Preparation and characterization of TiO2/Ti film electrodes by anodization at low voltage for photoelectrocatalytic application

Multiporous TiO₂/Ti film electrodes were prepared by different anodic oxidation processes at low voltage, in which the micro-structured TiO₂ thick films were prepared in H₂SO₄–H₂O₂–H₃PO₄–HF solution for 2 h and the nano-structured TiO₂ thin films were prepared in H₃PO₄–HF solution for 30 min with post-calcination. Both types of TiO₂/Ti films were characterized by scanning electron microscopy and X-ray diffraction analysis. The photocatalytic (PC) and photoelectrocatalytic (PEC) reactivity of the TiO₂/Ti electrodes were evaluated in terms of bisphenol A (BPA) degradation in aqueous solution. The experimental results demonstrated that the nano-structured TiO₂/Ti thin-film electrodes had higher reactivity in the BPA degradation reaction. The PEC degradation of BPA was further studied using different cathodes, either a reticulated vitreous carbon (RVC) electrode or a platinum (Pt) electrode. The experimental results confirmed that the efficiency of BPA degradation could be significantly enhanced in the TiO₂/Ti–RVC reaction system due to the generation of H₂O₂ on the RVC cathode. It is believed that such a H₂O₂-assisted TiO₂ PEC oxidation process may have good potential for water and wastewater treatment.     

Photoelectrocatalytic degradation of rhodamine B using Ti/TiO2 electrode prepared by laser calcination method

The method of Ti/TiO₂ photoelectrode prepared by using laser calcination method instead of oven calcination process was introduced. The prepared TiO₂ film was observed with AFM and XRD. Photoelectrocatalytic degradation of rhodamine B (RB) using this electrode was investigated, and anodic potential and pH were optimized. The laser power applied in this electrode preparation was also discussed, and it indicated that TiO₂ particle prepared with high laser power was crystallized adequately and the photoelectrocatalytic ability was satisfactory. RB degradation was investigated under different conditions, and it showed that photoelectrocatalytic degradation could achieve efficient and complete mineralization of organic pollutant. The photoelectrocatalytic oxidation using the Ti/TiO₂ electrode calcinated by laser was compared with that of the electrode calcinated by furnace, and it showed that the reaction rate of RB degradation using the electrode by laser was faster than that by furnace. Additionally, electrochemical impedance spectroscopy (EIS) was performed at the two different photoelectrodes, which verified the higher photocatalytic activity of the laser-treated electrode further.     

Low temperature preparation of a high performance Pt/SWCNT counter electrode for flexible dye-sensitized solar cells

A platinum/single-wall carbon nanotube (Pt/SWCNT) film was sprayed onto a flexible indium-doped tin oxide coated polyethylene naphthalate (ITO/PEN) substrate to form a counter electrode for use in a flexible dye-sensitized solar cell using a vacuum thermal decomposition method at low temperature (120 °C). The obtained Pt/SWCNT electrode showed good chemical stability and light transmittance and had lower charge transfer resistance and higher electrocatalytic activity for the I₃⁻/I⁻ redox reaction compared to the flexible Pt electrode or a commercial Pt/Ti electrode. The light-to-electric energy conversion efficiency of the flexible DSSC based on the Pt/SWCNT/ITO/PEN counter electrode and the TiO₂/Ti photoanode reached 5.96% under irradiation with a simulated solar light intensity of 100 mW cm⁻². The efficiency was increased by 25.74% compared to the flexible DSSC with an unmodified Pt counter electrode.     

Photocatalytic functional coatings of TiO2 thin films on polymer substrate by plasma enhanced atomic layer deposition

We prepared photocatalytic TiO₂ thin films which exhibited relatively high growth rate and low impurity on polymer substrate by plasma enhanced atomic layer deposition (PE-ALD) from Ti(NMe₂)₄ [tetrakis (dimethylamido) Ti, TDMAT] and O₂ plasma to show the self-cleaning effect. The TiO₂ thin films with anatase phase and bandgap energy about 3.3 eV were deposited at growth temperature of 250 °C and the photocatalytic effects were compared with commercial Activ glass. From contact angles measurement of water droplet and photo-induced degradation test of organic liquid, TiO₂ thin films with anatase phases showed superhydrophilic phenomena and decomposed organic liquid after UV irradiation. The anatase TiO₂ thin film on polymer substrate showed highest photocatalytic efficiency after 5 h UV irradiation. We attribute the highest photocatalytic efficiency of TiO₂ thin film with anatase structure to the formation of suitable crystalline phase and large surface area.     

Thickness effect in the photocatalytic activity of TiO2 thin films derived from sol-gel process

TiO₂ films in various thicknesses were prepared by sol-gel method, and their photocatalytic activities in the decomposition of gaseous 2-propanol were evaluated. It was found that the photocatalytic activities of transparent TiO₂ films increase with the increase of film thickness: The photocatalytic activity of TiO₂ films in 670 nm-thickness was 3.7 times that of films in 70 nm-thickness. We proposed that the higher photocatalytic activities for the thicker TiO₂ films originate from the greater amount of photogenerated electron and hole pairs, which are transferred from the inside to the surface of TiO₂ films. We also provided some experimental evidences supporting this mechanism.     

Effect of rapid thermal annealing on the structural and electrical properties of TiO2 thin films prepared by plasma enhanced CVD

Titanium oxide thin films were deposited on p-type Si(100), SiO₂/Si, and Pt/Si substrates by plasma enhanced chemical vapor deposition using high purity Ti(O-i-C₃H₇)₄ and oxygen. As-deposited amorphous TiO₂ thin films were treated by rapid thermal annealing (RTA) in oxygen ambient, and the effects of RTA conditions on the structural and electrical properties of TiO₂ films were studied in terms of crystallinity, microstructure, current leakage, and dielectric constant. The dominant crystalline structures after 600 and 800 ‡C annealing were an anatase phase for the TiO₂ film on SiO₂/Si and a rutile phase for the film on a Pt/Si substrate. The dielectric constant of the as-grown and annealed TiO₂ thin films increased depending on the substrate in the order of Si, SiO₂/Si, and Pt/ Si. The SiO₂ thin layer was effective in preventing the formation of titanium silicide at the interface and current leakage of the film. TEM photographs showed an additional growth of SiO_x from oxygen supplied from both SiO₂ and TiO₂ films when the films were annealed at 1000 ‡C in an oxygen ambient. Intensity analysis of Raman peaks also indicated that optimizing the oxygen concentration and the annealing time is critical for growing a TiO₂ film having high dielectric and low current leakage characteristics.     

The dependence of the photocatalytic activity of TiO2/carbon nanotubes nanocomposites on the modification of the carbon nanotubes

Nanostructural TiO₂/modified multi-wall carbon nanotubes photocatalysts were prepared by hydrolysis of Ti(iso-OC₃H₇)₄ providing chemical bonding of anatase TiO₂ nanoparticles onto oxidized- or amino-functionalized multi-wall carbon nanotubes (MWCNT). The processes of functionalization of the MWCNT and the deposition of TiO₂ influence the photocatalytic activity of the synthesized nanocomposites. The phase composition, crystallite size, and the structural and surface properties of the obtained TiO₂/modified-MWCNT nanocomposite were analyzed from XRD, FEG-SEM, TEM/HRTEM and FTIR data, as well low temperature N₂ adsorption. In the photocatalytic study, the TiO₂/oxidized-MWCNT catalyst showed the highest and the TiO₂/amino functionalized-MWCNT catalysts somewhat lower degradation rates, indicating that the enhancement of photocatalysis was supported by the more effective electron transfer properties of the oxygen- than amino-containing functional groups, which support the efficient charge transportation and separation of the photogenerated electron-hole pairs.     

Effect of Si doping on the photocatalytic activity and photoelectrochemical property of TiO2 nanoparticles

Si-doped TiO₂ nanoparticles with anatase crystalline phase were prepared by a hydrothermal method using acetic acid as the solvent. Photoelectrochemical studies showed that the photocurrent value for the 15% Si-doped TiO₂ electrode (54.4 μA) was much higher than that of the pure TiO₂ electrode (16.7 μA). In addition, the 15% Si-doped TiO₂ nanoparticles displayed the highest photocatalytic activity under ultraviolet light irradiation. So doping suitable amount of Si in TiO₂ nanoparticles was profitable for transferring photogenerated electrons and inhibiting the recombination of photogenerated electrons and holes. As a result, the photocatalytic activity of TiO₂ nanoparticles was improved.     

Nanoporous TiO<Subscript>2</Subscript> film electrode for electrocatalytic reduction of 2-pyridineethanol in ionic liquids

Nanoporous TiO₂ having enhanced surface area was synthesized by sol–gel method. On the nanoporous TiO₂ film electrode, electrocatalytic reduction of the 2-pyridineethanol in the ionic liquid electrolyte of 1-ethyl-3-methylimidazolium tetrafluoroborate ([EMI]BF₄) was investigated by cyclic voltammetry (CV). It was found that the indirect electroreduction of 2-pyridineethanol produced 2-piperidinoethanol by Ti(IV)/Ti(III) redox system on the nanoporous TiO₂ film surface. The current of cathodic reduction peak increased along with the increase of reactant concentration. The electrode reaction mechanism is called catalytic (EC′) mechanism.     

Photochemical diodes of a TiO2 film prepared by a sol-gel method

Photochemical diodes were prepared using a thin film of TiO₂ made from titanium isopropoxide by a sol-gel method. A half part of a conductive SnO₂ film plated on a quartz plate was coated with the TiO₂ film, and the other parts of the SnO₂ substrate were coated with a thin Pt film. The photochemical diode thus prepared shows photocatalytic activity for hydrogen evolution from aqueous ethanol solutions containing NaOH or HClO₄. No other products are detected in the gas phase. Hydrogen evolution from the Pt part is definitely observed, indicating electron transfer from the TiO₂ film to the Pt film through the SnO₂ film. Another type of photochemical diode, the TiO₂ film coated on a Pt plate, is found to show higher activity than the TiO₂/SnO₂/Pt device for the hydrogen photo-evolution without any support electrolyte. Hydrogen evolution on this device, however, occurs on the TiO₂ side but not on the Pt side. These results are discussed in terms of a photo-electrochemical mechanism at semiconductor surfaces.     

A novel hierarchical Pt- and FTO-free counter electrode for dye-sensitized solar cell

A novel hierarchical Pt- and FTO-free counter electrode (CE) for the dye-sensitized solar cell (DSSC) was prepared by spin coating the mixture of TiO₂ nanoparticles and poly(3,4-ethylenedioxy-thiophene):poly(styrenesulfonate) (PEDOT:PSS) solution onto the glass substrate. Compared with traditional Pt/FTO CE, the cost of the new CE is dramatically reduced by the application of bilayer TiO₂-PEDOT:PSS/PEDOT:PSS film and the glass substrate. The sheet resistance of this composite film is 35 Ω sq⁻¹ and is low enough to be used as an electrode. The surface morphologies of TiO₂-PEDOT:PSS layer and modified PEDOT:PSS layer were characterized by scanning electron microscope, which shows that the former had larger surface areas than the latter. Electrochemical impedance spectra and Tafel polarization curves prove that the catalytic activity of TiO₂-PEDOT:PSS/PEDOT:PSS/glass CE is higher than that of PEDOT:PSS/FTO CE and is similar to Pt/FTO CE''s. This new fabricated device with TiO₂-PEDOT:PSS/PEDOT:PSS/glass CE achieves a high power conversion efficiency (PCE) of 4.67%, reaching 91.39% of DSSC with Pt/FTO CE (5.11%).     

Hydrothermal growth of TiO2 nanowire membranes sensitized with CdS quantum dots for the enhancement of photocatalytic performance

In this paper, TiO₂ nanowires (NWs) on Ti foils were prepared using a simple hydrothermal approach and annealing treatment. CdS quantum dots (QDs) were assembled onto the crystallized TiO₂ NWs by sequential chemical bath deposition. Ultraviolet-visible absorption spectra showed that CdS adds bands in the visible to the TiO₂ absorption and exhibited a broad absorption band in the visible region, which extended the scope of absorption spectrum and helped improve the photocatalytic degradation efficiency. The results of photocatalytic experiment revealed that CdS-TiO₂ NWs possessed higher photocatalytic activities toward methyl orange than pure TiO₂ nanowires. The degradation efficiency of 96.32% after ten cycles indicated that the as-prepared CdS-TiO₂ composite exhibited excellent long-time recyclable ability and can be reused for the degradation of contaminants.     

Photocatalytic degradation rate of oxalic acid on a semiconductive layer of n-TiO2 particles in a batch mode plate photoreactor Part II: Light intensity limit

The effect of light intensity, flow rate and oxygen bubbling on the photocatalytic degradation rate of oxalic acid on a layer of TiO2 particles was investigated. At higher concentrations of oxalic acid ( 0.005 M) and photon flux intensity in the range 3.26 × 10–10 to 1.07 × 10–8 einstein cm–2 s–1, the rate of photocatalysis was controlled simultaneously by the flux of both oxygen and photons. This is probably caused by the ability of oxygen to react with photogenerated electrons and thus suppress the electron-hole recombination and increase the efficiency of the photocatalytic degradation.     

Photocatalytic reactivity and diffusing OH radicals in the reaction medium containing TiO2 particles

The generation of OH radicals on UV-illuminated TiO₂ surface is mainly responsible for the photocatalytic oxidation of pollutants in various contaminated environmental media. Although the reactivity of OH radicals is largely limited within the surface region, the possibility of OH desorption and diffusion into the reaction medium has been often raised. This study provides several examples for the presence of diffusing OH radicals in aqueous solution and polymer matrix containing TiO₂ particles. The photocatalytic degradation rates of (CH₃)₄N⁺ in TiO₂ suspension were comparable between acidic and alkaline conditions, which could not be explained by a simple electrostatic surface charge model. From the present mechanistic study, it is suggested that the photocatalytic oxidation of (CH₃)₄N⁺ at acidic pH mainly proceeds through free OH radicals in the solution bulk, not on the surface of TiO₂. The diffusing OH radicals also played the role of main oxidants in the solid phase. The photolysis of TiO₂-embedded PVC composite films generated cavities around the imbedded TiO₂ particles and the development of cavity diameter continued even after the direct contact between the PVC and TiO₂ was prohibited. This implied that active oxygen species that were photogenerated on TiO₂ surface desorbed and diffused across a few micrometers to react with the polymer matrix.     

Photocatalytic degradation of oxalic acid on a semiconductive layer of n-TiO2 particles in a batch plate reactor. Part III: Rate determining steps and nonsteady diffusion model for oxygen transport

The effect of oxygen concentration on the photocatalytic degradation rate of oxalic acid on a fixed layer of TiO₂ particles in a batch mode plate photoreactor was investigated at various light intensities. The regions where the photocatalytical decomposition rate is controlled by the flux of oxygen, photons, or both, were identified. For low oxygen concentration (0–0.15 mol m^–3) and photon flux intensity in the range from 10 to 24 × 10^–5 einstein m^–2 s^–1 the experimentally determined photocatalytical decomposition rate was in agreement with that theoretically calculated assuming the process to be controlled by the limiting flux of oxygen to the TiO₂ surface. At higher concentrations of oxygen (0.15–0.94 mol m^–3) the rate of photocatalysis was controlled simultaneously by both the flux of oxygen and photons. The influence of the oxygen concentration decreased with decreasing photon flux. For low photon flux intensities (3.5 × 10^–5 einstein m^–2 s^–1), the reaction rate was controlled by the photon flux. The concentration profile of oxygen in the diffusion layer along the reactor plate was calculated and showed a significant decrease in oxygen concentration on the TiO₂ surface.     

Titanium mesh-supported TiO2 nano-film for the photocatalytic degradation of ethylene under a UV-LED

In this paper, TiO₂ nano-films with different morphologies were synthesized on titanium mesh by a hydrothermal treatment. The crystalline structure and surface morphology of the TiO₂ nano-films were characterized by X-ray photoelectron spectroscopy (XRD), field emission scanning electron microscopy (FESEM), and high-resolution transmission electron microscope (HRTEM). The photocatalytic degradation of ethylene using the TiO₂ catalyst was carried out. The effect of the photoreaction temperature, initial concentration of ethylene and light intensity on photodegradation under ultraviolet-light emitting diode (UV-LED) light was investigated. The photocatalytic stability of the TiO₂ nano-film catalyst was also evaluated. The results revealed that the photodegradation of ethylene gas follows the pseudo-first-order kinetics model. The photoreactivity was enhanced by increasing the light intensity and the photoreaction temperature but decreased with the increase in the initial ethylene concentration. The nanowire-shaped TiO₂ film showed a superior photocatalytic performance and an excellent stability. The electrochemical impedance spectroscopy and transient photocurrent response studies revealed that the nanowire-shaped TiO₂ film possesses an excellent separation ability in the electron hole pair of the photogenerated electron-hole pairs due to the high degree of crystallinity and the heterojunction between the rutile and anatase phases of TiO₂. We expect that the findings will have practical applications in fruit preservation and other agricultural products.     

TiO2/ZnO Supported on Sepiolite: Preparation,Structural Characterization,and Photocatalytic Degradation of Flumequine Antibiotic in Aqueous Solution

In this study, TiO₂, ZnO, TiO₂/ZnO (Ti/Zn), and TiO₂/ZnO/Sep (Ti/Zn/Sep) catalysts have been synthesized using sol–gel and chemical precipitation method. Their photocatalytic performances have been compared using Flumequine (FLQ) antibiotic. X-ray diffraction (XRD), Fourier transform infrared spectra (FTIR), scanning electron microscopy (SEM), N₂-adsorption, and the determination of a zero point charge has been used to characterize the synthesized catalysts. The degradation studies showed that the catalytic efficiency of Ti/Zn/Sep is higher than that for other catalysts. The operational parameters such as pH, initial FLQ concentration, and catalyst dosage were evaluated. UV–vis and high-resolution mass spectroscopy (HRMS) analyses were used to determine the degradation efficiency and products. ZnO played a major role in the FLQ degradation process, and sepiolite contributed to adsorption of FLQ on the catalyst surface enormously. The catalysts exhibited 11%, 23%, 63%, and 85% degradation efficiency for ZnO, TiO₂, Ti/Zn, and Ti/Zn/Sep in the decomposition of FLQ, respectively.     

Applicability of coumarin for detecting and measuring hydroxyl radicals generated by photoexcitation of TiO2 nanoparticles

Applicability of coumarin (COU) as fluorescent probe to detect and measure hydroxyl radicals generated by UV irradiation of aqueous suspension of TiO₂ was investigated under aerobic and anaerobic conditions. The fluorescent 7-hydroxycoumarin (7HC) was formed in argon-saturated suspension when silver ion was used as electron acceptor. The luminescence intensity increased with irradiation time until the deposition of silver on the surface of TiO₂ was completed and then the luminescence intensity was constant and proportional to the initial concentration of the silver ion. The low yield of 7HC related to the deposited silver (0.32%) indicates the appearance of efficient side reactions of hydroxyl radicals and holes. It has also been demonstrated that efficient electron donors reacting directly with photogenerated holes such as oxalic acid significantly reduce the yield of 7HC. Using oxalic acid of relatively high concentration in aerated suspension leads to the production of hydroxyl radical in thermal reactions followed by primary electron transfer steps.     

Photocatalytic Decomposition of Lactic Acid in Water on a Photoelectrochemical Circuit System Consisting of a Rod-type TiO2 Electrode and Silicon Solar Cell

Lactic acid, a well-known substance causing dental caries, was dissolved in water and completely oxidized into CO₂ and H₂O on a powdered TiO₂ photocatalyst under UV light irradiation. Furthermore, a unique photoelectrochemical circuit system consisting of a rod-type TiO₂ electrode and counter electrode connected through a silicon solar cell was constructed and its photocatalytic activity for the decomposition of lactic acid was investigated. The photoelectrochemical circuit system was found to effectively mineralize the lactic acid in water into CO₂ while the negative bias applied on the rod-type TiO₂ electrode enhanced the photocatalytic decomposition rate of the lactic acid.     

Efficient visible-light photocatalysts from Gd–La codoped TiO2 nanotubes

Robust visible-light Gd–La codoped TiO₂ nanotubes were successfully synthesized via an ultrasonic hydrothermal method and the photocatalytic activities were evaluated by photodegrading Rhodamine B (RB). The calcined Gd–La codoped TiO₂ nanotubes have significantly enhanced photocatalytic activities than the uncalcined ones. The La³⁺ and Gd³⁺ in the lattices of rare earth oxides may be substituted by Ti⁴⁺, creating abundant oxygen vacancies and surface defects for electron trapping and dye adsorption, accelerating the separation of photogenerated electron–hole pairs and RB photodegradation. The formation of an excitation energy level below the conduction band of TiO₂ from the binding of electrons and oxygen vacancies decreases the excitation energy of Gd–La codoped TiO₂ nanotubes, resulting in robust photocatalysts. The results suggest that Gd–La codoped TiO₂ nanotubes calcined at 500 °C are very promising for enhancing the photocatalytic activity of photocatalysts in visible-light region.