Photoluminescence of anatase and rutile TiO2 particles

Nonaqueous reactions between titanium(IV) chloride and alcohols (benzyl alcohol or n-butanol) were used for the synthesis of anatase TiO2 particles, while rutile TiO2 particles were synthesized in aqueous media by acidic hydrolysis of titanium(IV) chloride. The X-ray diffraction measurements proved the exclusive presence of either the anatase or the rutile phase in prepared samples. The photoluminescence of both kinds of particles (anatase and rutile) with several well-resolved peaks extending in the visible spectral region was observed, and the quantum yield at room temperature was found to be 0.25%. Photon energy up-conversion from colloidal anatase and rutile TiO2 particles was observed at low excitation intensities. The energy of up-converted photoluminescence spans the range of emission of normal photoluminescence. The explanation of photon energy up-conversion involves mid-gap energy levels originating from oxygen vacancies.     

Gold particles supported on self-organized nanotubular TiO2 matrix as highly active catalysts for electrochemical oxidation of glucose

Au/TiO₂/Ti electrode was prepared by a two-step process of anodic oxidation of titanium followed by cathodic electrodeposition of gold on resulted TiO₂. The morphology and surface analysis of Au/TiO₂/Ti electrodes was investigated using scanning electron microscopy and EDAX, respectively. The results indicated that gold particles were homogeneously deposited on the surface of TiO₂ nanotubes. The nanotubular TiO₂ layers consist of individual tubes of about 60–90 nm in diameter, and the electrode surface was covered by gold particles with a diameter of about 100–200 nm which are distributed evenly on the titanium dioxide nanotubes. This nanotubular TiO₂ support provides a high surface area and therefore enhances the electrocatalytic activity of Au/TiO₂/Ti electrode. The electrocatalytic behavior of Au/TiO₂/Ti electrodes in the glucose electro-oxidation was studied by cyclic voltammetry. The results showed that Au/TiO₂/Ti electrodes exhibit a considerably higher electrocatalytic activity toward the glucose oxidation than that of gold electrode.     

Charge separation at the rutile/anatase interface: a dominant factor of photocatalytic activity

Epitaxial and polycrystalline anatase films were grown by pulse-powered magnetron sputtering. The photoreduction of Ag ions showed the difference in the distribution of the photocatalytic active sites in these films. The polycrystalline anatase film was covered with an Ag layer. In contrast, discrete Ag particles were interspatially deposited on the epitaxial anatase film. Evaluation of the epitaxial film by micro-Raman spectrometry revealed that the rutile coexisted at only the site where the Ag particle was precipitated. These results suggest that the rutile/anatase interface is the active site for photocatalysis and is one of the dominant factors of the photocatalytic activity.     

Efficient photoelectrodes from anatase TiO2 nanotube arrays decorated with particles/rods/3D microflower rutile crystals for photoelectrochemical water splitting

Journal of Solid State Electrochemistry - Efficient photoanodes are designed of vertically aligned anatase TiO2 nanotube arrays (anatase TNTAs) decorated with different shaped rutile TiO2...     

Preparation of self-supporting hierarchical nanostructured anatase/rutile composite TiO(2) film

Via the combination of an electrospinning method with a hydrothermal reaction, a large-scale cedar-like hierarchical nanostructured TiO(2) film with an anatase/rutile composite phase was fabricated.     

Short time deposition of TiO2 nanoparticles on SiC as photocatalysts for the degradation of organic dyes

The deposition of TiO₂ nanoparticles on SiC was carried out by mechanical milling under different conditions. SiC–TiO₂ samples were used as photocatalysts for the degradation of organic dyes such as methylene blue and rhodamine B. A short time deposition of TiO₂ nanoparticles was observed during mechanical milling (2 min at 200 rpm) to cover the SiC particles. The presence of SiC and TiO₂ (anatase and rutile) was confirmed by means of X-ray diffraction after thermal treatment at 450 °C. The deposition of TiO₂ on SiC was corroborated by scanning electron microscopy analysis; the thickness of the thin layer of TiO₂ deposited on SiC increases as the proportion of TiO₂ increases. The energy band gap values obtained for these compounds were around 3.0 eV. SiC–TiO₂ photocatalysts prepared by mechanical milling exhibited better activity under UV-light irradiation for the degradation of methylene blue and rhodamine B than commercial TiO₂ powder (titania P25).     

Hydrothermal synthesis and enhanced photocatalytic activity of mixed-phase TiO2 powders with controllable anatase/rutile ratio

In this study, mixed-phase TiO₂ powders were novelly synthesized via a facile and mild hydrothermal method without any post-heat treatment. TiOSO₄ and peroxide titanic acid (PTA) were used as inorganic titanium sources, while no special solvent or additive were introduced. The XRD and TEM results showed the mixed-phase TiO₂ powders were composed of anatase and rutile phases, and the PTA sol played an important role on forming the rutile nucleus. The proportion of rutile in the mixed-phase TiO₂ could be easily controlled in the range of 0%–70.5% by changing the amount of PTA sol used in the synthesis process. The UV-Visible absorption spectra indicated the prepared mixed-phase TiO₂ showed enhanced visible light absorption with the increase of rutile ratio. The photodegradation experiments revealed the mixed-phase TiO₂ exhibited the best photocatalytic activity at the rutile ratio of 41.5%, while a higher or lower rutile ratio both resulted in the decrease of photocatalytic activity.     

Highly sensitive photoelectrochemical immunosensor based on anatase/rutile TiO2 and Bi2S3 for the zero-biased detection of PSA

Journal of Solid State Electrochemistry - A novel label-free photoelectrochemical immunosensor was developed for the determination of prostate-specific antigen (PSA) based on fluorine-doped tin...     

A photoelectrochemical study on the features of carbonate-catalyzed water oxidation at illuminated TiO2/Solution interface

Photoelectrochemical (PEC) measurements were performed to investigate the catalytic effect of carbonate on water splitting over TiO₂ nanotube photoanode at low applied potentials. The photocurrent measured with the presence of carbonate with a low concentration of 5?×?10^?3?M in 0.5 M NaClO₄ solution of pH?=?6–13 was ca. two to seven times of that measured in the absence of carbonate in solution. By adding a small amount of formate as a precursor of in situ generated carbonate in solution, the significant catalytic effect of carbonate was further evidenced. The features of the photocurrents measured under both potential dynamic and potentiostatic conditions indicated that the existence of carbonate in solution can effectively prevent the surface recombination of the photogenerated electron–hole pairs occurring at the TiO₂/solution interface, which was regarded as the main reason for the catalytic effect of carbonate on the PEC water splitting in this work. The related charge transfer processes during water photooxidation at the TiO₂/solution interface were discussed.     

Gel-assisted synthesis of anatase TiO2 nanoparticles and application for electrochemical determination of L-tryptophan

Anatase titanium dioxide nanoparticles (TiO₂-NPs) were synthesized with and without gelatin via the sol-gel method. The TiO₂-NPs were characterized by a number of techniques, such as thermogravimetric analysis (TGA), X-ray diffraction analysis (XRD), transmission electron microscopy (TEM), fourier transform infrared spectroscopy (FT-IR) and ultraviolet visible spectroscopy (UV-Vis). The particle sizes of the TiO₂-NPs prepared with and without gelatin were ～13 and ～17 nm, respectively. The main advantage of using gelatin as a stabilizing agent is that it provides long-term stability for nanoparticles by preventing particles agglomeration. The results indicated that gelatin was a reliable green stabilizer, which can be used as a polymerization agent in the sol-gel method for synthesis of tiny size TiO₂-NPs. Moreover, the composite film was prepared by synthesized TiO₂-NPs nanoparticles and multi wall carbon nanotube (MWNT) on glassy carbon electrode (TiO₂-MWNT/GCE). The TiO₂-MWNT/GCE responded linearly to L-tryptophan (L-Trp) in the concentration of 1.0 × 10^?6 to 1.5 × 10^?4 M with detection limit of 5.2 × 10^?7 M at 3 using amperometry. The studied sensor exhibited good reproducibility and long-term stability.     

Synthesis of uniform anatase TiO2 nanoparticles by the gel-sol method 2. Adsorption of OH- Ions to Ti(OH)4 gel and TiO2 particles

The pH value in the gel-sol system for the preparation of uniform anatase TiO2 nanoparticles, as a decisive factor for controlling the size and shape of the final product, was found to be significantly changed during the formation process of the anatase TiO2 particles from a condensed Ti(OH)4 gel. The dramatic evolution of pH with the progress of the synthetic process has clearly been explained in terms of the adsorption and desorption of a hydroxide ion (OH-) ora proton (H+) on the solids transforming with time. The adsorption and desorption of OH- or H+ were enhanced by the presence of an inert electrolyte such as NaClO4, as explained by its shielding effect on the electrical interactions between the electrically charged precipitates and free OH- and H+ ions. The electrolyte also hampered the phase transformation of Ti(OH)4 precipitate to anatase TiO2. This effect of electrolytes was explained in terms of the inhibited nucleation of anatase TiO2 by enhanced adsorption of OH- ions toTiO2 embryos. The points of zero charge (PZC) of the amorphous Ti(OH)4 precipitate and the anatase TiO2 particles at 25 degrees C were obtained from the change in pH associated with the adsorption and desorption of OH- or H+, i.e., 4.6 for Ti(OH)4 precipitate and 6.0 for anatase TiO2 in the presence of 0.1 mol dm(-3) NaClO4. The PZCof the Ti(OH)4 precipitate measured at 25 degrees C after additional aging at 100 degrees C for 30 min was shifted to 4.1, owing to the promoted adsorption of OH-.     

Preparation and comparison of supported gold nanocatalysts on anatase, brookite, rutile, and P25 polymorphs of TiO2 for catalytic oxidation of CO

Nanosized anatase (< or = 10 nm), rutile (< or = 10 nm), and brookite (approximately 70 nm) titania particles have been successfully synthesized via sonication and hydrothermal methods. Gold was deposited with high dispersion onto the surfaces of anatase, rutile, brookite, and commercial titania (P25) supports through a deposition-precipitation (D-P) process. All catalysts were exposed to an identical sequence of treatment and measurements of catalytic CO oxidation activity. The as-synthesized catalysts have high activity with concomitant Au reduction upon exposure to the reactant stream. Mild reduction at 423 K produces comparably high activity catalysts for every support. Deactivation of the four catalysts was observed following a sequence of treatments at temperatures up to 573 K. The brookite-supported gold catalyst sustains the highest catalytic activity after all treatments. XRD and TEM results indicate that the gold particles supported on brookite are smaller than those on the other supports following the reaction and pretreatment sequences.     

Mechanistic studies of the photocatalytic oxidation of trichloroethylene with visible-light-driven N-doped TiO2 photocatalysts

Visible-light-driven TiO2 photocatalysts doped with nitrogen have been prepared as powders and thin films in a cylindrical tubular furnace under a stream of ammonia gas. The photocatalysts thus obtained were found to have a band-gap energy of 2.95 eV. Electron spin resonance (ESR) under irradiation with visible light (lambda > or = 430 nm) afforded the increase in intensity in the visible-light region. The concentration of trapped holes was about fourfold higher than that of trapped electrons. Nitrogen-doped TiO2 has been used to investigate mechanistically the photocatalytic oxidation of trichloroethylene (TCE) under irradiation with visible light (lambda > or = 420 nm). Cl and O radicals, which contribute significantly to the generation of dichloroacetyl chloride (DCAC) in the photocatalytic oxidation of TCE under UV irradiation, were found to be deactivated under irradiation with visible light. As the main by-product, only phosgene was detected in the photocatalytic oxidation of TCE under irradiation with visible light. Thus, the reaction mechanism of TCE photooxidation under irradiation with visible light clearly differs markedly from that under UV irradiation. Based on the results of the present study, we propose a new reaction mechanism and adsorbed species for the photocatalytic oxidation of TCE under irradiation with visible light. The energy band for TiO2 by doping with nitrogen may involve an isolated band above the valence band.     

Enhancement of the electrochemical capacitance of TiO2 nanotube arrays through controlled phase transformation of anatase to rutile

Here, we report the fabrication of self-organized titania (TiO(2)) nanotube array supercapacitor electrodes through controlled phase transformation of TiO(2), with aerial capacitances as high as 2.6 mF cm(-2), which far exceeds the values so far reported in the literature. The role of phase transformation in the electrochemical charge-discharge behaviour of nanocrystalline TiO(2) nanotubes is investigated and discussed in detail. The ease of synthesis and the exceptional electrochemical properties make these nanotube arrays an alternative candidate for use in energy storage devices.     

The reactivities of TiO2 (rutile and anatase) for the solid-state reactions with BaSO4 and BaCO3

DTA and isothermal kinetic studies were carried out on the reactions of BaSO₄ or BaCO₃ with TiO₂ (anatase and rutile) to BaTiO₃. In the initial steps, the reactions of BaSO₄ with TiO₂ (anatase) proceeded to BaTi₄O₉, of BaSO₄ with TiO₂ (rutile) to BaTi₃O₇, and of BaCO₃ with TiO₂ (anatase and rutile) to Ba₂TiO₄, respectively. These reactions were connected with the formation of binary metal oxide through some intermediates, which are BaSO₄ or BaCO₃ incorporated with TiO₂. The reactivity of anatase was higher than that of rutile in all reaction systems.