Surface characterization and photocatalytic reactivity of innovative Ti/TiO2 and Ti/Pt−TiO2 mesh photoelectrodes

Novel Ti/TiO₂ and Ti/Pt–TiO₂ mesh photoelectrodes were produced by anodizing titanium mesh in H₂SO₄ solution. Their structural and surface morphology were examined by X-ray diffraction (XRD), scanning electronic microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The analytical results indicated that the crystal structure, morphology and pore size were affected significantly by the voltage and current density applied in anodization and the percentage platinum content. The results of XPS measurement showed that the binding energy of O 1s and Ti 2p increased slightly owing to platinum deposition (Pt⁰, Pt²⁺ and Pt⁴⁺) onto the TiO₂ surface. The photoelectrocatalytic (PEC) oxidation of methyl orange in aqueous solution using the Ti/TiO₂ and Ti/Pt–TiO₂ meshes was investigated. The experimental results demonstrated that Ti/TiO₂ mesh prepared at 160 V and 110 mA cm^–2 achieved the best PEC oxidation. The efficiency of PEC oxidation could be further enhanced by applying an electrical bias between the working electrode and counter electrode. An optimal electrical bias voltage was found to be 0.6 V, while an optimal platinum content was 3.37%.     

Degradation of dye wastewater in a thin-film photoelectrocatalytic (PEC) reactor with slant-placed TiO2/Ti anode

A thin-film photoelectrocatalytic (PEC) reactor with slant-placed TiO₂/Ti anode was developed and successfully applied to degrade Rhodamine B (RhB) and textile effluent. Using a 5–150 mg L⁻¹ RhB solution as the model system, thin-film PEC removed total color and TOC by 99–28% and 78–15%, respectively, in 1 h, which is much higher than 82–7% and 60% to zero by conventional PEC. The enhanced treatment efficiency achieved by thin-film PEC process was attributed to the significantly reduced path length of irradiation light source. The wastewater was kept circulating during the experiments to timely refresh the aqueous film on the TiO₂/Ti anode and promote the mass transfer of the target pollutants and the degradation products in the bulk solution. The thin-film PEC reactor can degrade both simulated and real dye wastewater efficiently under UV light irradiation. Results suggested that thin-film PEC was particularly superior for treating a high concentration solution. The thin-film PEC reactor was also applied to treat RhB solution efficiently under solar light irradiation. The recycle experiments demonstrated excellent stability and reliability of the slant-placed TiO₂/Ti anode. This study proposed a simple and effective method to design PEC reactor applicable for industrial dye wastewater treatment.     

Electrocatalytic properties of Ti/TiO2 electrodes prepared by the Pechini method

The effects of three synthesis variables on the electrochemical properties of TiO₂ prepared by the Pechini method are described. To minimize the number of experiments, a factorial design was used. It was shown that, in the presence of nitrobenzene, the temperature and the number of layers were the most important variables. The effects of these variables on the cathodic charges measured by cyclic voltammetry were –0.75 and 2.76 mC cm^–2, respectively. Explanations of these findings are based on the effect of the conditions of preparation on the morphology and microstructure of the electrodes.     

Growth and characterization of TiO2 nanotubes from sputtered Ti film on Si substrate

In this paper, we present the synthesis of self-organized TiO₂ nanotube arrays formed by anodization of thin Ti film deposited on Si wafers by direct current (D.C.) sputtering. Organic electrolyte was used to demonstrate the growth of stable nanotubes at room temperature with voltages varying from 10 to 60 V (D.C.). The tubes were about 1.4 times longer than the thickness of the sputtered Ti film, showing little undesired dissolution of the metal in the electrolyte during anodization. By varying the thickness of the deposited Ti film, the length of the nanotubes could be controlled precisely irrespective of longer anodization time and/or anodization voltage. Scanning electron microscopy, atomic force microscopy, diffuse-reflectance UV–vis spectroscopy, and X-ray diffraction were used to characterize the thin film nanotubes. The tubes exhibited good adhesion to the wafer and did not peel off after annealing in air at 350 °C to form anatase TiO₂. With TiO₂ nanotubes on planar/stable Si substrates, one can envision their integration with the current micro-fabrication technique large-scale fabrication of TiO₂ nanotube-based devices.     

Preparation and characterization of SO42-/TiO2 and S2O82-/TiO2 catalysts

Nanosized solid superacids SO₄ ²⁻/TiO₂ and S₂O₈ ²⁻/TiO₂, as well as MCM-41-supported SO₄ ²⁻/ZrO₂, were prepared. Their structures, acidities, and catalytic activities were investigated and compared using XRD, N₂ adsorption-desorption, and in situ FTIR-pyridine adsorption, as well as an evaluation reaction with pseudoionone cyclization. The results showed that SO₄ ²⁻/TiO₂ and S₂O₈ ²⁻/TiO₂ possess not only nanosized particles with diameters < 7.0 nm, a BET surface greater than 140 cm²/g and relatively regular mesostructures with pores around 4.0 nm, but also a pure anatase phase and strong acidity. Different from the Lewis acid nature of SO₄ ²⁻/ZrO₂/MCM-41, SO₄ ²⁻/TiO₂ and S₂O₈ ²⁻/TiO₂ exhibit mainly Bronsted acidities. The strongest Bronsted acid sites were produced on SO₄ ²⁻/TiO₂ promoted with H₂SO₄, while Lewis acid sites on S₂O₈ ²⁻/TiO₂ even stronger than those on SO₄ ²⁻/ZrO₂/MCM-41 were generated when persulfate solution was used as sulfating agent. Because of their distinct acid natures, SO₄ ²⁻/TiO₂ and S₂O₈ ²⁻/TiO₂ exhibited catalytic activities for the cyclization of pseudoionone that were much higher than that of SO₄ ²⁻/ZrO₂/MCM-41. It can be concluded that the existence of more Br?nsted acid sites was favorable for proton participation in the cyclization reaction. Translated from Journal of Chemical Engineering of Chinese Universities, 2006, 20(2): 239–244 [译自: 高校化学工程学报]     

Photoelectrocatalytic degradation of bisphenol A in aqueous solution using a Au–TiO2/ITO film

A series of Au–TiO₂/ITO films with nanocrystaline structure was prepared by a procedure of photo-deposition and subsequent dip-coating. The Au–TiO₂/ITO films were characterized by X-ray diffraction, scanning electronic microscopy, electron diffraction, X-ray photoelectron spectroscopy, and UV–VIS diffuse reflectance spectroscopy to examine the surface structure, chemical composition, the chemical state of metal, and the light absorption properties. The photocatalytic activity of the Au–TiO₂/ITO films was evaluated in the photocatalytic (PC) and photoelectrocatalytic (PEC) degradation of bisphenol A (BPA) in aqueous solution. Compared with a TiO₂/ITO film, the degree of BPA degradation using the Au–TiO₂/ITO films was significantly higher in both the PC and PEC processes. The enhancement is attributed to the action of Au deposits on the TiO₂ surface, which play a key role by attracting conduction band photoelectrons. In the PEC process, the anodic bias externally applied on the illuminated Au–TiO₂/ITO film can further drive away the accumulated photoelectrons from the metal deposits and promote a process of interfacial charge transfer.     

Photocatalytic and Photoelectrocatalytic Performance of 1% Pt Doped TiO2 for the Detoxification of Water

The degradation of formic acid (HCOOH), FA (a surrogate contaminant) using titanium dioxide (TiO₂) and 1% Pt doped TiO₂ electrodes, prepared by sol—gel methods, was investigated in a photoelectrocatalytic (PEC) system in order to determine the effect of Pt doping on the oxidation potential of TiO₂. Pt doping shifts the position of band edge and therefore the direct and indirect oxidation potentials of TiO₂ in PEC systems. As a result, the degradation of formic acid via the generation of hydrogen peroxide production on 1%Pt—TiO₂ electrodes was much better than that on non-doped electrodes. The degradation of HCOOH was also examined with respect to the faradaic efficiency of this process. It was found that the 1%Pt—TiO₂ photoanode had a 30% higher efficiency than that of non-doped TiO₂ photoanodes.     

Electrochemical characterization of TiO2/WOx nanotubes for photocatalytic application

TiO₂/WO_x nanotubes have unique photo-energy retention properties that have gathered scientific interest. Herein, we report the synthesis, morphological characterization, and the electrochemical characterization of TiO₂/WO_x nanotubes compared with pure TiO₂ nanotubes, prepared by anodization technique. Significant structural differences were not observed in TiO₂/WO_x nanotubes as observed by using scanning electron microscopy and transmission electron microscopy. The charge transfer resistance of TiO₂/WO_x before and after photo irradiation determined by using electrochemical impedance spectroscopy proves the inherent energy retention property which was not observed in pure TiO₂ nanotubes.     

Enhanced visible light-induced photoelectrocatalytic degradation of phenol by carbon nanotube-doped TiO2 electrodes

We used a modified sol-gel method to prepare titanium dioxide and multi-walled carbon nanotube (CNT) composites that we subsequently deposited onto indium tin oxide (ITO) conductive glass plates. We characterized these CNT-doped TiO₂ (CNT-TiO₂) films using X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and diffuse reflectance UV-vis spectroscopy. The photoelectrocatalytic (PEC) activity of the composites was evaluated through their ability to mediate the degradation of phenol. XRD measurements indicated that the TiO₂ component existed solely in the anatase phase and that the crystallinity of the CNTs was low. XPS indicated that carbon atoms could substitute for both oxygen and titanium atoms in the TiO₂ lattice to form Ti-C and Ti-O-C structures, which were responsible for the extra photoabsorption and PEC activity under illumination with visible light, in addition to those provided by the CNTs and carbonaceous and Ti³⁺ species. An interphase interaction between TiO₂ and the CNTs elevated the photoabsorbance of the composites in the visible light region. A sample of TiO₂ doped with 10% CNTs and calcined at 400 °C exhibited the highest photocurrent and PEC efficiency. We systematically investigated the effects of several parameters of the PEC process, including the applied potential and pH, on the phenol conversion.     

Preparation, characterization, and application of titanium nano-tube array in dye-sensitized solar cells

ABSTRACT: The vertically orientated TiO2 nanotube array (TNA) decorated with TiO2 nano-particles was successfully fabricated by electrochemically anodizing titanium (Ti) foils followed by Ti-precursor post-treatment and annealing process. The TNA morphology characterized by SEM and TEM was found to be filled with TiO2 nano-particles interior and exterior of the TiO2 nano-tubes after titanium (IV) n-butoxide (TnB) treatment, whereas TiO2 nano-particles were only found inside of TiO2 nano-tubes upon titanium tetrachloride (TiCl4) treatment. The efficiency in TNA-based DSSCs was improved by both TnB and TiCl4 treatment presumably due to the increase of dye adsorption.     

Electrochemical decomposition of bisphenol A using Pt/Ti and SnO2/Ti anodes

Methodology for the electrochemical decomposition of bisphenol A is described. The electrochemical behaviour of bisphenol A at a Pt electrode was investigated by means of cyclic voltammetric techniques. The electrochemical oxidation of bisphenol A led to the deactivation of the electrode as a result of the deposition of an electropolymerized film. However the electrochemical decomposition of bisphenol A could be achieved by the use of a platinum coated titanium (Pt/Ti) electrode and a tin dioxide coated (SnO₂/Ti) electrode. The electrolysis was carried out galvanostatically at a constant current of 0.3 A. The mineralization of bisphenol A was monitored by determining the amount of total organic carbon. Furthermore, the generation and nature of intermediates produced in the electrochemical reactions was investigated. Although large amounts of aliphatic acids were generated by electrolysis with the Pt/Ti anode, they were produced only to a small extent in at the SnO₂/Ti anode. In the case of the SnO₂/Ti anode, bisphenol A is rapidly oxidized to carbon dioxide and water, compared to the Pt/Ti anode.     

Properties of sol-gel SnO2/TiO2 electrodes and their photoelectrocatalytic activities under UV and visible light illumination

A visible light active binary SnO₂-TiO₂ composite was successfully prepared by a sol-gel method and deposited on Ti sheet as a photoanode to degrade orange II dye. Titanium and SnO₂ can promote the development of rutile phase of TiO₂ and inhibit the formation of anatase phase of TiO₂. Formation of SnO₂ crystalline is insignificant even when the calcination temperature increases to 700 °C. Heterogenized interface between SnO₂ and TiO₂ inhibits growth of TiO₂ linkage and leads to the particle-filled surface morphology of SnO₂-containing films. The carbonaceous, Ti-O-C bonds and Ti³⁺ species are likely to account for the photoabsorption and photoelectrocatalytic (PEC) activity under visible light illumination. The electrode with 30% SnO₂ exhibits higher photocurrent when compared with those in the region of 0-50%. The 600 °C-calcined SnO₂-TiO₂ electrode indicates higher activity when compared with those at 400, 500, 700 and 800 °C. PEC degradation of orange II follows the Langmuir-Hinshelwood model and takes place much effectively in a solution of pH 3.0 than those in pH 7.0 and pH 11.0.     

Preparation and Characterization of Titanium Dioxide (TiO2) from Sludge produced by TiCl4 Flocculation with FeCl3, Al2(SO4)3 and Ca(OH)2 Coagulant Aids in Wastewater

Abstract

In this study, TiCl₄ coagulant together with coagulant aids such as FeCl₃, Al₂(SO₄)₃, and Ca(OH)₂ were investigated to improve the photoactivity of titanium dioxide (TiO₂) produced from sludge and to increase the resulting low pH value. After TiCl₄ flocculation with three coagulant aids, the settled floc (sludge) was incinerated at 600°C to produce TiO₂ doped with Fe, Al, and Ca elements. Fe-, Al-, and Ca-doped TiO₂ was characterized in terms of structural, chemical, and photo-electronic properties. All the coagulant aids used together with Ti-salt flocculation effectively increased the pH values. The surface area of TiO₂-WO (without any coagulant aids), Fe/TiO₂, Al/TiO₂, and Ca/TiO₂ was 122 m²/g, 77 m²/g, 136 m²/g and 116 m²/g, respectively. The TiO₂-WO, Fe/TiO₂, Al/TiO₂, and Ca/TiO₂ was found to be of anatase phase. The XRD pattern on the Fe/TiO₂ included an additional peak of hematite (α-Fe₂O₃). The majority of gaseous acetaldehyde with TiO₂-WO and Ca/TiO₂ for photocatalytic activity was completely removed within 40 minutes under UV irradiation.     

Conductive and transparent multilayer films for low-temperature TiO2/Ag/SiO2 electrodes by E-beam evaporation with IAD

Conductive and transparent multilayer thin films consisting of three alternating layers (TiO₂/Ag/SiO₂, TAS) have been fabricated for applications as transparent conducting oxides. Metal oxide and metal layers were prepared by electron-beam evaporation with ion-assisted deposition, and the optical and electrical properties of the resulting films as well as their energy bounding characteristics and microstructures were carefully investigated. The optical properties of the obtained TAS material were compared with those of well-known transparent metal oxide glasses such as ZnO/Ag/ZnO, TiO₂/Ag/TiO₂, ZnO/Cu/ZnO, and ZnO/Al/ZnO. The weathering resistance of the TAS film was improved by using a protective SiO₂ film as the uppermost layer. The transmittance spectra and sheet resistance of the material were carefully measured and analyzed as a function of the layer thickness. By properly adjusting the thickness of the metal and dielectric films, a low sheet resistance of 6.5 ohm/sq and a high average transmittance of over 89% in the 400 to 700 nm wavelength regions were achieved. We found that the Ag layer played a significant role in determining the optical and electrical properties of this film.     

Rutile TiO2-modified multi-wall carbon nanotubes in TiO2 film electrodes for dye-sensitized solar cells

The beneficial influence of incorporation of acid-treated and rutile TiO₂ (r-TiO₂)-modified multi-wall carbon nanotubes (MWNTs) in TiO₂ films on photocurrent–voltage characteristics of dye-sensitized solar cells (DSSCs) was studied. Two different routes were adopted for the modification of acid-treated MWNTs (a-MWNTs) with r-TiO₂. The films and MWNTs were characterized by electron microscopy, energy dispersive X-ray spectroscopy, XRD and Raman spectroscopy. In the case of incorporation of a-MWNTs with r-TiO₂ modification, short-circuit photocurrent (J _sc) of the pertinent DSSC increased by 35% compared with that of a cell with bare TiO₂ film. The open-circuit voltage remained almost the same for all cases. The enhanced J _sc is explained by the increased surface area of the film, enhanced cluster formation of TiO₂ particles around a-MWNTs, and improved interconnectivity of TiO₂ particles in the presence of a-MWNTs.     

Graphite-supported TiO2 for 4-nitrophenol degradation in a photoelectrocatalytic reactor

Amorphous TiO₂, prepared at room temperature through a sol–gel method implementing hydrolysis of TiCl₄, has been supported on graphite rods and then annealed at 673 K. In this way graphite was completely covered by a porous anatase TiO₂ layer, with an external thickness of about 1 μm, with graphite pores completely filled by the semiconductor particles. The obtained electrode was structurally characterized by SEM microscopy coupled to EDAX mapping and by Raman spectroscopy. A Pyrex annular reactor was designed in order to test the prepared electrodes for the photoelectrocatalytic degradation of 4-nitrophenol, a target pollutant dissolved in aqueous conductive solution. The continuous reactor worked in total recirculation mode and the degradation runs were carried out by applying near UV-light, bias or both energy sources. The influence of flow rate, initial 4-nitrophenol concentration and applied potential on the degradation rate was studied.     

Monolithic-like TiO2 nanotube supported Ru catalyst for activation of CH4 and CO2 to syngas

Highly-ordered TiO₂ nanotube arrays (TiNTA) were prepared by an electrochemical anodization method and used as the carrier material to load 1 wt.% Ru. The Ru/TiNTA catalyst was then applied to the combination reactions of the partial oxidation of methane reaction (POM) with the carbon dioxide reforming with methane reaction (CRM) for syngas production. In comparison with the commercial TiO₂ powder (P25) supported 1 wt.% Ru catalyst, Ru/TiNTA shows higher activity and much better stability. The superior performance of Ru/TiNTA is attributed to the specific monolithic-like structure and confinement effect of TiNTA.     

A low-temperature combustion synthesis process for production of Ti from TiO2

Calciothermic reduction of titanium dioxide is suggested as an alternative to the conventional Kroll process for production of metallic titanium. In this study, a simple reactor was used to carry out the reaction of TiO₂ with 20 wt % excess Ca at 1000°C to obtain titanium product with a mean size of Ti particles around 20 μm. A sharp decrease in reaction temperature can be achieved by using KClO₄ as an additive. In this case, sub-micron agglomerated titanium particles were obtained.      

A novel photoelectrocatalytic system for organic contaminant degradation on a TiO2 nanotube (TNT)/Ti electrode

A novel degradation system, combined with photon-efficient thin-film photocatalysis, conventional bulk-phase photocatalysis and photocarrier-efficient electrocatalysis (TBPE), was developed on a vertically ordered one-dimensional (1D) TiO₂ nanotube (TNT)/Ti electrode for the purification of organics. The TBPE system possessed excellent optical, electrochemical, photoelectrochemical and photoelectrocatalytic properties as well as a high mass-transfer coefficient and interfacial activity. The combined degradation of methyl orange (MO) was optimized by varying the rotation angular velocity, applied bias and substrate concentration, and a photoelectrochemical synergetic effect of 62.2% was observed under the optimized conditions for TBPE compared to the individual electrocatalytic (EC) and photocatalytic (PC) systems. To explore the mechanisms, the combined thin-film degradation system of photon-efficient thin-film photocatalysis with photocarrier-efficient electrocatalysis (TPE), and the combined bulk-phase degradation system of conventional bulk-phase photocatalysis with photocarrier-efficient electrocatalysis (BPE), were comparatively estimated. A dramatic increase of 29.4-74.4% was observed in the MO removal efficiency via the thin-film TPE system compared to the bulk-phase BPE system. The results indicated that in the proposed TBPE system on the 1D TNT electrode, the predominant degradation occurred via the TPE system due to its excellent UV utilization efficiency and resultant interfacial photoactivity.     

Preparation and characterization of CeO2/TiO2 nanoparticles by flame spray pyrolysis

Nanocrystalline TiO₂, CeO₂ and CeO₂-doped TiO₂ have been successfully prepared by one-step flame spray pyrolysis (FSP). Resulting powders were characterized with X-ray diffraction (XRD), N₂-physisorption, Transmission Electron Microscopy (TEM) and UV-Vis spectrophotometry. The TiO₂ and CeO₂-doped TiO₂ nanopowders were composed of single-crystalline spherical particles with as-prepared primary particle size of 10-13 nm for Ce doping concentrations of 5-50 at%, while square-shape particles with average size around 9 nm were only observed from flame-made CeO₂. The adsorption edge of resulting powder was shifted from 388 to 467 nm as the Ce content increased from 0 to 30 at% and there was an optimal Ce content in association with the maximum absorbance. This effect is due to the insertion of Ce^3+/4+ in the TiO₂ matrix, which generated an n-type impurity band.