Efficient carbon-doped nanostructured TiO<Subscript>2</Subscript> (anatase) film for photoelectrochemical solar cells

In this paper, we have demonstrated that carbon-doped nanostructured TiO₂ (CD ns-TiO₂) films could be prepared simply and cheaply with oxalic acid and tetrabutylammonium bromide (Bu₄N·Br) as the carbon sources. The surface morphology of the films was a multiple-porous network structure.The average size of nanoparticle was about 40 nm. Carbon doped into substitutional sites of TiO₂ has also proven to be indispensable for band-gap narrowing and photovoltaic effect. Carbon doping lowered the band gap of n-TiO₂ to 1.98, 1.64, and 1.26 eV. The CD ns-TiO₂ film was first used as photoanode for solar cells, exhibiting high photocurrent densities (l.34 mA/cm²) and yielding an overall conversion efficiency (η) of 4.42 %.     

Effect of surface roughness of TiO2 films on short-circuit current density of photoelectrochemical cell of ITO/TiO2/PVC-LiClO4/graphite

This paper reports the effect of surface topography of titanium dioxide films on short-circuit current density of photoelectrochemical solar cell of ITO/TiO₂/PVC-LiCLO₄/graphite. The films were deposited onto ITO-covered glass substrate by screen-printing technique. The films were tempered at 300 °C, 350 °C, 400 °C, 450 °C and 500 °C for 30 min to burn out the organic parts and to achieve the films with porous structure. The surface roughness of the films were studied using scanning electron microscope (SEM). Current–voltage relationship of the devices were characterized in dark at room temperature and under illumination of 100 mW cm⁻² light from tungsten halogen lamp at 50 °C. The device utilising the TiO₂ film annealed at 400 °C produces the highest short-circuit current density and open-circuit voltage as it posses the smoothest surface topography with the electrolyte. The short-circuit current density and open-circuit voltage of the devices increase with the decreasing grain size of the TiO₂ films. The short-circuit current density and open-circuit voltage are 0.6 μA/cm² and 109 mV respectively.     

Characterization of TiO<Subscript>2</Subscript> nanoparticle suspensions for electrophoretic deposition

The rheology of suspensions is critically important for the successful achievement of defect-free TiO₂ deposits by electrophoretic deposition (EPD). The rheological behaviour of TiO₂ nanoparticle suspensions in acetylacetone with and without iodine was investigated over a broad solid-concentration range (0.3–2.5 wt.%) and at different shear rates ( = 10–250 s⁻¹). The influence of these parameters on the quality of TiO₂ films obtained by EPD on stainless steel substrates was assessed. The pure solvent and the 1 wt.% TiO₂ nanoparticles suspension without iodine exhibited shear-thickening flow behaviour. For other concentrations, the suspensions showed shear-thinning behaviour followed by an apparent shear-thickening effect at a critical shear rate (100 s⁻¹). For the suspension with 1 wt.% TiO₂ containing iodine, a shear-thickening flow behaviour was observed over the whole shear rate range investigated. The maximum solids fraction (ϕ_m) was experimentally determined from a linear relationship between solid concentration and viscosity. The estimated value was ϕ_m = 7.94 wt.% for this system. Using a suspension with 1 wt.% concentration, good-quality TiO₂ deposits on stainless steel planar substrates were obtained by EPD at constant voltage condition. The influence of pH on suspension stability was determined in the range pH = 1–9, being pH ≈ 5 the optimal value for this system in terms of EPD results.     

Electrical properties of polycrystalline TiO<Subscript>2</Subscript>: Equilibration kinetics

The equilibration kinetics was determined for high purity polycrystalline TiO₂ in the temperature range of 1,123–1,323 K, within a wide range of oxygen activity, . The equilibration kinetics experiments were performed within narrow p(O₂) ranges. The obtained kinetic data were used for the determination of the chemical diffusion coefficient, D _chem, which exhibits a complex dependence of p(O₂). The D _chem data are considered in terms of the effect of defect disorder on the mass transport kinetics in the chemical potential gradient. The reported diffusion data may be used for prediction of optimized processing conditions required to impose a homogeneous distribution of oxygen activity within the TiO₂ specimen. This project was performed as part of University of New South Wales R&D program on solar hydrogen.     

Electrical properties of polycrystalline TiO<Subscript>2</Subscript>. Prolonged oxidation kinetics

The equilibration kinetics for polycrystalline TiO₂ was monitored during prolonged oxidation at 1,323 K and p(O₂)=75 kPa using the measurements of the electrical conductivity and thermoelectric power. The determined kinetic data indicate the presence of two kinetics regimes; the Regime I (rapid kinetics) and the Regime II (slow kinetics). The prolonged oxidation of TiO₂ is considered in terms of the formation of Ti vacancies at the surface and their subsequent transport into the bulk. This effect, also observed for TiO₂ single crystal, allows to obtain p-type TiO₂ without the incorporation of acceptor-type foreign ions into the TiO₂ lattice. This project was performed as part of the University of New South Wales Research and Development programme on solar-hydrogen.     

Photogreying of TiO<Subscript>2</Subscript> nanoparticles

Photogreying, the change in brightness on UV irradiation in the absence of oxygen, of TiO₂ nanoparticulate dispersions is shown to depend on the nature of the liquid, consistent with a surface reaction. Measurements on a series of TiO₂ particles (mainly 75×10 nm) dispersed in, e.g., alkyl benzoate correlate well with those on the same TiO₂’s dispersed in a second liquid (e.g. propan-2-ol). Photogreying in propan-2-ol is paralleled by photocatalytic-oxidation activity, indicating a common origin – UV-generation of charge carriers. Further, photogreying parallels Ti³⁺ formation. Hence, although appearance and the visible spectra of photogreyed particles both differ from those of Ti³⁺ in ≤10 nm colloidal TiO₂, we suggest that photogreying is caused by capture of UV excited electrons to form Ti³⁺. Surface treatment reduces photogreying, and we speculate that differences between uncoated samples reflect differences in the number of potentially reducible Ti’s.     

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.     

H<Subscript>2</Subscript>O/CuIn<Subscript>3</Subscript>Se<Subscript>5</Subscript> photoelectrochemical cells: Fabrication and properties

Single-phase coarse-grained CuIn₃Se₅ ingots are grown by horizontal oriented crystallization from the near-stoichiometric melt. Photosensitive structures based on the interface between these crystals and an electrolyte (H₂O) are created. It is shown that the CuIn₃Se₅ ternary compound is a direct-gap semiconductor with an energy gap Eg ≃ 1.1 eV (T = 300 K). H₂O/CuIn₃Se₅ photoelectrochemical cells seem to be promising for efficient wide-band photodetectors of natural light.     

Effects of Gd<Superscript>3+</Superscript> modifications on the photoelectrochemical properties of TiO<Subscript>2</Subscript>-based dye-sensitized solar cells

In this paper, TiO₂ particles (~30 nm) modified with Gd₂O₃-coating layer (~2 nm) for dye-sensitized solar cells (DSSCs) were fabricated via the hydrothermal method. Among the solar cells based on the Gd³⁺-doped TiO₂ photoanodes, the optimal conversion efficiency was obtained from the 0.025Gd³⁺-modified TiO₂-based cell, with a 17.7% improvement in the efficiency as compared to the unmodified one (7.18%). This enhancement was probably due to the improved UV radiation harvesting via a down-conversion luminescence process by Gd³⁺ ions, enhancement of visible light absorption and improved dye loading capacity. In addition, after Gd modification, a thin coating could be formed on the TiO₂ nanoparticles, which worked as an energy barrier and resulted in a lower charge recombination.     

Impedance spectroscopy study of Na<Subscript>1/2</Subscript>Sm<Subscript>1/2</Subscript>TiO<Subscript>3</Subscript> ceramic

Complex impedance analysis of a valence-compensated perovskite ceramic oxide Na_1/2Sm_1/2TiO₃, prepared by a mixed oxide (solid-state reaction) method, has been carried out. The formation of single-phase material was confirmed by X-ray diffraction studies, and it was found to be an orthorhombic phase at room temperature. In a scanning electron microscope, grains separated by well-defined boundaries are visible, which is in good agreement with that of impedance analysis. Alternating current impedance measurements were made over a wide temperature range (31–400 °C) in an air atmosphere. Complex impedance and modulus plots helped to separate out the contributions of grain and grain boundaries to the overall polarization or electrical behavior. The physical structure of the samples was visualized most prominently at higher temperatures (275 °C) from the Nyquist plots showing inter- and intragranular impedance present in the material. The frequency dependence of electrical data is also analyzed in the framework of the conductivity and modulus formalisms. The bulk resistance, evaluated from the impedance spectrum, was observed to decrease with rise in temperature, showing a typical negative temperature coefficient of resistance-type behavior like that of semiconductors. The modulus mechanism indicates the non-Debye type of conductivity relaxation in the materials, which is supported by the impedance data. PACS 77.22.Ch; 77.22.Ej; 77.22.Gm; 77.22.Jp; 77.84.Bw     

Fowler-nordheim tunnelling in Au−TiO<Subscript>2</Subscript>−Ag film structures

I-V-characteristics have been measured for Au−TiO₂−Ag structures with TiO₂ layers of 30 and 180 nm thickness. The TiO₂ films were grown by atomic layer deposition (ALD) technique. In the case of negative bias on the Au electrode, the conduction currents through TiO₂ layers follow the Fowler-Nordheim formula for field emission over several orders of magnitude. The bulk of the currents may be attributed to tunnelling, seemingly through a Schottky barrier at the Au−TiO₂ junction. In the case of reversed polarity the currents are also observed, but cannot be interpreted as tunnelling.     

Colloidal nanocrystal ZnO- and TiO<Subscript>2</Subscript>-modified electrodes sensitized with chlorophyll a and carotenoids: a photoelectrochemical study

Heterostructures formed of films of organic-capped ZnO and TiO₂ nanocrystals (both with the size of ca. 6 nm) and photosynthetic pigments were prepared and characterized. The surface of optically transparent electrodes (Indium Tin Oxide) was modified with nanocrystals and prepared by colloidal synthetic routes. The nanostructured electrodes were sensitized by a mixture of chlorophyll a and carotenoids. The characterization of the hybrid structures, carried out by means of steady-state optical measurements, demonstrated such class of dyes able to extend the photoresponse of the large band-gap semiconductors. The charge-transfer processes between the components of the heterojunction were investigated, and photoelectrochemical measurements taken on the sensitized ZnO and TiO₂ nanocrystals electrodes elucidated the photoactivity of the heterojunctions as a function of the dyes and of the red–ox mediator used in solution. The effect of methyl viologen as different red–ox mediator was also evaluated in order to show its effect on the heterojunction photoactivity. The overall results contributed to describe the photoelectrochemical potential of the investigated heterojunctions, highlighting a higher response of the dye-sensitized ZnO nanocrystals, and then provided the TiO₂-modified counterparts.     

Synthesis,characterization, and thermal stability of SiO<Subscript>2</Subscript>/TiO<Subscript>2</Subscript>/CR-Ag multilayered nanostructures

The controllable synthesis and characterization of novel thermally stable silver-based particles are described. The experimental approach involves the design of thermally stable nanostructures by the deposition of an interfacial thick, active titania layer between the primary substrate (SiO₂ particles) and the metal nanoparticles (Ag NPs), as well as the doping of Ag nanoparticles with an organic molecule (Congo Red, CR). The nanostructured particles were composed of a 330-nm silica core capped by a granular titania layer (10 to 13 nm in thickness), along with monodisperse 5 to 30 nm CR-Ag NPs deposited on top. The titania-coated support (SiO₂/TiO₂ particles) was shown to be chemically and thermally stable and promoted the nucleation and anchoring of CR-Ag NPs, which prevented the sintering of CR-Ag NPs when the structure was exposed to high temperatures. The thermal stability of the silver composites was examined by scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM). Larger than 10 nm CR-Ag NPs were thermally stable up to 300 °C. Such temperature was high enough to destabilize the CR-Ag NPs due to the melting point of the CR. On the other hand, smaller than 10 nm Ag NPs were stable at temperatures up to 500 °C because of the strong metal-metal oxide binding energy. Energy dispersion X-ray spectroscopy (EDS) was carried out to qualitatively analyze the chemical stability of the structure at different temperatures which confirmed the stability of the structure and the existence of silver NPs at temperatures up to 500 °C.     

The effect of anodising time on the electrochemical behaviour of the Ti/TiO<Subscript>2</Subscript> NTs/IrO<Subscript>2</Subscript>-RuO<Subscript>2</Subscript>-Ta<Subscript>2</Subscript>O<Subscript>5</Subscript> anode

Nowadays, mixed metal oxide (MMO) anodes are a superior alternative to lead alloys in electrowinning processes. Passivation of titanium substrate is the most common mechanism of deactivation in these anodes. In this research, titanium oxide nanotubes have been utilised as an interlayer between the substrate and a mixed metal oxide coating in order to improve the anode electrochemical behaviour and life via retardation of titanium passivation. Anodising of the substrate was done in 0.5 wt% hydrofluoric acid for 30, 60 and 240 min. The samples were subsequently coated with a coating composed of IrO₂-RuO₂-Ta₂O₅. The microstructure of different samples was observed by scanning with an electron microscope, and the electrochemical behaviour of the samples was studied by accelerated life test, cyclic voltammetry and electrochemical impedance spectroscopy. The studies showed that formation of titanium oxide nanotubes with anodising times of 60 and 240 min increases the life of the anode through the provision of a compact coating. The life of the anode which was anodised for 240 min lasted about 20% longer than the sample which had a substrate without any anodised layer.     

Melting temperature of H<Subscript>2</Subscript>, D<Subscript>2</Subscript>, N<Subscript>2</Subscript> and CH<Subscript>4</Subscript> under high pressure

The melting temperatures of H₂, D₂; N₂ and CH₄ are analysed. The computed results are in very good agreement with the experimental data in each solid. Further, the analysis indicates the presence of the melting maximum in these solids.     

Effects of sintering temperature on the structure and electrochemical performance of Mg<Subscript>2</Subscript>SiO<Subscript>4</Subscript> cathode materials

The objective of the present study was to investigate the effects of sintering temperature on the structure and electrochemical performance of Mg₂SiO₄ cathode materials using sol-gel method. X-ray diffraction and Fourier-transform infrared analysis were used to study the structural properties of the materials. The temperatures applied in the sintering process influenced the structure, morphology, as well as particle size distribution of the Mg₂SiO₄. All samples sintered at temperatures of 900, 1000, and 1100 °C yielded pure Mg₂SiO₄ compounds consisting of orthorhombic crystalline phase with a space group of Pbnm. Particle size and lattice parameters of Mg₂SiO₄ samples increased with the increases of sintering temperature due to an increase of the nucleation and crystal growth rates. The cyclic voltammetry analysis showed the presence of redox reaction. This result shows that the Mg₂SiO₄ material has potential to be used as cathode materials in magnesium rechargeable batteries.     

Preparation of TiO<Subscript>2</Subscript>-coated LiCo<Subscript>1/3</Subscript>Ni<Subscript>1/3</Subscript>Mn<Subscript>1/3</Subscript>O<Subscript>2</Subscript> by electrostatic self-assembly method and its properties

A precursor of TiO₂–LiCo_1/3Ni_1/3Mn_1/3O₂ was prepared by electrostatic self-assembly method. The final product was obtained by heating the precursor at 400–450 °C for 4–6 h in air. X-ray diffraction (XRD), scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), and electrochemical tests were used to examine the structural, morphology, elementary valence, and electrochemical characteristics. XRD indicated that the TiO₂-coated material can be indexed by α-NaFeO₂ layered structure, which belongs to hexagonal-type space group R3m. XPS results confirmed the existence of TiO₂ compound on the surface of the coated sample. The SEM image showed that the material had spherically porous morphology with the uniform size about 6 μm. The initial charge–discharge capacity of the TiO₂-coated LiCo_1/3Ni_1/3Mn_1/3O₂ material was 168.8/160.0 mAh/g. After 60 cycles, the discharge capacity of the TiO₂-coated LiCo_1/3Ni_1/3Mn_1/3O₂ sample was 147.0 mAh/g, and the coulombic efficiency was 94.0%. Compared with the uncoated sample, the electrochemical performance of TiO₂-coated LiCo_1/3Ni_1/3Mn_1/3O₂ was improved.