ has remarkable high thermal stability. The anatase structure of the prepared TiO₂ is maintained even after calcination up to temperatures as high as 800 °C. The photocatalytic activity of the prepared TiO₂ calcined at 800 °C in degradation of reactive brilliant red X-3B is comparable to commercially available nanosized P25 TiO₂.     

Photocatalytic activities of TiO2 thin films prepared on Galvanized Iron substrate by plasma-enhanced atomic layer deposition

Titanium dioxide (TiO₂) thin films were prepared on Galvanized Iron (GI) substrate by plasma-enhanced atomic layer deposition (PE-ALD) using tetrakis-dimethylamido titanium and O₂ plasma to investigate the photocatalytic activities. The PE-ALD TiO₂ thin films exhibited relatively high growth rate and the crystal structures of TiO₂ thin films depended on the growth temperatures. TiO₂ thin films deposited at 200 °C have amorphous phase, whereas those with anatase phase and bandgap energy about 3.2 eV were deposited at growth temperature of 250 °C and 300 °C. From contact angles measurement of water droplet, TiO₂ thin films with anatase phase and Activ™ glass exhibited superhydrophilic surfaces after UV light exposure. And from photo-induced degradation test of organic solution, anatase TiO₂ thin films and Activ™ glass decomposed organic solution under UV illumination. The anatase TiO₂ thin film on GI substrate showed higher photocatalytic efficiency than Activ™ glass after 5 h UV light exposure. Thus, we suggest that the anatase phase in TiO₂ thin film contributes to both superhydrophilicity and photocatalytic decomposition of 4-chlorophenol solution and anatase TiO₂ thin films are suitable for self-cleaning applications.     

Synthesis and characterization of CdS doped TiO2 nanocrystalline powder: A spectroscopic study

This report aimed to study the effect of CdS doping in TiO₂ on the phase transformation of TiO₂ from anatase to rutile using X-ray diffraction (XRD) and Raman spectroscopy. CdS-doped TiO₂ nanocomposites have been prepared and characterized using Fourier transform infrared spectroscopy (FTIR) and transmission electron microscopy (TEM). We have observed that contrary to bare TiO₂, phase transformation of TiO₂ from anatase to rutile is hindered when doped with CdS at high temperature. Raman spectroscopy is found to be more sensitive for detection of the surface of TiO₂ as compared to XRD.     

Influence of high velocity oxy-fuel parameters on properties of nanostructured TiO<Subscript>2</Subscript> coatings

A liquid fuel high velocity oxy-fuel (HVOF) thermal spray process has been used to deposit TiO₂ nanostructured coatings utilizing a commercially available nanopowder as the feedstock. The coatings were characterized by means of X-ray diffraction analysis (XRD), scanning electron microscopy (SEM) and transmission electron microscope (TEM), respectively. Photocatalytic activity was evaluated as a rate constant of decomposition reaction of methylene blue (MB) determined from the changes of relative concentration of MB with UV irradiation time. The results indicate that the sprayed TiO₂ coatings were composed of both TiO₂ phases viz. anatase and rutile, with different phase contents and crystallite sizes. A high anatase content of 80% by volume was achieved at 0·00015, fuel-to-oxygen ratio with nanostructure coating by grain size smaller than feedstock powder. Photocatalytic activity evaluation results indicated that all the TiO₂ coatings are effective to degradation MB under UV radiation and their activities differ in different spray conditions. It is found that fuel flow rate strongly influenced on phase transformation of anatase to rutile and by optimizing the rate which can promote structural transformation and grain coarsening in coating and improving photocatalytic activity.     

Self-assembly and photocatalysis of mesoporous TiO2 nanocrystal clusters

Mesoporous nanocrystal clusters of anatase TiO₂ with large surface area and enhanced photocatalytic activity have been successfully synthesized. The synthesis involves the self-assembly of hydrophobic TiO₂ nanocrystals into submicron clusters, coating of these clusters with a silica layer, thermal treatment to remove organic ligands and improve the crystallinity of the clusters, and finally removing silica to expose the mesoporous catalysts. With the help of the silica coating, the clusters not only maintain their small grain size but also keep their mesoporous structure after calcination at high temperatures (with BET surface area as high as 277 m²/g). The etching of SiO₂ also results in the clusters having high dispersity in water. We have been able to identify the optimal calcination temperature to produce TiO₂ nanocrystal clusters that possess both high crystallinity and large surface area, and therefore show excellent catalytic efficiency in the decomposition of organic molecules under illumination by UV light. Convenient doping with nitrogen converts these nanocrystal clusters into active photocatalysts in both visible light and natural sunlight. The strategy of forming well-defined mesoporous clusters using nanocrystals promises a versatile and useful method for designing photocatalysts with enhanced activity and stability.     

WO3 Nanofiber‐Based Biomarker Detectors Enabled by Protein‐Encapsulated Catalyst Self‐Assembled on Polystyrene Colloid Templates

A novel catalyst functionalization method, based on protein‐encapsulated metallic nanoparticles (NPs) and their self‐assembly on polystyrene (PS) colloid templates, is used to form catalyst‐loaded porous WO₃ nanofibers (NFs). The metallic NPs, composed of Au, Pd, or Pt, are encapsulated within a protein cage, i.e., apoferritin, to form unagglomerated monodispersed particles with diameters of less than 5 nm. The catalytic NPs maintain their nanoscale size, even following high‐temperature heat‐treatment during synthesis, which is attributed to the discrete self‐assembly of NPs on PS colloid templates. In addition, the PS templates generate open pores on the electrospun WO₃ NFs, facilitating gas molecule transport into the sensing layers and promoting active surface reactions. As a result, the Au and Pd NP‐loaded porous WO₃ NFs show superior sensitivity toward hydrogen sulfide, as evidenced by responses (R_air/R_gas) of 11.1 and 43.5 at 350 °C, respectively. These responses represent 1.8‐ and 7.1‐fold improvements compared to that of dense WO₃ NFs (R_air/R_gas = 6.1). Moreover, Pt NP‐loaded porous WO₃ NFs exhibit high acetone sensitivity with response of 28.9. These results demonstrate a novel catalyst loading method, in which small NPs are well‐dispersed within the pores of WO₃ NFs, that is applicable to high sensitivity breath sensors.