Influence of particle size on the photoactivity of Ti/TiO2 thin film electrodes,and enhanced photoelectrocatalytic degradation of indigo carmine dye

Photoanodes based on Ti/TiO₂ thin films were prepared by the sol–gel method, using either tetraisopropoxide (Ti(OPri)₄) or modified tetraisopropoxide, producing electrodes with different sized nanoparticle coatings, termed nanoporous (20 nm) or nanoparticulated (10 nm) electrodes. The anatase form dominated the composition of the nanoparticulated electrode, which presented a higher surface area, a flat band potential shift of ?160 mV and a 50% improvement in photoactivity, compared to the nanoporous electrode. 100% color removal, and 75% mineralization, of indigo carmine dye were achieved after 15 min of photoelectrocatalytic treatment using a nanoparticulated Ti/TiO₂ electrode operated at a current density of 0.4 mA cm^?2. Our findings indicate that the use of nanoparticulated electrodes, under UV irradiation and with controlled current density, is an efficient alternative for the removal of food dye contaminants during wastewater treatment.     

X-ray induced photocatalysis on TiO2 and TiO2 nanotubes: Degradation of organics and drug release

The photocatalytic activity of titanium dioxide under X-ray radiation is of great interest for biomedical applications. In the present work we explore the use of compact TiO₂ layers and TiO₂ nanotubes for X-ray induced photocatalysis, in particular the degradation of organics and monolayer chain scission for drug release. The radiation was done with a conventional X-ray source and doses up to 50 × 10^?3 J/kg. The results show the feasibility of X-ray catalysis on TiO₂ and X-ray induced monolayer chain scission by the release of surface attached Zn–porphyrin molecules. Furthermore, a higher efficiency for anatase films and nanotubes is obtained than for amorphous morphologies.     

Improved efficiency of TiO2 nanotubes in dye sensitized solar cells by decoration with TiO2 nanoparticles

In the present work we investigate the effect of TiCl₄ treatments on the photoconversion efficiency of TiO₂ arrays used in dye sensitized solar cell. The results clearly show that by an appropriate treatment the decoration of the TiO₂ nanotube arrays with TiO₂ nanocrystallites of a typical size of 3 nm can be achieved. These particles can be converted to mixture of anatase and rutile phase by annealing in air. This decoration of the TiO₂ nanotubes leads to a significantly higher specific dye loading and, for certain annealing treatments, to a doubling of the solar cell efficiency (in our case from 1.9% to 3.8% of AM 1.5 conditions) can be achieved.     

Photocatalytic activity of nitrogen and copper doped TiO2 nanoparticles prepared by microwave-assisted sol-gel process

Cu and N-doped TiO₂ photocatalysts were synthesized from titanium (IV) isopropoxide via a microwave-assisted sol-gel method. The synthesized materials were characterized by X-ray diffraction, UV-vis diffuse reflectance, photoluminescence (PL) spectroscopy, SEM, TEM, FT-IR, Raman spectroscopy, photocurrent measurement technique, and nitrogen adsorption–desorption isotherms. Raman spectra and XRD showed an anatase phase structure. The SEM and TEM images revealed the formation of an almost spheroid mono disperse TiO₂ with particle sizes in the range of 9-17 nm. Analysis of N₂ isotherm measurements showed that all investigated TiO₂ samples have mesoporous structures with high surface areas. The optical absorption edge for the doped TiO₂ was significantly shifted to the visible light region. The photocurrent and photocatalytic activity of pure and doped TiO₂ were evaluated with the degradation of methyl orange (MO) and methylene blue (MB) solution under both UV and visible light illumination. The doped TiO₂ nanoparticles exhibit higher catalytic activity under each of visible light and UV irradiation in contrast to pure TiO₂. The photocatalytic activity and photocurrent ability of TiO₂ have been enhanced by doping of the titania in the following order: (Cu, N) - codoped TiO₂ > N-doped TiO₂ > Cu-doped TiO₂ > TiO₂. COD result for (Cu, N)-codoped TiO₂ reveals ∼92% mineralization of the MO dye on six h of visible light irradiation.     

Li-ion batteries from LiFePO4 cathode and anatase/graphene composite anode for stationary energy storage

Li-ion batteries made from LiFePO₄ cathode and anatase TiO₂/graphene composite anode were investigated for potential application in stationary energy storage. Fine-structured LiFePO₄ was synthesized by a novel molten surfactant approach whereas anatase TiO₂/graphene nanocomposite was prepared via self-assembly method. The full cell that operated at 1.6 V demonstrated negligible fade even after more than 700 cycles at measured 1 C rate. While with relative lower energy density than traditional Li-ion chemistries interested for vehicle applications, the Li-ion batteries based on LiFePO₄/TiO₂ combination potentially offers long life and low cost, along with safety, all which are critical to the stationary applications.     

Doping level effect on visible-light irradiation W-doped TiO2–anatase photocatalysts for Congo red photodegradation

A series of W-modified TiO₂ (W–TiO₂) photocatalysts were synthesized by a simple sol–gel method. The new photocatalysts were characterized by X-ray diffraction (XRD), X-ray fluorescence (XRF), scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV–vis-diffuse reflectance spectroscopy (DRS), and Brunauer, Emmett and Teller (BET) surface area analyzer. The photoactivity of the W–TiO₂ photocatalysts was evaluated by the photocatalytic oxidation of Congo red (CR) dye. It was found that the average size of the prepared photocatalysts is 10 nm. Moreover, they have high surface areas (∼ 216 m² g⁻¹) and their light-absorption extends to the visible region compared to pure TiO₂. The effects of W-loading and of the calcination temperature of the prepared photocatalysts on their photocatalytic activity were also studied. The obtained results show that the W_0.5–TiO₂ photocatalyst calcined at 350 °C is much highly photoactive than non-doped or highly doped TiO₂. The enhanced photocatalytic activity of the weakly doped TiO₂ may be attributed to the increase in the charge separation efficiency and the presence of surface acidity on the W_0.5–TiO₂ photocatalyst.     

F–B-codoping of anodized TiO2 nanotubes using chemical vapor deposition

Chemical vapor deposition (CVD) was firstly used to simultaneously codope fluorine and boron into TiO₂ nanotubes anodized Ti in C₂H₂O₄ · 2H₂O + NH₄F electrolyte. F–B-codoping was successfully carried out by annealing the anodized TiO₂ nanotubes through CVD, as evidenced from XPS analysis. SEM images showed that the higher the annealing temperature, the greater structure damage of F–B-codoped sample. XRD results confirmed that annealing temperature had an influence on the phase structure and boron and fluorine impurities could retard anatase–rutile phase transition. F–B-codoped samples displayed remarkably strong absorption in both UV and visible range. Under visible-light irradiation, F–B-codoped samples showed the higher I_ph and catalytic activity in methyl orange photoelectrodegradation than F-doped sample and B-doped sample. This showed a convincing evidence of F–B-codoping of TiO₂ had an obvious synergistic effect on the enhancement of photocurrents and photoelectrocatalytic activity.     

Impact of surface hydroxylation in MgO-/SnO-nanocluster modified TiO2 anatase (101) composites on visible light absorption,charge separation and reducibility

Anatase TiO₂ surfaces, whether oxidised or hydroxylated, can be modified by nanoclusters of SnO and MgO to give a red shift in light absorption, enhanced charge separation and high reducibility.     

Solar active nano-TiO2 for mineralization of Reactive Red 120 and Trypan Blue: 1st Nano Update

Nano-TiO₂ was synthesized by sol–gel method. The catalyst was characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) images, transmission electron microscope (TEM), BET surface area measurement and DRS analysis. The formation of anatase phase nano-TiO₂ was confirmed by XRD measurements and its crystalline size is found to be 15.2 nm. SEM images depict the crystalline nature of prepared TiO₂. The BET surface area of prepared TiO₂ is found to be 86.5 m² g^?1 which is higher than that of commercially available TiO₂–P25. The photocatalytic activity of prepared anatase phase TiO₂ has been tested for the degradation of two azo dyes: Reactive Red 120 (RR 120) and Trypan Blue (TB) using solar light. The photocatalytic activity of nano-TiO₂ is higher than TiO₂–P25 under solar light. The mineralization of dyes has been confirmed by chemical oxygen demand (COD) measurements.     

The adsorption and activation of formic acid on different anatase TiO_2 surfaces

Formic acid photodegradation is one of the most important reactions in organic pollution control, and helps to improve the hydrogen generation efficiency in titanium dioxide catalyzed water photodecomposition. Based on density functional theory and Reax FF molecular dynamics, the adsorption, diffusion and activation of formic acid on the different anatase TiO_2(101),(001),(010) surfaces are investigated.The result shows that the adsorption of COOH on anatase TiO_2 surface shrinks the energy gap between the dehydrogenation intermediate COOH and HCOO. On the anatase TiO_2(101) surface, the formic acid breaks the O–H bond at the first step with activation energy 0.24 eV, and the consequent break of α-H become much easier with activation energy 0.77 eV. The dissociation of α-H is the determination step of the HCOOH decomposition.     

Effect of water content of ethylene glycol as electrolyte for synthesis of ordered titania nanotubes

Anodization of Ti using fluoride containing polyhydric alcohols such as ethylene glycol or glycerol as electrolyte results in ordered arrays of TiO₂ nanotubes with a smooth surface and a very high aspect ratio. However, the reproducibility of the result is affected by many experimental parameters, notably the water content. In this investigation, anodizations of Ti foil in anhydrous ethylene glycol +0.2 wt% NH₄F solution (EG solution) with 0–1.0 wt% water additions were carried out at 20 V for 45 min in a dry-argon filled controlled-atmosphere glove box. It was observed that a minimum amount of 0.18 wt% of water addition was required to form a well ordered TiO₂ nanotubular arrays. When the anhydrous EG solution was reused for third time, ordered arrays of nanotubes started to form. When the water addition to the EG solution was more than 0.5 wt%, formation of ridges was observed on the nanotubes. XPS results showed presence of un-anodized Ti element in the anhydrous condition and presence of organic and (NH₄)₂TiF₆ type compounds in all the anodized samples in addition to the regular TiO₂ phase. The results underline the influence of water content and local pH condition to form the ordered nanotubular arrays.     

Novel synthesis of high-surface-area ordered mesoporous TiO2 with anatase framework for photocatalytic applications

Ordered mesoporous TiO₂ materials with an anatase frameworks have been synthesized by using a cationic surfactant cetyltrimethylammonium bromide (C₁₆TMABr) as a structure-directing agent and soluble peroxytitanates as Ti precursor through a self-assembly between the positive charged surfactant S⁺ and the negatively charged inorganic framework I^? (S⁺I^? type). The low-angle X-ray diffraction (XRD) pattern of the as-prepared mesoporous TiO₂ materials indicates a hexagonal mesostructure. XRD and transmission electron microscopy results and nitrogen adsorption–desorption isotherms measurements indicate that the calcined mesoporous TiO₂ possesses an anatase crystalline framework having a maximum pore size of 6.9 nm and a maximum Brunauer–Emmett–Teller specific surface area of 284 m² g^?1. This ordered mesoporous anatase TiO₂ also demonstrates a high photocatalytic activity for degradation of methylene blue under ultraviolet irradiation.     

RuO2-wired high-rate nanoparticulate TiO2 (anatase): Suppression of particle growth using silica

To enhance the high-rate capability (up to 120 C, 20 A/g) of nanoparticulate TiO₂ (anatase) formed by thermal treatment of protonated TiO₂ nanotubes, we used two types of additives: RuO₂ as an electron-conductive material [Y.-G. Guo, Y.-S. Hu, W. Sigle, J. Maier, Adv. Mater. 19 (2007) 2087] and silica as a suppressant of particle growth during heat treatment. We show systematically that both additives, when used separately, improve the high-rate performance of anatase by 25–55 mA h/g at 60 C. The combined use of both additives in a total amount of merely 2.5 wt.% leads to an improvement of more than 70 mA h/g at 60 C. The underlying mechanisms for these significant effects are briefly discussed.     

Effect of Hg2+doping and of the annealing temperature on the nanostructural properties of TiO2 thin films obtained by sol–gel method

This work is a study of Hg²⁺-doped TiO₂ thin films deposited on silicon substrates prepared by sol–gel method and treated at temperatures ranging between 600 to 1000 °C for 2 h. The structural and optical properties of thin films have been studied using different techniques. We analyzed the vibrations of the chemical bands by Fourier transform infrared (FTIR) spectroscopy and the optical properties by UV–Visible spectrophotometry (reflection mode) and photoluminescence (PL). The X-ray diffraction and Raman spectra of TiO₂ thin films confirmed the crystallization of the structure under the form of anatase, rutile, mercury titanate (HgTiO₃) as a function of the annealing temperature. The observation by scanning electron microscopy (SEM) showed the changing morphology, with respect to nanostructures, nanosheets, nanotubes, with the annealing temperature. The diameters of nanotubes ranged from 50 nm to 400 nm. The photoluminescence and reflectance spectra indicated that these structures should enhance photocatalytic activity.     

Photocatalytic activity of TiO2 nanotube layers loaded with Ag and Au nanoparticles

Ag and Au nanoparticles were found to significantly enhance the photocatalytic activity of self-organized TiO₂ nanotubular structures. The catalyst systems are demonstrated to be highly efficient for the UV-light induced photocatalytic decomposition of a model organic pollutant – Acid Orange 7. The metallic nanoparticles with a diameter of ∼10 ± 2 nm (Ag) and ∼28 ± 3 nm (Au) were attached to a nanotubular TiO₂ layer that consists of individual tubes of ∼100 nm of diameter, ∼2 μm in length and approx. 15 nm of wall thickness. Both metal particle catalyst systems enhance the photocatalytic decomposition significantly more on the nanotubes support than placed on a compact TiO₂ surface.     

TiO2 nanotube arrays fabricated by anodization in different electrolytes for biosensing

Titania nanotube arrays were fabricated by anodic oxidation of titanium foil in different electrolytes. The morphology, crystallinity and composition of the as-prepared nanotube arrays were studied by XRD, SEM and EDX. Electrochemical impedance spectroscopy (EIS) was employed to investigate their electrical conductivity and capacitance. Titania nanotube arrays co-adsorbed with horseradish peroxidase (HRP) and thionine chloride (Th) were studied for their sensitivity to hydrogen peroxide by means of cyclic voltammetric and galvanostatic measurements. The experiments showed that TiO₂ nanotube arrays possessed appreciably different sensitivities to H₂O₂ due to their different conductivity. Further experiments revealed that TiO₂ nanotubes have noticeably different ability of adsorbing HRP and Th, and the best sensitivity was achieved when the density of HRP is the highest. The TiO₂ nanotube arrays fabricated in potassium fluoride solution demonstrated the best sensitivity on hydrogen peroxide in the range of 10⁻⁵–3 × 10⁻³ M at pH 6.7 and at a potential of −600 mV (vs. Ag/AgCl).     

Synthesis and characterization of high surface area TiO2/SiO2 mesostructured nanocomposite

Recently titania synthesis was reported using various structuration procedures, leading to the production of solid presenting high surface area but exhibiting moderate thermal stability. The study presents the synthesis of TiO₂/SiO₂ nanocomposites, a solid that can advantageously replace bulk titania samples as catalyst support. The silica host support used for the synthesis of the nanocomposite is a SBA-15 type silica, having a well-defined 2D hexagonal pore structure and a large pore size. The control of the impregnation media is important to obtain dispersed titania crystals into the porosity, the best results have been obtained using an impregnation in an excess of solvent. After calcination at low temperature (400 °C), nanocomposites having titania nanodomains (～2–3 nm) located inside the pores and no external aggregates visible are obtained. This nanocomposite exhibits high specific surface area (close to that of the silica host support, even with a titania loading of 55 wt.%) and a narrow pore size distribution. Surprisingly, the increase in calcination temperature up to 800 °C does not allow to detect the anatase to rutile transition. Even at 800 °C, the hexagonal mesoporous structure of the silica support is maintained, and the anatase crystal domain size is evaluated at ～10 nm, a size close to that of the silica host support porosity (8.4 nm). Comparison of their physical properties with the results presented in literature for bulk samples evidenced that these TiO₂/SiO₂ solids are promising in term of thermal stability.     

Tio2@Sn core–shell nanotubes for fast and high density Li-ion storage material

TiO₂@Sn core–shell nanotube material prepared by thermal decomposition of SnCl₄ on TiO₂ nanotubes at 300 °C has been demonstrated superior Li-ion storage capability of 176 mA h/g even at high current rate of 4000 mA/g (charge and discharge of all TiO₂ within 5 min) in spite of using low carbon content (5 wt%). This value corresponds to volumetric energy densities of 317 mA h/cm³, and its value was 3.5-fold larger than that of the bare TiO₂ nanotubes.     

Anatase TiO2 nanosheet: An ideal host structure for fast and efficient lithium insertion/extraction

Anatase TiO₂ nanosheets with largely exposed (0 0 1) facets have been synthesized by a modified method. Exploitation of these nanosheets as a host structure for reversible lithium insertion/extraction has been investigated. It is found that these TiO₂ nanosheets manifest much lower initial irreversible losses compared to other anatase TiO₂ nanostructures, and excellent cycling performance at a charge–discharge rate as high as 20 C. The superior reversible lithium storage capability can be attributed to the ultrathin nanosheet structure: a large exposed effective area and a very short diffusion path. It thus attests the promising use of these anatase TiO₂ nanosheets in high-power lithium–ion batteries.