Temperature dependence of the lowest frequency <Emphasis Type="BoldItalic">E</Emphasis><Subscript><Emphasis Type="Bold">g</Emphasis></Subscript> Raman mode in laser-synthesized anatase TiO<Subscript>2</Subscript> nanopowder

Nanosized titanium dioxide (TiO₂) powder was prepared by a laser-induced pyrolysis. Specific surface area of the as-grown powder measured by BET method was 109 m²/g. The grain size (14.5 nm) estimated from these data coincides well with the crystallite size (12.3 nm) determined by XRD measurements. The average grain size (∼35 nm) obtained from the subsequent SEM measurements refers to considerable agglomeration of nanoparticles. Raman spectroscopy has been used to investigate the structural properties of TiO₂ nanopowder and its anatase structure is confirmed. The blueshift and broadening of the lowest frequency E_g Raman mode at temperature range ∼25–550 K have been analyzed using a phonon-confinement model. Dominant influence of the strong anharmonic effect at higher temperatures was demonstrated. PACS 81.07.Wx; 78.30.-j; 63.22.+m     

Anodic TiO<Subscript>2</Subscript> nanotubes powder and its application in dye-sensitized solar cells

An increasing energy demand and environmental pollution create a pressing need for clean and sustainable energy solutions. TiO₂ semiconductor material is expected to play an important role in helping solve the energy crisis through effective utilization of solar energy based on photovoltaic devices. Dye-sensitized solar cells (DSSCs) are potentially lower cost alternative to inorganic silicon-based photovoltaic cells. In this study, we report on the fabrication of DSSCs from anodic TiO₂ nanotubes (NT) powder, produced by rapid breakdown potentiostatic anodization of Ti foil in 0.1 M HClO₄ electrolyte, as photoanode. TiO₂ NT powders with a typical NT outer diameter of approximately 40 nm, wall thickness of approximately 8–15 nm, and length of about 20–25 μm, have been synthesized. The counter electrode was made by electrodeposition of Pt from an aqueous solution of 5 mM H₂PtCl₆ onto fluorine-doped tin oxide (FTO) glass substrate. The above front-side illuminated DSSCs were compared with back-side illuminated DSSCs fabricated from anodic TiO₂ NTs that were grown on the top of Ti foil as photoanode. The highest cell efficiency was 3.54% under 100 mW/cm² light intensity (1 sun AM 1.5G light, Jsc = 14.3 mA/cm², Voc = 0.544 V, FF = 0.455). To the best of our knowledge, this is the first report on the fabrication of DSSC from anodic TiO₂ NTs powder. The TiO₂/FTO photoanodes were characterized by FE-SEM, XRD, and UV–Visible spectroscopy. The catalytic properties of Pt/FTO counter electrodes have been examined by cyclic voltammetry.     

Synthesis,characterization of Cr-doped TiO<Subscript>2</Subscript> nanotubes with high photocatalytic activity

Cr-doped TiO₂ nanotubes (Cr/TiO₂ NTs) with high photocatalytic activity were prepared by the combination of sol–gel process with hydrothermal treatment. XRD, TEM and UV–vis DRS techniques were employed for microstructural characterization. TEM images show that Cr/TiO₂ NTs are in good tubular structure and have diameter of about 10 nm. The Cr doping induces the shift of the absorption edge to the visible light range and the narrowing of the band gap. The photocatalytic experiment reveals that the photocatalytic performance of TiO₂ NTs can be improved by the doping of chromium ions.     

Preparation and properties of Zn<Subscript>0.9</Subscript>Ni<Subscript>0.1</Subscript>O diluted magnetic semiconductor nanoparticles

With a view to study the structural, electronic, magnetic, and electrical properties of Zn_0.9Ni_0.1O diluted magnetic semiconductor nanoparticles, systematic investigation has been undertaken. Samples were prepared for the first time by hydrazine-assisted polyol method, and the powders were annealed at various temperatures in order to obtain the samples with different grain sizes. From the Rietveld refined XRD data, lattice parameters, the average crystallite size values, and r.m.s micro-strain values were computed. From the AFM and TEM studies, the average particle sizes were obtained and are found to be in the range 12–46 nm. XPS measurements clearly indicate that the chemical states as +2 for both Zn and Ni ions and are stable with varying annealing temperature. Further, using XPS and optical studies, the electronic structure of the materials was analyzed. A careful phase analysis of the Rietveld refined XRD data (at logarithmic scale) selected area electron diffraction patterns, FTIR, Raman, and XPS studies; it was concluded that all the samples are having hexagonal wurtzite structure without any detectable impurity phases. The optical band gap values are found to exhibit a clear blue shift. The influence of oxygen vacancies on the emission spectra was studied by Photo Luminescence measurement. The magnetization studies were undertaken by VSM, MFM, and FMR techniques and confirmed the presence of clear room temperature ferromagnetism without any magnetic clusters. The carrier concentration (n) values obtained from the thermo power studies are found to decrease with increasing annealing temperature and depend on the local defects which are critically influenced by the annealing temperature and crystallite size of the nanomaterials.     

The magnetic and hyperthermia studies of bare and silica-coated La<Subscript>0.75</Subscript>Sr<Subscript>0.25</Subscript>MnO<Subscript>3</Subscript> nanoparticles

The magnetic nanoparticles of La_0.75Sr_0.25MnO₃ perovskite manganite with a controlled size were prepared via sol–gel procedure, followed by thermal treatment and subsequent mechanical processing of the resulting raw product. The prepared materials were structurally studied by the XRD and TEM methods and probed by DC magnetic measurements. The nanoparticles of the mean crystallite sizes 11–40 nm exhibit T _C in the range of ≈310–347 K and the sample possessing 20-nm crystallites was identified as the most suitable for hyperthermia experiments. In order to obtain a colloidally stable suspension and prevent toxic effects, the selected magnetic cores were further encapsulated into silica shell using tetraethoxysilane. The detailed magnetic studies were focused on the comparison of the raw product, the bare nanoparticles after mechanical processing and the silica-coated nanoparticles, dealing also with effects of size distribution and magnetic interactions. The heating experiments were carried out in an AC field of frequencies 100 kHz–1 MHz and amplitude 3.0–8.9 kA m⁻¹ on water dispersions of the samples, and the generated heat was deduced from their warming rate taking into account experimentally determined thermal losses into surroundings. The experiments demonstrate that the heating efficiency of the coated nanoparticles is generally higher than that of the bare magnetic cores. It is also shown that the aggregation of the bare nanoparticles increases heating efficiency at least in a certain concentration range.     

Thermostable photocatalytically active TiO<Subscript>2</Subscript> anatase nanoparticles

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

Microwave-induced solid-state synthesis of TiO<Subscript>2</Subscript>(B) nanobelts with enhanced lithium-storage properties

A fast and economical route based on an efficient microwave-induced solid-state process has been developed to synthesize metastable TiO₂(B) nanobelts with widths of 30–100 nm and lengths up to a few micrometers on a large scale. This new method reduces the synthesis time for the preparation of TiO₂(B) nanobelts to less than half an hour, allowing the screening of a wide range of reaction conditions for optimizing and scaling up the production and facilitating the formation of metastable phase TiO₂(B). The as-formed TiO₂(B) nanobelts exhibit enhanced lithium-storage performances, compared with the TiO₂(B) product obtained by the conventional heating. This study provides a new way for large-scale industrial production of high-quality metastable TiO₂(B) nanostructures. The products were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and Raman spectroscopy.     

TiO<Subscript>2</Subscript> nanotube height effect on the efficiency of dye-sensitized solar cells

Performance of dye-sensitized solar cells (DSSCs) based on TiO₂ nanotubes (NTs) filled with TiO₂ nanoparticles (NPs) was studied as a function of NT height (h). The NT height was varied in the range of 1.5–7.0 μm, while the NT diameter was kept constant at ~80 nm. The studies showed that DSSC efficiency, current density, and fill factor linearly increased with h and ranged in 1.76–6.5%, 3.62–13.2 mA/cm², and 0.66–0.76, respectively, within the h range studied. The electrochemical impedance spectroscopy was also performed to study DSSC electron transport properties. Based on both photovoltaic and electrochemical impedance spectroscopy data, the results were explained as being due to the increased dye loading that led to higher light-harvesting efficiency.     

Nanoparticles dispersion in processing functionalised PP/TiO<Subscript>2</Subscript> nanocomposites: distribution and properties

Future innovations in textiles and fibrous materials are likely to demand fibres with enhanced multifunctionality. The fibres can be functionalized by dispersing nanoadditives into the polymer during melt compounding/spinning. TiO₂ nanoparticles have the potential to improve UV resistance, antistatic, as well as impart self-cleaning by photocatalysis and thereby de-odour and antimicrobial effects. In this study, a micro-lab twin-screw extruder was used to produce samples of polypropylene (PP) nanocomposite monofilaments, doped with nano titanium oxide (TiO₂)/manganese oxide (MnO) compound having size ranging from 60 to 200 nm. As a control sample, PP filaments without additives were also extruded. Three samples were produced containing different concentrations (wt%) of the TiO₂ compound, i.e. 0.95, 1.24 and 1.79%. Nano metal-oxide distribution in the as-spun and drawn nanocomposite filaments was analysed. Although, there are small clusters of the nanoparticles, the characterizing techniques showed good dispersion and distribution of the modified TiO₂ along and across the processed filaments. From UV spectroscopy and TGA, a significant enhancement of polypropylene UV protection and thermal stability were observed: PP with higher percentage of TiO₂ absorbed UV wavelength of 387 nm and thermally decomposed at 320.16 °C accompanied by 95% weight loss.     

Fabrication and characterization of CdS-sensitized TiO<Subscript>2</Subscript> nanotube photoelectrode

CdS quantum dot (Qd)-sensitized TiO₂ nanotube array photoelectrode is synthesised via a two-step method on tin-doped In₂O₃-coated (ITO) glass substrate. TiO₂ nanotube arrays are prepared in the ethylene glycol electrolyte solution by anodizing titanium films which are deposited on ITO glass substrate by radio frequency sputtering. Then, the CdS Qds are deposited on the nanotubes by successive ionic layer adsorption and reaction technique. The resulting nanotube arrays are characterized by scanning electron microscopy, X-ray diffraction (XRD) and UV–visible absorption spectroscopy. The length of the obtained nanotubes reaches 1.60 μm and their inner diameter and wall thickness are around 90 and 20 nm, respectively. The XRD results show that the as-prepared TiO₂ nanotubes array is amorphous, which are converted to anatase TiO₂ after annealed at 450 °C for 2 h. The CdS Qds deposited on the TiO₂ nanotubes shift the absorption edge of TiO₂ from 388 to 494 nm. The results show that the CdS-sensitized TiO₂ nanotubes array film can be used as the photoelectrode for solar cells.     

Biological impacts of TiO<Subscript>2</Subscript> on human lung cell lines A549 and H1299: particle size distribution effects

Increasing use of titanium dioxide (TiO₂) nanoparticles in many commercial applications has led to emerging concerns regarding the safety and environmental impact of these materials. In this study, we have investigated the biological impact of nano-TiO₂ (with particle primary size of 20 nm Aeroxide P25) on human lung cell lines in vitro and also the effect of particle size distribution on the particle uptake and apparent toxicity. The biological impact of nano-TiO₂ is shown to be influenced by the concentration and particle size distribution of the TiO₂ and the impact was shown to differ between the two cell lines (A549 and H1299) investigated herein. A549 cell line was shown to be relatively resistant to the total amount of TiO₂ particles uptaken, as measured by cell viability and metabolic assays, while H1299 had a much higher capacity to ingest TiO₂ particles and aggregates, with consequent evidence of impact at concentrations as low as 30–150 μg/mL TiO₂. Evidence gathered from this study suggests that both viability and metabolic assays (measuring metabolic and mitochondrial activities and also cellular ATP level) should be carried out collectively to gain a true assessment of the impact of exposure to TiO₂ particles.     

Polyol-assisted synthesis of TiO2 nanoparticles in a semi-aqueous solvent

TiO₂ (anatase and rutile) nanoparticles with an average crystallite size of 20-40 nm have been prepared at room temperature by polyol-mediated synthesis technique in a semi-aqueous solvent medium using titanium iso-propoxide as the titanium source, acetone as the oil phase and ethylene glycol as the stabilizer. Phase and microstructure of the resultant materials have been characterized by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy and Raman spectroscopy. Photocatalytic degradation of acetaldehyde using TiO₂ nanoparticles was investigated by gas-chromatography technique.     

Magnetic and dielectric properties of Mn<Subscript>0.2</Subscript>Ni<Subscript>0.8</Subscript>Fe<Subscript>2</Subscript>O<Subscript>4</Subscript> nanoparticles synthesized by PEG-assisted hydrothermal method

We present a systematic investigation on the structural and magnetic properties of Mn_0.2Ni_0.8Fe₂O₄ nanoparticles synthesized by a polyethylene glycol (PEG)-assisted hydrothermal route. XRD, FT-IR, TEM and VSM were used for the structural, morphological, dielectric properties and magnetic investigation of the products, respectively. Average crystallite size of product was estimated using Line profile fitting as 6 ± 1 nm and particle size as 6.5 ± 1.0 nm from TEM micrographs. Magnetization measurements have shown that the particles have a blocking temperature of 134 K. Magnetization and the coercive field of the sample increase by decreasing the temperature. The conductivity measurements reveal the semiconducting behaviour for the sample. Temperature-dependent dielectric properties: dielectric permittivity (ε) and ac conductivity (σ_ac) for the sample were studied as a function of applied frequency in the range from 1 Hz to 3 MHz. These studies indicated that the dielectric dispersion curve for the sample showed usual dielectric dispersion which can be explained on the basis of Koop’s theory, which is based on the Maxwell–Wagner model for the interfacial polarization of homogeneous double structure.     

Growth of AgInSe<Subscript>2</Subscript> on Si(100) substrate by thermal evaporation technique

AgInSe₂ films were prepared by a thermal evaporation technique onto Si(100) substrates at a pressure of 10⁻⁵ mbar. Structural and optical properties of films deposited at 300 and 473 K have been investigated. The film composition was studied by energy dispersive analysis through X-rays. X-ray diffraction patterns indicate that AgInSe₂ films have chalcopyrite structure with strong preferred orientation in the (112) direction. Average vertical crystallite size of 25 nm was observed. The optical energy gaps of 1.20 and 1.90 eV were obtained due to the fundamental absorption edge and a transition originating from crystal field splitting, respectively. Field emission scanning electron microscopy shows loosely packed grains of spherical symmetry with some facets.     

Kinetics of the plasmon optical response of Au nanoparticles/TiO<Subscript>2</Subscript> catalyst under O<Subscript>2</Subscript> and H<Subscript>2</Subscript> followed by differential diffuse reflectance spectroscopy

The changes in the optical properties of Au/TiO₂ powder catalyst, prepared by the deposition-precipitation method, are measured in the visible range by use of a home-made diffuse differential reflectance spectrometer, when the ambient atmosphere is switched between H₂ and O₂. Two main features are observed: (i) a short wavelength one, located between 400 and 600 nm, is shown to be related to the modifications of the plasmon resonance of the 3-dimensional metallic gold particles with mean size around 4 nm, induced by the exposure to oxygen or by its removal; (ii) a second feature, observed at long wavelengths between 600 and 1100 nm, is extremely sensitive to the exposure to oxygen. This optical feature could be due to the presence in the catalyst, either of Au⁰ clusters of several tens atoms, which are expected to display molecular-like transitions in this optical range, or to specific sites of the Au particles (edge atoms or peripheral atoms at the interface with the TiO₂ support), which could be highly reactive to oxygen.     

Study of mechanochemically prepared nanocrystalline La<Subscript>0.8</Subscript>Sr<Subscript>0.2</Subscript>MnO<Subscript>3</Subscript>

The nanocrystalline La_0.8Sr_0.2MnO₃ (LSM) is prepared by varying the revolutions per minute and milling time of planetary monomill during the mechanochemical method. The LSM forms in a relatively shorter milling time with an increase in the milling speed from 250 to 600 rpm. The structural phase transition from orthorhombic to rhombohedral phase in the LSM prepared by ball milling at the speed 250 rpm for 36 h is seen due to sintering it at 700 °C for 4 h. The crystallite size reduces with the increase in both the milling speed and the milling time individually or combined. The microhardness (HV) and sintered density increase with the reduction in the crystallite size. The temperature-activated transition temperature is suppressed by reducing the grain size in the nanometer range. The electrical dc conductivity increases with the reduction in the grain/crystallite size.     

Experimental and statistical analysis of dielectric barrier discharge plasma effect on sonochemically TiO2 coated cotton fabric using complete composite design

A single step ultrasonic biosynthesis method was used to synthesize and coat TiO₂ nanoparticles onto DBD plasma functionalized raw cotton. Titanium isopropoxide was reduced with aloe vera plant extract into TiO₂ nanoparticles. The effect of DBD plasma treatment on self-cleaning property of TiO₂ coated fabric was optimized statistically by using a complete composite design. To induce functional groups on the cotton fabric surface, the fabric was pre-treated with DBD plasma over various periods of time. The plasma exposure time, molarity of solution and ultrasonication time were optimized using complete composite design package. TiO₂ nanoparticles revealed spherical shape and anatase phase with average crystallite size of 10.46 nm. The statistically optimized plasma exposure time, molarity and sonication time was 7 min, 0.80 and 75 min, respectively. The plasma activation of fabric significantly improved the adsorption, tensile strength and self-cleaning ability of TiO₂ coated fabric.     

Methane sensor based on SnO<Subscript>2</Subscript>/In<Subscript>2</Subscript>O<Subscript>3</Subscript>/TiO<Subscript>2</Subscript> nanostructure

Two sets of samples of SnO₂/In₂O₃/TiO₂ system have been fabricated with different concentrations of component materials. In the first set TiO₂ with rutile structure was used, while in the second set it has the structure of anatase. Thin films (up to 50 nm) of obtained mixtures were deposited. Their sensitivity and selectivity with respect to methane (CH4) were studied. Nanostructure on the basis of 70%SnO₂ — 10%In₂O₃ — 20%TiO₂(anatase) exhibits sufficient sensitivity to methane.     

Peroxide-based route assisted with inverse microemulsion process to well-dispersed Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> nanocrystals

Well-dispersed bismuth titanate (BIT) nanocrystals with an average size ranged from 3 to 60 nm were synthesized via a peroxide-based route assisted with an inverse microemulsion process. The crystallite size and lattice parameter of BIT upon variable-temperature were determined by X-ray diffraction (XRD). The particle size was confirmed by transmission electron microscopy (TEM). Thermal decomposition behaviour of Ti-peroxy and BIT gel and crystallization kinetics of BIT nanocrystals were investigated by differential scanning calorimetry/thermogravimetry (DSC/TG) and Fourier-Transform infrared spectroscopy (FTIR). Analysis of nonisothermal DSC data yielded a value of 220.84 ± 2.73 KJ/mol and 2.25 ± 0.26 for the activation energy of crystallization (E _a) and the Avrami exponent (n), respectively.     

Photoconductivity studies on amorphous and crystalline TiO<Subscript>2</Subscript> films doped with gold nanoparticles

In this work, amorphous and crystalline TiO₂ films were synthesized by the sol–gel process at room temperature. The TiO₂ films were doped with gold nanoparticles. The films were spin-coated on glass wafers. The crystalline samples were annealed at 100°C for 30 minutes and sintered at 520°C for 2 h. All films were characterized using X-ray diffraction, transmission electronic microscopy and UV-Vis absorption spectroscopy. Two crystalline phases, anatase and rutile, were formed in the matrix TiO₂ and TiO₂/Au. An absorption peak was located at 570 nm (amorphous) and 645 nm (anatase). Photoconductivity studies were performed on these films. The experimental data were fitted with straight lines at darkness and under illumination at 515 nm and 645 nm. This indicates an ohmic behavior. Crystalline TiO₂/Au films are more photoconductive than the amorphous ones.