3D hierarchical rutile TiO2 and metal-free organic sensitizer producing dye-sensitized solar cells 8.6% conversion efficiency

Three-dimensional (3D) hierarchical nanoscale architectures comprised of building blocks, with specifically engineered morphologies, are expected to play important roles in the fabrication of 'next generation' microelectronic and optoelectronic devices due to their high surface-to-volume ratio as well as opto-electronic properties. Herein, a series of well-defined 3D hierarchical rutile TiO2 architectures (HRT) were successfully prepared using a facile hydrothermal method without any surfactant or template, simply by changing the concentration of hydrochloric acid used in the synthesis. The production of these materials provides, to the best of our knowledge, the first identified example of a ledgewise growth mechanism in a rutile TiO2 structure. Also for the first time, a Dye-sensitized Solar Cell (DSC) combining a HRT is reported in conjunction with a high-extinction-coefficient metal-free organic sensitizer (D149), achieving a conversion efficiency of 5.5%, which is superior to ones employing P25 (4.5%), comparable to state-of-the-art commercial transparent titania anatase paste (5.8%). Further to this, an overall conversion efficiency 8.6% was achieved when HRT was used as the light scattering layer, a considerable improvement over the commercial transparent/reflector titania anatase paste (7.6%), a significantly smaller gap in performance than has been seen previously.

Implications of precursor chemistry on the alkaline hydrothermal synthesis of titania/titanate nanostructures

A systematic study of four parameters within the alkaline hydrothermal treatment of three commercial titania powders—anatase, rutile, and Degussa P25—was made. These powders were treated with 5, 7.5, 9, and 10 M NaOH between 100 and 220 °C for 20 h. The effects of alkaline concentration, hydrothermal temperature, and precursor phase and crystallite size on the resultant nanostructure formation have been studied through X-ray diffraction, Raman spectroscopy, transmission electron microscopy, and nitrogen adsorption. Through the correlation of these data, morphological phase diagrams were constructed for each commercial powder. Interpretation of the resultant morphological phase diagrams indicates that alkaline concentration and hydrothermal temperature affect nanostructure formation independently, where nanoribbon formation is significantly influenced by temperature for initial formation. The phase and crystallite size of the precursor also significantly influenced nanostructure formation, with rutile displaying a slower rate of precursor consumption compared with anatase. Small crystallite titania precursors formed nanostructures at reduced hydrothermal temperatures.

Investigation of inclusions trapped inside Libyan Desert glass by Raman microscopy

Several specimens of Libyan Desert Glass (LDG), an enigmatic natural glass from Egypt, were subjected to investigation by micro-Raman spectroscopy. The spectra of inclusions inside the LDG samples were successfully measured through the layers of glass and the mineral species were identified on this basis. The presence of cristobalite as typical for high-temperature melt products was confirmed, together with co-existing quartz. TiO2 was determined in two polymorphic species, rutile and anatase. Micro-Raman spectroscopy proved also the presence of minerals unusual for high-temperature glasses such as anhydrite and aragonite.

Alkaline hydrothermal treatment of titanate nanostructures

Since its initial proposal in 1998, alkaline hydrothermal processing has rapidly become an established technology for the production of titanate nanostructures. This simple, highly reproducible process has gained a strong research following since its conception. However, complete understanding and elucidation of nanostructure phase and formation have not yet been achieved. Without fully understanding phase, formation, and other important competing effects of the synthesis parameters on the final structure, the maximum potential of these nanostructures cannot be obtained. Therefore this study examined the influence of synthesis parameters on the formation of titanate nanostructures produced by alkaline hydrothermal treatment. The parameters included alkaline concentration, hydrothermal temperature, the precursor material‘s crystallite size and also the phase of the titanium dioxide precursor (TiO2, or titania). The nanostructure‘s phase and morphology was analysed using X-ray diffraction (XRD), Raman spectroscopy and transmission electron microscopy. X-ray photoelectron spectroscopy (XPS), dynamic light scattering (non-invasive backscattering), nitrogen sorption, and Rietveld analysis were used to determine phase, for particle sizing, surface area determinations, and establishing phase concentrations, respectively. This project rigorously examined the effect of alkaline concentration and hydrothermal temperature on three commercially sourced and two self-prepared TiO2 powders. These precursors consisted of both pure- or mixed-phase anatase and rutile polymorphs, and were selected to cover a range of phase concentrations and crystallite sizes. Typically, these precursors were treated with 5–10 M sodium hydroxide (NaOH) solutions at temperatures between 100–220 °C. Both nanotube and nanoribbon morphologies could be produced depending on the combination of these hydrothermal conditions. Both titania and titanate phases are comprised of TiO6 units which are assembled in different combinations. The arrangement of these atoms affects the binding energy between the Ti–O bonds. Raman spectroscopy and XPS were therefore employed in a preliminary study of phase determination for these materials. The change in binding energy from a titania to a titanate binding energy was investigated in this study, and the transformation of titania precursor into nanotubes and titanate nanoribbons was directly observed by these methods. Evaluation of the Raman and XPS results indicated a strengthening in the binding energies of both the Ti (2p3/2) and O (1s) bands which correlated to an increase in strength and decrease in resolution of the characteristic nanotube doublet observed between 320 and 220 cm.1 in the Raman spectra of these products. The effect of phase and crystallite size on nanotube formation was examined over a series of temperatures (100.200 �‹C in 20 �‹C increments) at a set alkaline concentration (7.5 M NaOH). These parameters were investigated by employing both pure- and mixed- phase precursors of anatase and rutile. This study indicated that both the crystallite size and phase affect nanotube formation, with rutile requiring a greater driving force (essentially �\harsher. hydrothermal conditions) than anatase to form nanotubes, where larger crystallites forms of the precursor also appeared to impede nanotube formation slightly. These parameters were further examined in later studies. The influence of alkaline concentration and hydrothermal temperature were systematically examined for the transformation of Degussa P25 into nanotubes and nanoribbons, and exact conditions for nanostructure synthesis were determined. Correlation of these data sets resulted in the construction of a morphological phase diagram, which is an effective reference for nanostructure formation. This morphological phase diagram effectively provides a .recipe book�e for the formation of titanate nanostructures. Morphological phase diagrams were also constructed for larger, near phase-pure anatase and rutile precursors, to further investigate the influence of hydrothermal reaction parameters on the formation of titanate nanotubes and nanoribbons. The effects of alkaline concentration, hydrothermal temperature, crystallite phase and size are observed when the three morphological phase diagrams are compared. Through the analysis of these results it was determined that alkaline concentration and hydrothermal temperature affect nanotube and nanoribbon formation independently through a complex relationship, where nanotubes are primarily affected by temperature, whilst nanoribbons are strongly influenced by alkaline concentration. Crystallite size and phase also affected the nanostructure formation. Smaller precursor crystallites formed nanostructures at reduced hydrothermal temperature, and rutile displayed a slower rate of precursor consumption compared to anatase, with incomplete conversion observed for most hydrothermal conditions. The incomplete conversion of rutile into nanotubes was examined in detail in the final study. This study selectively examined the kinetics of precursor dissolution in order to understand why rutile incompletely converted. This was achieved by selecting a single hydrothermal condition (9 M NaOH, 160 °C) where nanotubes are known to form from both anatase and rutile, where the synthesis was quenched after 2, 4, 8, 16 and 32 hours. The influence of precursor phase on nanostructure formation was explicitly determined to be due to different dissolution kinetics; where anatase exhibited zero-order dissolution and rutile second-order. This difference in kinetic order cannot be simply explained by the variation in crystallite size, as the inherent surface areas of the two precursors were determined to have first-order relationships with time. Therefore, the crystallite size (and inherent surface area) does not affect the overall kinetic order of dissolution; rather, it determines the rate of reaction. Finally, nanostructure formation was found to be controlled by the availability of dissolved titanium (Ti4+) species in solution, which is mediated by the dissolution kinetics of the precursor.

An ultraviolet selective photodetector based on a nanocrystalline TiO2 photoelectrochemical cell

Solar ultraviolet (UV) radiation causes a range of skin disorders as well as affecting vision and the immune system. It also inhibits development of plants and animals. UV radiation monitoring is used routinely in some locations in order to alert the population to harmful solar radiation levels. There is ongoing research to develop UV-selective-sensors [1–3]. A personal, inexpensive and simple UV-selective-sensor would be desirable to measure UV intensity exposure. A prototype of such a detector has been developed and evaluated in our laboratory. It comprises a sealed two-electrode photoelectrochemical cell (PEC) based on nanocrystalline TiO2. This abundant semiconducting oxide, which is innocuous and very sta-ble, is the subject of intense study at present due to its application in dye sensitized solar cells (DSSC) [4]. Since TiO2 has a wide band gap (EG = 3.0 eV for rutile and EG = 3.2 eV for anatase), it is inher-ently UV-selective, so that UV filters are not required. This further reduces the cost of the proposed photodetector in comparison with conventional silicon detectors. The PEC is a semiconductor–electrolyte device that generates a photovoltage when it is illuminated and a corresponding photocur-rent if the external circuit is closed. The device does not require external bias, and the short circuit current is generally a linear function of illumination intensity. This greatly simplifies the elec-trical circuit needed when using the PEC as a photodetector. DSSC technology, which is based on a PEC containing nanocrystalline TiO2 sensitized with a ruthenium dye, holds out the promise of solar cells that are significantly cheaper than traditional silicon solar cells. The UV-sensor proposed in this paper relies on the cre-ation of electron–hole pairs in the TiO2 by UV radiation, so that it would be even cheaper than a DSSC since no sensitizer dye is needed. Although TiO2 has been reported as a suitable material for UV sensing [3], to the best of our knowledge, the PEC configuration described in the present paper is a new approach. In the present study, a novel double-layer TiO2 structure has been investigated. Fabrication is based on a simple and inexpensive technique for nanostructured TiO2 deposition using microwave-activated chemical bath deposition (MW-CBD) that has been reported recently [5]. The highly transparent TiO2 (anatase) films obtained are densely packed, and they adhere very well to the transparent oxide (TCO) substrate [6]. These compact layers have been studied as contacting layers in double-layer TiO2 structures for DSSC since improvement of electron extraction at the TiO2–TCO interface is expected [7]. Here we compare devices incorporating a single mesoporous nanocrystalline TiO2 structure with devices based on a double structure in which a MW-CBD film is situated between the TCO and the mesoporous nanocrystalline TiO2 layer. Besides improving electron extraction, this film could also help to block recombination of electrons transferred to the TCO with oxidized species in the electrolyte, as has been reported in the case of DSSC for compact TiO2 films obtained by other deposition tech-niques [8,9]. The two types of UV-selective sensors were characterized in detail. The current voltage characteristics, spectral response, inten-sity dependence of short circuit current and response times were measured and analyzed in order to evaluate the potential of sealed mesoporous TiO2-based photoelectrochemical cells (PEC) as low cost personal UV-photodetectors.

Preparation and characterization of TiO2/acid leached serpentinite tailings composites and their photocatalytic reduction of Chromium(VI)

Composite TiO2/acid leached serpentine tailings (AST) were synthesized through the hydrolysis–deposition method and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energydispersive X-ray spectrometry (EDS), Fourier-transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and surface area measurement (BET). The XRD analysis showed that TiO2 coated on the surface of acid leached serpentine tailings was mixed crystal phases of rutile and anatase, the grain size of which is 10–30 nm. SEM, TEM, and EDS analysis exhibited that nano-TiO2 particles were deposited on the surface and internal cavities of acid leaching serpentine tailings. The XPS and FT-IR analysis demonstrated that the coating process of TiO2 on AST was a physical adsorption process. The large specific surface area, porous structure, and plentiful surface hydroxyl group of TiO2/AST composite resulted in the high adsorption capacity of Cr(VI). The experimental results demonstrated that initial concentration of Cr(VI), the amount of the catalyst, and pH greatly influenced the removal efficiency of Cr(VI). The removal kinetics of Cr(VI) at a relative low initial concentration was fitted well with Langmuir–Hinshelwood kinetics model with R2 value of about unity. The asprepared composites exhibited strong adsorption and photocatalytic capacity for the removal of Cr(VI), and the possible photocatalytic reduction mechanism was studied. The photodecomposition of Cr(VI) was as high as 95% within 2 h, and the reusability of the photocatalysis was proven.

Investigation on bioactivity of titanium dioxide thin films fabricated by electron cyclotron resonance plasma aided pulsed laser deposition

Titanium dioxide thin films with a rutile crystallinite size around 20 nm were fabricated by pulsed laser deposition (PLD) aided with an electron cyclotron resonance (ECR) plasma. With annealing treatment, the crystal size of the rutile crystallinite increased to 100 nm. The apatite-forming ability of the films as deposited and after annealing was investigated in a kind of simulated body fluid with ion concentrations nearly equal to those of human blood plasma. The results indicate that ECR aided PLD is an effective way both to fabricate bioactive titanium dioxide thin films and to optimize the bioactivity of titanium dioxide, with both crystal size and defects of the film taken into account.

Synthesis, characterization and activity of an immobilized photocatalyst : natural porous diatomite supported titania nanoparticles

Diatomite, a porous non-metal mineral, was used as support to prepare TiO2/diatomite composites by a modified sol–gel method. The as-prepared composites were calcined at temperatures ranging from 450 to 950 _C. The characterization tests included X-ray powder diffraction (XRD), scanning electron microscopy (SEM) with an energy-dispersive X-ray spectrometer (EDS), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), and nitrogen adsorption/desorption measurements. The XRD analysis indicated that the binary mixtures of anatase and rutile exist in the composites. The morphology analysis confirmed the TiO2 particles were uniformly immobilized on the surface of diatom with a strong interfacial anchoring strength, which leads to few drain of photocatalytic components during practical applications. In further XPS studies of hybrid catalyst, we found the evidence of the presence of Ti–O–Si bond and increased percentage of surface hydroxyl. In addition, the adsorption capacity and photocatalytic activity of synthesized TiO2/diatomite composites were evaluated by studying the degradation kinetics of aqueous Rhodamine B under UV-light irradiation. The photocatalytic degradation was found to follow pseudo-first order kinetics according to the Langmuir–Hinshelwood model. The preferable removal efficiency was observed in composites by 750 _C calcination, which is attributed to a relatively appropriate anatase/rutile mixing ratio of 90/10.

Atomistic investigation into the mechanical behaviour of crystalline and amorphous TiO2 nanotubes

Titanium dioxide (TiO2) nanotubes are appealing to research communities due to their excellent functional properties. However, there is still a lack of understanding of their mechanical properties. In this work, we conduct molecular dynamics (MD) simulations to investigate the mechanical behaviour of rutile and amorphous TiO2 nanotubes. The results indicate that the rutile TiO2 nanotube has a much higher Young's modulus (∼800 GPa) than the amorphous one (∼400 GPa). Under tensile loading, rutile nanotubes fail in the form of brittle fracture but significant ductility (up to 30%) has been observed in amorphous nanotubes. This is attributed to a unique ‘repairing’ mechanism via bond reconstruction at under-coordinated sites as well as bond conversion at over-coordinated sites. In addition, it is observed that the fracture strength of rutile nanotubes is strongly dependent on their free surfaces. These findings are considered to be useful for development of TiO2 nanostructures with improved mechanical properties.

Morphology-controllable 1D–3D nanostructured TiO2 bilayer photoanodes for dye-sensitized solar cells

Morphology-controlled bilayer TiO2 nanostructures consisting of one-dimensional (1D) nanowire bottom arrays and a three-dimensional (3D) dendritic microsphere top layer were synthesized via a one-step hydrothermal method. These novel 1D-3D bilayer photoanodes demonstrated the highest energy conversion efficiency of 7.2% for rutile TiO2 dye-sensitized solar cells to date, with TiCl4 post-treatment.