Synthesis and characterization of TiO2-doped Polyaniline nanocomposites by chemical oxidation method

Polyaniline (PANI)/TiO₂ nanocomposite samples with various dopant percentages of TiO₂ were synthesized at room temperature using a chemical oxidative method. The samples were characterized by ultraviolet-visible spectrometer, Fourier transform infrared (FTIR) spectrometer, X-ray diffraction (XRD), scanning electron microscopy (SEM), EDAX and conductivity measurements. Incorporation of TiO₂ nanoparticles caused a slight red shift at 310 nm in the absorption spectra due to the interactions between the conjugated polymer chains and TiO₂ nanoparticles with π–π^? transition. FTIR confirmed the presence of TiO₂ in the molecular structure. In PANI/TiO₂ composites, two additional bands at 1623 cm^?1 and 1105 cm^?1 assigned to Ti–O and Ti–O^–C stretching modes were present. It can be concluded that Ti organic compounds are formed with an alignment structure of TiO₂ particles. XRD patterns revealed that, as the TiO₂ percentage was increased, the amorphous nature disappeared and the composites became more strongly oriented along the (1 1 0) direction, which showed the tetragonal structure of nanocrystalline TiO₂. SEM studies revealed the formation of uniform granular morphology with average grain size of 200 nm for (50%) PANI/TiO₂ nanocomposite samples.     

Hydrothermal synthesis of WO3 films on the TiO2 substrates and their photochromic properties

Tungsten oxide (WO₃) films have been prepared on the synthesized TiO₂ substrates from a sodium tungsten precursor via a hydrothermal method. X-ray diffraction, scanning electron microscopy and transmission electron microscopy analyses were used to investigate the effect of precursor concentrations on the structures and morphologies of the films. Ordered WO₃ films were successfully synthesized on the as-grown TiO₂ substrates. With the concentrations increasing from 0.001 M to 0.024 M, the morphologies of the films changed from multi-layer laminated structure to ladder-shaped lamellar structure finally columnar structure. The results also showed that with an increase in precursor concentration, the observed absorptions at 365 nm of the films increased until precursor concentration of 0.016 M, and then decreased with higher concentration. The film obtained with precursor concentration of 0.016 M on the TiO₂ substrate had the best photochromic properties.     

Preparation of highly photocatalytically active rutile titania nanorods decorated with anatase nanoparticles produced by a titanyl-oxalato complex solution

Rutile phase titania (TiO₂) nanorods and anatase nanoparticles were successfully synthesized from a titanyl-oxalato complex solution prepared using titanium (IV) sulfate and oxalic acid by a hydrothermal process. The impact of various hydrothermal conditions on the formation, morphology, phase, and grain size of the TiO₂ nanocrystals was investigated using fourier transformation infrared spectroscopy, X-ray diffraction, transmission electron microscopy, high-resolution transmission electron microscopy, and nitrogen adsorption. The photocatalytic activities have been evaluated for the photo-decomposition of phenol under ultraviolet visible illumination. The results revealed that the TiO₂ rutile nanorods decorated with anatase nanoparticles (with ~22% anatase) prepared at 160 °C for 72 h exhibit a higher photocatalytic activity than those pure anatase nanoparticles. This behavior was closely related to the better charge carrier separation in the cases of rutile–anatase mixtures. In addition, the possible growth mechanism and phase development of the rutile nanorods and anatase nanoparticles were illustrated.     

Unipolar nonvolatile memory devices with composites of poly(9-vinylcarbazole) and titanium dioxide nanoparticles

Organic-based devices with an 8 × 8 array structure using titanium dioxide nanoparticles (TiO₂ NPs) embedded in poly(9-vinylcarbazole) (PVK) film exhibited bistable resistance states and a unipolar nonvolatile memory effect. TiO₂ NPs were a key factor for realizing the bistability and the concentration of TiO₂ NPs influenced ON/OFF ratio. From electrical measurements, switching mechanism of PVK:TiO₂ NPs devices was closely associated with filamentary conduction model and it was found that the OFF state was dominated by thermally activated transport while the ON state followed tunneling transport. PVK:TiO₂ NPs memory devices in 8 × 8 array structure showed a uniform cell-to-cell switching, stable switching endurance, and a high retention time longer than 10⁴ s.     

The optoelectronic properties and applications of solution-processable titanium oxide nanoparticles

In this study, the surface modified TiO₂ nanoparticles have been prepared through microwave-assisted reaction with oleic acid as surfactant. The as-synthesized TiO₂ nanoparticles reveal uniform particle size distribution and high dispersibility in organic solvents which can be easily integrated into solution-process. The organic capped TiO₂ (OC-TiO₂) has been applied as filler for LED encapsulant and electron collection layer for organic solar cells. With 1.0 wt% loading of TiO₂ nanoparticles, the refractive index (RI) of TiO₂/silicone composites increase from 1.51 for neat silicone to 1.575. As a result, a high-power LED encapsulated with this composite showed more than 9% increase in the light output. Moreover, the organic solar cell with the OC-TiO₂ as electron collection layer shows an enhanced long-term durability due to the hydrophobic property of OC-TiO₂.     

Effect of seed layer on the growth of rutile TiO2 nanorod arrays and their performance in dye-sensitized solar cells

In order to improve the performance of TiO₂ photoanode-based dye sensitized solar cells (DSSCs), rutile TiO₂ nanorod arrays (NRAs) were grown on SnO₂:F (FTO) conductive glass coated with TiO₂ seed layer by a hydrothermal method. The TiO₂ seed layer was obtained by spin-coating titanium tetraisopropoxide (TTIP) isopropanol solution with concentration in the range of 0~0.075 M. Then the effect of the thin TiO₂ seed layer on the crystal structure and surface morphology of TiO₂ NRAs and the photoelectric conversion properties of the corresponding DSSCs were investigated. It is found that TiO₂ NRAs are vertically oriented, about 1.7 μm long and the average diameter is about 35 nm for the samples derived from TTIP in the range of 0.005~0.05 M, which are more uniform and better separated from each other than those without TiO₂ seed layer (average diameter 35~85 nm). The photoelectric conversion efficiency of DSSCs based on TiO₂ NRAs with TiO₂ seed layer is larger than that without TiO₂ seed layer. Typically, the energy efficiency of DSSCs obtained from the seed solution of 0.025 M TTIP is 1.47%, about 1.8 times greater than that without TiO₂ seed layer. The performance improvement is attributed to the thinner, denser and better oriented NRAs grown on seeded-FTO substrate absorbing more dye and suppressing charge recombination at the FTO substrate/electrolyte interface.     

Effect of sol–gel MgO spin-coating on the performance of TiO2-based dye-sensitized solar cells

This paper is concerned with the improvement of dye-sensitized solar cell (DSSC) efficiency upon MgO post-treatment of the TiO₂ electrode. A simple sol–gel technique, involving magnesium acetate as precursor, ethanol as solvent and nitric acid as stabilizer, is applied to prepare a solution of suspended MgO nanoparticles. A single drop of MgO sol at 0.1 M precursor concentration was spin-coated at 3000 rpm for 30 s onto the TiO₂ electrode and sintered at 500 K for 1 h. Dye-loading using N3-dye was applied for 6 h. An increase in the average efficiency of the DSSC from 2.5% to 3.9% (over 50% enhancement) was recorded. Measurements of the dark I–V characteristics, the open circuit voltage decays, the SEM images and the dye absorbance spectra, for both uncoated and MgO-coated electrodes were examined. The improvement of the DSSC efficiency was attributed to an upward shift of the TiO₂ flat band energy and a reduction of the rate of back-transport and recombination.     

Effect of preparation techniques on infrared emissivities of Zn0.9Co0.1O powders

Zn_0.9Co_0.1O powders were prepared by chemical solution deposition, solid-state reaction and sol–gel route at different calcination temperatures. The structure and morphologies of samples were determined by X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. The infrared absorption spectra and infrared emissivities in the range of 8–14 μm were investigated by Fourier transform infrared spectroscopy and IR-2 dual-band infrared emissometer. XRD patterns confirmed the hexagonal wurtzite structure of as-synthesized samples but the peaks of the secondary phase, ZnCo₂O₄, were observed below 1000 °C. Scanning electron micrographs showed large grain sizes of the samples prepared by solid-state reaction and sol–gel processing. The infrared emissivities of samples fabricated by chemical solution deposition and sol–gel route decreased with increasing temperature. Powders obtained using solid-state reaction showed the lowest emissivities, with a minimum value (0.755) at 1150 °C.     

Effect of CdS layers on opto-electrical properties of chemically prepared ZnS/CdS/TiO2 photoanodes

In the present work, CdS nanoparticles as a sensitizer were grown on the spin coated nanoporous TiO₂ film by repeated cycles of a Successive Ionic Layer Adsorption and Reaction (SILAR) method. ZnS layer was coated on the CdS/TiO₂ anodes to act as a protection layer on CdS. The crystallite size of CdS nanocrystals is calculated to be 3 nm from XRD spectra. The optical band gap of the film determined from transmittance spectra decreases from 3.46 to 2.15 eV with the increase in the number of CdS SILAR cycles. SEM and TEM analysis depict the enabled penetration of CdS (1 1 1) nanoparticles into the nanoporous TiO₂ (1 0 1) structure. EDX study confirms the presence of all the elements (Ti, Cd, S, Zn and O) found on the photoanode. The attachment of cubic structured CdS on anatase phase of TiO₂ in the photoanode is verified using Raman spectra. Photoluminescence (PL) study shows that the emission peak corresponding to TiO₂ has been slightly blueshifted due to the interaction of CdS nanoparticles in TiO₂ nanoporous structures. The electrical measurement shows that the dark and light illuminated resistivity of the preferred photoanode is 7.91 and 5.65 Ω cm respectively.     

Rapid synthesis of TiO2/MWCNTs nanocatalyst with enhanced photocatalytic activity using modified microwave technique

This work described the rapid synthesis procedure for TiO₂/MWCNT nanocatalyst using a modified microwave method. Transmission electron micrographs suggested TiO₂ nanoparticles were strongly attached to the MWCNT. The surface area of the nanocatalysts determined by the Brunauer–Emmett–Teller method proved that the hybrid nanocatalyst have higher surface area (262.3 m²/g) than pristine TiO₂ (172.3 m²/g). The photocatalytic activity of the nanocatalyst was investigated under visible light (VL) illumination by studying the degradation of methylene blue dye (MB) with concentration of 10 ppm in 100 mL H₂O as a model compound. The results showed that the degradation efficiency obtained by using TiO₂/MWCNTs is about 40% higher than bare TiO₂. This signification enhancement was attributed to higher surface area and the ability of MWCNTs to act as a visible-light photosensitising agent revealing potential application in the treatment of wastewater.     

Template free titiania photoanodes modified with carbon black or multi-wall carbon nanotubes: Thermal treatment at low and high temperature for the fabrication of quasi-solid state dye sensitized solar cells

A simple procedure was developed to prepare modified titiania (TiO₂) photoanodes for dye sensitized solar cells at low and high temperature in order to improve overall cell efficiency. Modification of TiO₂ films achieved by the incorporation of either carbon black powder (CBP) or multi-wall carbon nanotubes (MWCNTs). A small quantity of titanium alkoxide was added in a dispersion of titiania (TiO₂) powder consisting of nanoparticles at room temperature, which after alkoxide׳s hydrolysis helps to the connection between titiania (TiO₂) particles and to the formation of mechanically stable relatively thick films on conductive glass substrates. The absence of surfactant allowed us to prepare films at relatively low temperature (~100 °C), while the effect of sintering at a higher temperature (500 °C) was also studied. The structural properties of the films were examined with porosimetry method and microscopy analysis. Better electrical results were obtained for the MWCNT (0.1 wt%) modified TiO₂ films, with 3.14% and 4.68% conversion efficiencies under 1 sun illumination after treatment at 100 °C and 500 °C, respectively. The enhancement in photocurrent for MWCNT-TiO₂ films compared to pure TiO₂ films is attributed to the improved interconnectivity between TiO₂ nanoparticles, which further improved the electron transport through the film. For carbon doped CBP-TiO₂ cells, lower efficiencies were observed compared to pure TiO₂.     

Effect of lattice distortion on bandgap decrement due to vanadium substitution in TiO2 nanoparticles

Here we present a simple and effective way of bandgap tuning by V-substitution in TiO₂. The nanoparticles of Ti_(1-x)V_xO₂ (for 0≤x≤0.09) were prepared by controlled and simplified sol-gel method. The pure anatase phase of TiO₂ was confirmed by X-ray diffraction and Raman spectroscopy. Debye-scherrer formula and Williamson-Hall plot give crystallite size decreases from 10.8 to 8.2 nm when strain increases from 0.019 to 0.027 for x=0 to x=0.09. Rietveld refinement show the systematic change in crystal structure with the amount of V-substitutions. Raman shift and broadening of FWHM of first E_g (145.52 cm⁻¹) mode observed in Raman spectroscopy follow interestingly the similar and correlated observation with XRD outcomes. FESEM and UHRTEM represent pictorial view of the morphology of the nanoparticles with information about different micro-agglomerations and crystallinity. The oxidation states and local environment of elements in nanoparticles were studied using XANES. V-substitution in TiO₂ shows band gap moderation: band gap decreases gradually with substitution from 3.06–2.02 eV as concentration of V increases from x=0.0 to 0.09. This extends the application of TiO₂ in UV as well as visible light whereas the application of pure TiO₂ is limited in only UV region. The results of SEM, XRD, Raman spectroscopy and UV-vis spectroscopy are correlated well with lattice distortion and the lattice distortion gives the Urbach energy. We reach to the conclusion that the effective bandgap decreases may be due to creation of impurity energy levels or Urbach energy tails just above valance band and below conduction band.     

Thermally induced structural changes and optical properties of tin dioxide nanoparticles synthesized by a conventional precipitation method

Tin dioxide (SnO₂) nanoparticles were synthesized by a conventional precipitation method using the reaction between tin chloride pentahydrate and ammonia solutions. The obtained powders were calcined at varied temperatures from 300 to 1050 °C, and then characterized by using thermogravimetric analysis, differential thermal analysis and Fourier transformation infrared spectroscopy. The average crystallite size, determined by x-ray diffraction, was found to be in the range of 3.45–23.5 nm. The analysis exhibited a tetragonal phase. The activation energy of crystal growth was calculated and found to be 12.12 kJ/mol. The microstructure of nanoparticles was examined by high resolution transmission electron microscopy. Optical properties were investigated by a UV–vis absorption spectrophotometer. The calculated optical band gap lies between 4.75–4.25 eV as a result of increasing the calcination temperatures and crystallite size.     

The environment effect on the electrical conductivity and photoconductivity of anatase TiO2 nanoplates with silver nanoparticles photodeposited on {101} crystal facets

The electrical conductivity and the transient photoconductivity of Ag/TiO₂ nanoplates were studied at 300 K, both in vacuum and in air. A solvothermal method was used for the preparation of anatase TiO₂ nanoplates and the embedding of Ag nanoparticles was achieved via the photoreduction of AgNO₃ under UVA irradiation. The particle size was controlled by varying the time of illumination and the obtained Ag nanoparticles sizes were in a range of 5–20 nm. The Ag/TiO₂ nanoplates were characterized by X-ray diffraction (XRD) and transition electron microscopy (TEM). The electrical conductivity and the photoconductivity responses were investigated. The influence of environment was also discussed. For some periods of UVA illumination time, photoconductivity reaches higher values in comparison with the pure TiO₂ anatase nanoplates. In air, the influence of the adsorbed on the surface oxygen is obvious, resulting in high recombination rates.     

Preparation and photocatalytic activity of Ag/bamboo-type TiO2 nanotube composite electrodes for methylene blue degradation

Photocatalysis phenomena in TiO₂ have been intensively investigated for its potential application in environmental remediation. The present work reports improved photocatalytic degradation of methylene blue dye in aqueous solution by using bamboo-type TiO₂ nanotubes deposited with Ag nanoparticles via electrochemical deposition. The photocatalytic processes are performed on Ag-modified TiO₂ bamboo-type nanotube arrays, Ag-modified smooth-walled nanotube arrays, and bare smooth-walled nanotube arrays. Both Ag-modified bamboo-type and smooth-walled nanotube arrays show improved photocatalytic degradation efficiencies (64.4% and 52.6%) compared to smooth-walled TiO₂ nanotubes of the same length (44.4%), due to the enhanced electron–hole seperation and more surface area provided by bamboo ridges. The photocatalytic activity and kinetic behavior of Ag-modified bamboo-type nanotube arrays are also optmized by tuning pulse deposition time of Ag nanoparticles. Bamboo-type nanotubes deposited with Ag nanoparticles via pulse deposition time of 0.5 s/1.5 s shows the highest methylene blue degradation efficiency of 78.5%, which represents 21.9% and 76.8% enhancement of efficiency compared to those of bare bamboo-type and smooth-walled nanotubes, respectively, indicating that a proper amount of Ag nanoparticles on TiO₂ can maximize the photocatalytic processes. In addition, overly long pulse deposition time will not further increase photocatalytic activity due to agglomeration of Ag paticles. For example, when the pulse deposition time is increased to 2 s/6 s, Ag-modified bamboo-type nanotube array exhibits a lower photocatalytic degradation efficiency of 62.9%.     

Synthesis of Sn doped ZnO/TiO2 nanocomposite film and their application to H2 gas sensing properties

Tin doped Zinc oxide/Titanium oxide nanocomposite (TZO/TiO₂) was prepared by two methods: TiO₂ nanotube (Nt) arrays are grown by anodic oxidation of titanium foil and TZO films was deposited on the TiO₂ Nt obtained by hydrothermal process. The morphological characteristics and structures of ZnO/TiO₂ and TZO/TiO₂ were examined by (scanning elecron miscroscopy) SEM, (X rays diffraction) XRD and (energy dispersive spectroscopy) EDS analysis. The diameter of TiO₂ Nts was ranged from 40 nm to 90 nm with wall thicknesses of approximately 10 nm. The anatase structure of Titania, the hexagonal Zincite crystal of zinc oxide and tetragonal structure of tin oxide were identified by XRD. EDS analysis revealed the presence of O, Zn, Ti and Sn elements in the obtained deposits.These nanocomposites have been used as active layer in hydrogen gas sensing application. The hydrogen sensing characteristics of the sensor was analyzed by measuring the sensor responses in the temperature of 100 °C and 160 °C. The highest gas response is approximately 1.48 at 160 °C.The sensing mechanism of the nanocomposite sensor was explained in terms of H₂ chimisorption on the highly active nanotube surface.     

Influence of Ti film thickness and oxidation temperature on TiO2 thin film formation via thermal oxidation of sputtered Ti film

Single-phase rutile TiO₂ films with good crystallinity were obtained by thermal oxidation of sputtered Ti films on Si and quartz substrates. The influence of the Ti film thickness on oxidation was systematically investigated. A temperature of 823 K was sufficient to fully oxidize Ti films of <0.2 μm in thickness, but 923 K was required for complete oxidation of thicker films. The crystal structure, phase, composition, and optical properties of the TiO₂ films were investigated using X-ray diffraction (XRD), Raman spectroscopy, energy-dispersive X-ray analysis (EDAX), and UV-vis-NIR spectroscopy. XRD and Raman analyses showed that the TiO₂ films are rutile phase. The bandgap of the TiO₂ films decreased with increasing thickness. A growth mechanism for TiO₂ thin films due to thermal oxidation of sputtered Ti films is proposed. Oxidation commences from the surface and proceeds inside the bulk and Ti→TiO₂ phase transformation occurs via different intermediate phases. We found that the oxidation temperature rather than the duration is the dominant factor in the growth of TiO₂ thin films.     

Efficient dye-sensitized solar cells based on CNTs and Zr-doped TiO2 nanoparticles

The light scattering, harvesting and adsorption effects in dye-sensitized solar cells (DSSCs) are studied by preparation of coated carbon nanotubes (CNTs) with TiO₂ and Zr-doped TiO₂ nanoparticles in the forms of mono- and double-layer cells. X-ray diffraction (XRD) analysis reveals that the phase composition of Zr-doped TiO₂ electrode is a mixture of anatase and rutile phases with major rutile content, whereas it is the same mixture with major anatase content for coated CNTs with TiO₂. Furthermore, the average crystallite size of Zr-doped TiO₂ electrode is slightly decreased with Zr introduction. Field emission scanning electron microscope (FE-SEM) images show that the porosity of Zr-doped TiO₂ electrodes is higher than that of undoped electrode, enhancing dye adsorption. UV–visible spectroscopy analysis reveals that the absorption onset of Zr-doped TiO₂ electrodes is slightly shifted to longer wavelength (the red-shift) in comparison with that of undoped TiO₂ electrode. Moreover, the band gap energy of TiO₂ nanoparticles is decreased by Zr introduction, enhancing light absorption. It is found that electron injection of monolayer TiO₂ electrode is improved by introduction of 0.025 mol% Zr, resulted in enhancement of its power conversion efficiency (PCE) up to 6.81% compared with 6.17% for pure TiO₂ electrode. Moreover, electron transport and light scattering are enhanced by incorporation of 0.025 wt% coated CNTs with TiO₂ in the over-layer of double layer electrode. Therefore, double layer solar cell composed of 0.025 mol% Zr-doped TiO₂ nanoparticles as the under-layer and mixtures of these nanoparticles and 0.025 wt% coated CNTs with TiO₂ as the over-layer shows the highest PCE of 8.19%.     

Binder-free MWCNT/TiO2 multilayer nanocomposite as an efficient thin interfacial layer for photoanode of dye sensitized solar cell

Multiwalled carbon nanotube/TiO₂ multilayer nanocomposite was successfully deposited on the fluorine-doped tin oxide (FTO) glass via layer-by-layer assembly technique to modify interfacial contact between the FTO surface and nanocrystalline TiO₂ layer as well as carbon nanotube/TiO₂ contacts in photoanode of dye sensitized solar cell. Using this approach, binder-free interfacial thin film was developed with nonagglomerated, well-dispersed MWCNTs on FTO and into TiO₂ matrix and with maximum covering of TiO₂ nanoparticles on MWCNTs. Introduction of MWCNTs/TiO₂ interfacial layer into the TiO₂ photoanode increased short circuit current density (J_sc) from 11.90 to 17.25 mA/cm² and open circuit voltage (V_oc) from 730 mV to 755 mV, whereas there was no notable change in the fill factor (FF). Consequently, power conversion efficiency (η) was enhanced from 5.32% to 7.53%, yielding a 41.5% enhancement. The results suggest that our simple strategy can integrate reduction of back electron reaction at FTO/TiO₂ interface with the effective charge transport ability of carbon nanotubes and possessing high surface area for efficient dye loading.     

Hydrothermal synthesis and characterization of α-Fe2O3 nanoparticles

Iron oxide (Fe₂O₃) nanoparticles were synthesized by a simple hydrothermal synthesis method using only Fe(NO₃)₃·9H₂O and NH₃·H₂O as raw materials. The effect of reaction temperature and time on the crystalline phase and morphology of Fe₂O₃ products was investigated. The products were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and Fourier transform infrared (FTIR) spectroscopy. The XRD and TEM results show that reaction temperature and time play an important role in the formation of the crystalline phase and morphology of the products. With increasing reaction temperature and time, the diffraction peaks of α-Fe₂O₃ become stronger and sharper, and the morphologies of the samples have an obvious change from floccules to nanoparticles. FTIR peaks show that α-Fe₂O₃ nanoparticles have about a 25 cm^?1 shift to higher frequency compared with those of α-Fe₂O₃ with other morphologies.