Enhanced inactivation of E. coli bacteria using immobilized porous TiO2 photoelectrocatalysis

Immobilized TiO₂ nanotube electrodes with high surface areas were grown via electrochemical anodization in aqueous solution containing fluoride ions for photocatalysis applications. The photoelectrochemical properties of the grown immobilized TiO₂ film were studied by potentiodynamic measurements (linear sweep voltammetry), in addition to the calculation of the photocurrent response. The nanotube electrode properties were compared to mesoporous TiO₂ electrodes grown by anodization in sulfuric acid at high potentials (above the microsparking potential) and to 1 g/l P-25 TiO₂ powder. Photocatalyst films were evaluated by high resolution SEM and XRD for surface and crystallographic characterization. Finally, photoelectrocatalytic application of TiO₂ was studied via inactivation of E. coli. The use of the high surface area TiO₂ nanotubes resulted in a high photocurrent and an extremely rapid E. coli inactivation rate of ∼10⁶ CFU/ml bacteria within 10 min. The immobilized nanotube system is proven to be the most potent electrode for water purification.     

Improved performance of dense TiO2/CdSe coupled thin films by low temperature process

Dense TiO₂ and TiO₂/CdSe coupled nanocrystalline thin films were synthesized onto ITO coated glass substrate by chemical route at relatively low temperature (≤100 °C). TiO₂ films were nanocrystalline and crystallinity disappears after CdSe deposition as evidenced by X-ray powder diffraction. Surface morphology and physical appearance of films were studied from SEM and actual photo-images, reveals dense nature of TiO₂ (10-12 nm spherical grains, faint violet) and CdSe (80-90 nm spherical grains, deep brown), respectively. Presence of two absorption edges in UV spectra implies existence of separate phases rather than composite formation. TiO₂ film was found to have higher water contact angle (71°) than TiO₂/CdSe (61°) and CdSe (56°). I-V and stability tests of photo-electrochemical cells were performed with TiO₂ and TiO₂/CdSe film electrodes (under light of illumination intensity 80 mW/cm²) in lithium iodide as an electrolyte using two-electrode system.     

Photoelectrochemical decomposition of bio-related compounds at a nanoporous semiconductor film photoanode and their photocurrent-photovoltage characteristics

Photoelectrochemical decomposition of bio-related compounds such as amino acids was investigated with a biophotochemical cell comprising a mesoporous TiO₂ thin film photoanode and an O₂-reducing cathode. It was concluded that a kind of Schottky junction formed at the surface of the TiO₂ (called as liquid junction) induced the photodecomposition followed by generation of photocurrent/photovoltage. Complete photodecomposition was investigated by the CO₂ formation yield. The photocurrent-photovoltage (J-V) characteristics of amino acids and other typical bio-related compounds were investigated, and the short circuit photocurrent (J_sc), open circuit photovoltage (V_oc), and Fill factor (ff) were exhibited. Effect of pH on the photodecomposition of phenylalanine and cysteine were studied; for cysteine alkaline conditions gave a high efficiency, which was interpreted by the high electron-donating ability of the dissociated -S⁻ group. The incident light-to-current conversion efficiency (IPCE) of cysteine was 25% at 350 nm. It was for the first time shown that organic acids gave high internal quantum efficiency (η′) over 8 (=800%) in the photodecomposition; for oxalic acid it was 9.3 (=930%) and for butyric acid 8.2. The alternating current impedance spectroscopy of glycine showed that the cell performance is determined by the chemical reactions at TiO₂ or Pt electrodes.     

Electrophoretic deposition of nanocrystalline TiO2 films on Ti substrates for use in flexible dye-sensitized solar cells

Nanocrystalline TiO₂ films were prepared on flexible Ti-metal sheets by electrophoretic deposition followed by chemical treatment with tetra-n-butyl titanate (TBT) and sintering at 450 °C. X-ray diffraction (XRD) analysis indicates that TBT treatment led to the formation of additional anatase TiO₂, which plays an important role in improving the interconnection between TiO₂ particles, as well as the adherence of the film to the substrate, and in modifying the surface properties of the nanocrystalline particles. The effect of TBT treatment on the electron transport in the nanocrystalline films was studied by intensity-modulated photocurrent spectroscopy (IMPS). An increase in the conversion efficiency was obtained for the dye-sensitized solar cells with TBT-treated nanocrystalline TiO₂ films. The cell performance was further optimized by designing nanocrystalline TiO₂ films with a double-layer structure composed of a light-scattering layer and a transparent layer. The light-scattering effect of the double-layer nanocrystalline films was evaluated by diffuse reflectance spectra. Employing the double-layer nanocrystalline films as the photoelectrodes resulted in a significant improvement in the incident photo-to-current conversion efficiency of the corresponding cells due to enhanced solar absorption by light scattering. A high conversion efficiency of 6.33% was measured under illumination with 100 mW cm⁻² (AM 1.5) simulated sunlight.     

Light management in dye-sensitized solar cell

Dye-sensitized solar cell (DSSC) is composed of a nanocrystalline TiO₂ film whose surface is covered with dye molecules, an iodide/tri-iodide electrolyte and a platinum counter electrode. Charge generation occurs when dye absorbs photon energy, which is separated by injection of photo-excited electrons into the conduction band of TiO₂. The photo-injected electrons are transported through TiO₂ network and collected at transparent conducting electrode. The oxidized dyes are regenerated by oxidation of iodide. Light-to-electricity conversion efficiency depends on photocurrent density, open-circuit voltage and fill factor. Photocurrent density is related to the incident photon-to-current conversion efficiency (IPCE) that is a collective measure of light harvesting, charge separation and charge collection efficiency. Since the higher IPCE, the higher photocurrent density becomes, light management in DSSC is one of most important issues. In this paper, effective methods to improve IPCE are described including size-dependent light scattering effect, bi-functionality design in material synthesis and panchromatic approach such as selective position of different dyes in a mesoporous TiO₂ film.     

Aerosol assisted chemical vapour deposited (AACVD) of TiO2 thin film as compact layer for dye-sensitised solar cell

Compact TiO₂ has been introduced onto the surface of an indium tin oxide glass slide (ITO), using an aerosol-assisted chemical vapour deposition method. This serves as a blocking layer for a dye-sensitised solar cell (DSSC). The thickness of the compact TiO₂ could be controlled by deposition time. X-ray diffraction and Raman spectroscopy analyses reveal that the compact TiO₂ is made up of mixed anatase and rutile phases. The field emission scanning electron microscopy image displays a pyramidal morphology of the compact TiO₂. A layer of P25 paste was then smeared onto the compact TiO₂-modified ITO, using the doctor's blade method. A post-treatment procedure was applied to remove the contaminants from the prepared hybrid film, by immersing in a hydrochloric acid solution. The photoelectrochemical measurements and J–V characterisation of the hybrid film show an approximately fourfold increase in photocurrent density generation (114.22 µA/cm²), and approximately 25% enhancement of DSSC conversion efficiency (4.63%), compared to the acid-treated P25 paste alone (3.68%).     

Fabrication and photoelectrochemical properties of TiO2 films on Ti substrate for flexible dye-sensitized solar cells

The dye-sensitized solar cells (DSSCs) using Ti foil supporting substrate for fabricating nanocrystalline TiO₂ flexible film electrodes were developed, intending to improve the photoelectrochemical properties of flexible substrate-based DSSCs. The obtained cells were characterized by electrochemical impedance spectra (EIS), open circuit voltage decay (OCVD) measurement and Tafel plots. The experimental results indicate that the most important advantage of a Ti foil-based TiO₂ flexible electrode over a FTO glass-based electrode lies in its reduced sheet resistance, electron traps, and the retarded back reaction of electrons with tri-iodine ions in DSSCs. All above characteristics for the Ti substrate TiO₂ films are beneficial for decreasing the charge recombination in the TiO₂ electrode and prolonging the electron lifetimes for the DSSCs, as well as improvement of the overall solar conversion efficiency. The photocurrent of the cell fabricated with the Ti foil-based flexible electrode increased significantly, leading to a much higher overall solar conversion efficiency of 5.45% at 100 mW/cm² than the cell made with FTO glass-based TiO₂ electrodes. Above results demonstrate that Ti foil is a potential alternative to the conventional FTO glass substrate for the DSSCs.     

Anodic TiO2 Nanotube Arrays for Dye-Sensitized Solar Cells Characterized by Electrochemical Impedance Spectroscopy

This paper reports on the microstructure of anodic titanium oxide (TiO₂) and its use in a dye-sensitized solar cell (DSSC) device. When voltages of 60 V were applied to titanium foil for 2 hr under 0.25 wt% NH₄F+ 2 vol% H₂O+C₂H₄(OH)₂, TiO₂ with a nanotube structure was formed. The film, which had a large surface area, was used as an electron transport film in the DSSC. The DSSC device had a short-circuit current density (J_sc) of 12.52 mA cm⁻², a fill factor (FF) of 0.65, an open-voltage (V_oc) of 0.77 V, and a photocurrent efficiency of 6.3% under 100% AM 1.5 light. The internal impedance values under 100%, 64%, 11%, and 0% (dark) AM 1.5 light intensities were measured and simulated using the electrical impedance spectroscopy (EIS) technique. The impedance characteristics of the DSSC device were simulated using inductors, resistors, and capacitors. The Ti/TiO₂, TiO₂/Electrolyte, electrolyte, and electrolyte/(Pt/ITO) interfaces were simulated using an RC parallel circuit, and the bulk materials, such as the Ti, ITO and conducting wire, were simulated using a series of resistors and inductors. The impedance of the bulk materials was simulated using L₀+R₀+R_b, the impedance of the working electrode was simulated using (C₁//R₁)//(R_a+(C₂//R₂), the electrolyte was simulated using C₃//R₃, and the counter electrode was simulated using C₄//R₄.     

Horseradish peroxidase immobilized in TiO2 nanoparticle films on pyrolytic graphite electrodes: direct electrochemistry and bioelectrocatalysis

Horseradish peroxidase (HRP)-TiO₂ film electrodes were fabricated by casting the mixture of HRP solution and aqueous titania nanoparticle dispersion onto pyrolytic graphite (PG) electrodes and letting the solvent evaporate. The HRP incorporated in TiO₂ films exhibited a pair of well-defined and quasi-reversible cyclic voltammetric peaks at about −0.35 V versus saturated calomel electrode (SCE) in pH 7.0 buffers, characteristic of HRP-Fe(III)/Fe(II) redox couple. The electron exchange between the enzyme and PG electrodes was greatly enhanced in the TiO₂ nanoparticle film microenvironment. The electrochemical parameters such as apparent heterogeneous electron transfer rate constant (k_s) and formal potential (E°′) were estimated by fitting the data of square wave voltammetry with nonlinear regression analysis. The HRP-TiO₂ film electrodes were quite stable and amenable to long-time voltammetric experiments. The UV-Vis spectroscopy showed that the position and shape of Soret absorption band of HRP in TiO₂ films kept nearly unchanged and were different from those of hemin or hemin-TiO₂ films, suggesting that HRP retains its native-like tertiary structure in TiO₂ films. The electrocatalytic activity of HRP embedded in TiO₂ films toward O₂ and H₂O₂ was studied. Possible mechanism of catalytic reduction of H₂O₂ with HRP-TiO₂ films was discussed. The HRP-TiO₂ films may have a potential perspective in fabricating the third-generation biosensors based on direct electrochemistry of enzymes.     

Enhancement of photocurrents due to the oxidation of water and organic compounds at BiZn2VO6 particulate thin film electrodes by treatment with a TiCl4 solution

Photocurrents due to water oxidation at BiZn₂VO₆ (E_g 2.4 eV) particulate thin film electrodes were largely enhanced by pre-treatment with an aqueous TiCl₄ solution. Photocurrents for BiZn₂VO₆ electrodes with no TiCl₄ treatment were also enhanced by the addition of organic compounds such as methanol and trimethyl amine to the aqueous electrolyte. Interestingly, such enhanced photocurrents by organic compounds were further enhanced by the TiCl₄ pre-treatment. EDAX and SEM investigations showed the formation of a flock-like TiO₂ overlayer on BiZn₂VO₆ particles after the TiCl₄ treatment. The photocurrent enhancement by the TiCl₄ pre-treatment is thus mainly attributed to the necking effect of the flock-like TiO₂ overlayer, which facilitates the transport of photogenerated electrons within the BiZn₂VO₆ particulate thin film electrode.     

Photosensitization of TiO2 nanorods with CdS quantum dots for photovoltaic devices

CdS quantum dots (QDs) coated TiO₂ nanorod arrays have been prepared via a two-step method. TiO₂ nanorod arrays were synthesized by a facile hydrothermal method, and CdS QDs were deposited on the nanorods by a sequential chemical bath deposition (S-CBD) technique. The surface morphology, structure, optical and photoelectrochemical behaviors of the core-shell nanorod array films are considered. A photocurrent of 2.5 mA/cm², an open circuit photovoltage of 1.10 V, and a conversion efficiency of 1.91% were obtained under an illumination of 100 mW/cm², when the CdS QDs deposited on TiO₂ nanorods film for about 7 cycles. The results demonstrate that the composite films are of excellence with respect to photovoltaic conversion.     

Immobilization of horseradish peroxidase in three-dimensional macroporous TiO2 matrices for biosensor applications

Three-dimensional macroporous TiO₂ was synthesized by a sol-gel procedure using polystyrene colloidal crystals as templates. SEM showed that a face-centered cubic (FCC) 3D macroporous structure was obtained. Horseradish peroxidase (HRP) was successfully immobilized on the surface of an optically transparent electrode (OTE). Photoelectrochemical properties were characterized using a three electrodes system and an ultraviolet lamp. The HRP/TiO₂/OTE displays a rapid photocurrent response, approximately 178.7 nA, under UV illumination (380 nm). The sensitivity of H₂O₂ detection was 70.04 μA/mM without UV illumination, and it increased to 102.97 μA/mM when illuminated by UV. The amperometric response was also enhanced. The high response was due to the good biocompatibility of TiO₂ and excellent photoelectrical property and the large effective surface of the three-dimensionally ordered macroporous structure.     

Effect of TiO2 supporting layer on Fe2O3 photoanode for efficient water splitting

For an electrochemical water splitting system, titanate nanotubular particles with a thickness of ∼700 nm produced by a hydrothermal process were repetitively coated on fluorine-doped tin oxide (FTO) glass via layer-by-layer self-assembly method. The obtained titanate/FTO films were dipped in aqueous Fe solution, followed by heat treatment for crystallization at 500 °C for 10 min in air. The UV–vis absorbance of the Fe-oxide/titanate/FTO film showed a red-shifted spectrum compared with the TiO₂/FTO coated film; this red shift was achieved by the formation of thin hematite-Fe₂O₃ and anatase-TiO₂ phases verified using X-ray diffraction and Raman results. The cyclic voltammetry results of the Fe₂O₃/TiO₂/FTO films showed distinct reversible cycle characteristics with large oxidation–reduction peaks with low onset voltage of I–V characteristics under UV–vis light illumination. The prepared Fe₂O₃/TiO₂/FTO film showed much higher photocurrent densities for more efficient water splitting under UV–vis light illumination than did the Fe₂O₃/FTO film. Its maximum photocurrent was almost 3.5 times higher than that obtained with Fe₂O₃/FTO film because of the easy electron collection in the current collector. The large current collection was due to the existence of a TiO₂ base layer beneath the Fe₂O₃ layer.     

A pH sensor based on the TiO2 nanotube array modified Ti electrode

In this paper, a novel solid state pH sensor was fabricated by anodization of titanium substrate electrode. The relationship between pH sensitivity and hydrophilicity or surface morphology of TiO₂ film was investigated. Amorphous TiO₂ nanotube has better pH response than anatase TiO₂ nanotube. After being irradiated by ultraviolet light (UV), the potential response of the electrode modified by amorphous TiO₂ nanotube was close to Nernst equation (59 mV/pH). SEM, XRD, and XPS were used to characterize electrodes. Possible mechanism was discussed by analyzing surface hydroxyl groups, crystal structure and hydrophilicity of the electrodes. The electrode has been used to detect some kinds of soft drinks and shows good response.     

TiO2 nanotubes manufactured by anodization of Ti thin films for on-chip Li-ion 2D microbatteries

The use of self-organized TiO₂ nanotube arrays electrochemically grown onto Si is investigated for the fabrication of an alternative electrode dedicated to on-chip Li-ion 2D microbatteries. Discharge/charge curves and cycling performance are studied in lithium-anode electrochemical test cells for both amorphous and crystalline titania nanotubes. At 5 μA cm⁻² amorphous TiO₂ nanotube layers onto Si deliver a maximum areal capacity of 89 μAh cm⁻² in the first reversible discharge and 56 μAh cm⁻² over 50 cycles. We demonstrate that these nanostructured thin film electrodes showing such electrochemical performances are compatible with IC technology.     

Novel graphite/TiO2 electrochemical cells as a safe electric energy storage system

A graphite/TiO₂ full cell has been developed as a new safety energy storage system using a highly safety process. The crystal structures of the anatase TiO₂ electrode have been investigated with respect to the performance of the electrodes. Due to the large anion intercalation into the graphite positive electrode, the possible charging potential can be raised to around 5.3 V against the Li/Li⁺ electrode, which is a higher charging voltage than lithium-ion batteries (maximum voltage is around 4.3 V vs. Li/Li⁺). In situ XRD measurements have been carried out on both the cathode and anode electrodes of the graphite/TiO₂ cell during the charge process to elucidate the intercalation mechanism.     

Enhancement of photoelectric conversion by high-voltage electric field assisted crystallization of a novel ternary-encapsulated spherical TiO2 aggregate for solar cells

A novel ternary-encapsulated spherical TiO₂ aggregate (TES-TiO₂) with submicron particle sizes was formed by blending commercial P25 TiO₂ and two different sizes of TiO₂ particles (synthesized by modified sol-gel and hydrothermal methods). A double-layered TiO₂ electrode for dye-sensitized solar cells (DSSCs) was fabricated by depositing TES-TiO₂ particles onto nanocrystalline mesoporous TiO₂ (Meso-TiO₂)-coated FTO glass by a cathodic electrophoresis technique and then calcined at 450 °C for 30 min. Compared to double-layered Meso-TiO₂/P25 electrodes, the energy conversion efficiency (η) of DSSCs from the obtained Meso-TiO₂/TES-TiO₂ electrode was improved by 9.3%, from 5.94% to 6.49%. When the prepared double-layered Meso-TiO₂/TES-TiO₂ electrode was calcined at high temperature, a high-voltage electric field (HVEF) was introduced to assist crystallization. As a result, η was further enhanced by 8.6%, from 6.49% to 7.05%. Notably, compared to typical 20 nm TiO₂ nanocrystallites applied in the active layer of DSSCs, the prepared loosely porous TES-TiO₂ with submicron size increased the light-scattering effect and promoted dye molecule adsorption and the diffusion of electrolytes. In addition, introduction of the HVEF provided better connection among TiO₂ particles, which facilitated electron transport and avoided charge recombination.     

Large-scale preparation of nanoporous TiO2 film on titanium substrate with improved photoelectrochemical performance

Fabrication of three-dimensional TiO₂ films on Ti substrates is one important strategy to obtain efficient electrodes for energy conversion and environmental applications. In this work, we found that hierarchical porous TiO₂ film can be prepared by treating H₂O₂ pre-oxidized Ti substrate in TiCl₃ solution followed by calcinations. The formation process is a combination of the corrosion of Ti substrate and the oxidation hydrolysis of TiCl₃. According to the characterizations by scanning electron microscopy (SEM), X-ray diffraction (XRD), and diffuse reflectance spectroscopy (DRS), the anatase phase TiO₂ films show porous morphology with the smallest diameter of 20 nm and possess enhanced optical absorption properties. Using the porous film as a working electrode, we found that it displays efficient activity for photoelectrocatalytic decolorization of rhodamine B (RhB) and photocurrent generation, with a photocurrent density as high as 1.2 mA/cm². It represents a potential method to fabricate large-area nanoporous TiO₂ film on Ti substrate due to the scalability of such chemical oxidation process.     

Enhancing the performance of dye-sensitized solar cells based on an organic dye by incorporating TiO2 nanotube in a TiO2 nanoparticle film

The photoelectrochemical properties of a high molar extinction coefficient charge transfer organic dye containing thienylfluorene segment called FL, and the effect of incorporating TiO₂ nanotube (TiNT) in TiO₂ nanoparticle film along with the above dye on the photovoltaic performance of dye-sensitized solar cells (DSSCs) were investigated. The influence of soaking time of the TiO₂ electrode in dye solution and the effect of varying its concentration, on the solar cell efficiency was also studied. Cyclic voltammetric (CV) analysis revealed the linear relationship between the anodic peak current and the scan rate, indicating a surface-confined diffusion process.The surface morphology of TiNT was characterized using SEM, TEM and XRD. The open-circuit voltage (V_OC) of the DSSC increased with the increase in the wt% of TiNT and shows optimal value at about 5 wt%, which is correlated with the suppression of the electron recombination as found out from the electron lifetime studies.The electrochemical impedance spectroscopy (EIS) technique was employed to quantify the charge transport resistance (R_ct) and electron lifetime under different ratios of the TiNT/nanoparticle. The electron lifetimes of the DSSCs based on FL and N3 dye were very close to one another and the DSSC based on the FL showed respectable photovoltaic performance of ca. 7.8% under the light intensity of 100 mW cm⁻² (AM 1.5G).     

Study on photocatalytic deposition of bismuth onto nanocrystalline TiO2 by quartz crystal microbalance and electrochemical method

In situ techniques of quartz crystal microbalance (QCM), differential pulse voltammetry (DPV) and amperometric measurement were employed to investigate the adsorption Bi(III) ions and the photocatalytic deposition Bi process at the surface of nanocrystalline TiO₂. It was obtained that the adsorption of Bi(III) ions onto nanocrystalline TiO₂ accords with the pseudo-second-order reaction and the reaction rate constant k was about 13.3 g mol⁻¹ min⁻¹. In addition, the photocatalytic deposition of Bi onto the surface of TiO₂ was further investigated. It was found that photocatalytic deposition rate at the surface of TiO₂ was enhanced by increasing pH value or initial concentration of Bi(III) ions. The influence of organic hole-scavegeners on the photocatalytic deposition of Bi was also investigated, and it was obtained that formic acid may be the best for the photocatalytic reduction of Bi. The mass ratio between the Bi(III) and Bi metal deposition was calculated as 7.48:1. Therefore, it can be concluded that QCM, DPV and amperometric measurement may be effective and reliable for the investigation of the photocatalytic deposition of Bi onto the surface of nanocrystalline TiO₂.