Formation of hydrated titanium dioxide from seeded titanyl sulphate solution

The paper analyses the influence of various kinds and amounts of titanium dioxide nuclei addition to a solution of titanyl sulphate on the conversion degree of TiOSO₄ to hydrated titanium dioxide and sulphuric acid. An industrial solution of titanyl sulphate used to produce titanium white was used in the present investigations. It was found that the course of hydrolysis clearly depended on the investigated parameters. The anatase nuclei calcined at 373 K and 333 K and rutile nuclei increased the degree of titanyl sulphate hydrolysis as compared to non-nucleation hydrolysis. The final degree of hydrolysis was by 1–2 % higher than that achieved without any nuclei addition. The constant rates of both colloidal intermediate and final crystalline products formation were higher in the hydrolysis process with both anatase nuclei after heat treatment at lower temperature and rutile nuclei in comparison to the same processes conducted in the absence of these nuclei. Presented at the 35th International Conference of the Slovak Society of Chemical Engineering, Tatranské Matliare, 26–30 May 2008.     

Photocatalytic lithography based on thin films of amorphous hydrated titanium dioxide

The mechanism of photoactivation of amorphous hydrated titanium dioxide thin films containing palladium ions toward the reaction of electroless deposition of nickel was studied. It was shown that the photocatalytic reduction of palladium ions during UV irradiation results in the formation of intermediate Pd(I) states that subsequently disproportionate, yielding a Pd nanophase. The palladium nanoparticle-catalyzed electroless deposition of nickel on exposed areas of the titanium dioxide photolayer makes it possible to fabricate metal patterns having a 5-μm resolution, with the fast and irreversible capture of photoelectrons at the latent image formation step preventing the image from blurring, including the process on conducting substrates.     

Mechanism and kinetics of the hydrothermal synthesis of titanium dioxide

In situ heat-flow calorimetry, powder X-ray diffraction, and X-ray diffraction analysis are used to study titanium dioxide formation under hydrothermal conditions. The effect of the chemical history on the formation mechanism and micromorphology of the resulting nanocrystalline TiO₂ powders is studied.     

Study of ion-exchange properties of hydrated titanium dioxide towards cesium and strontium cations

Acid-base and sorption properties of spherically granulated material based on hydrated titanium dioxide were studied. It was shown that the sorption capacity of the ion exchanger is due both to the structure (cross-linking density of gels and, consequently, their porosity) and to the number of active acid centers. The kinetic specific features of the sorption of cations were considered and it was found that the sorption kinetics is limited by the intraparticle diffusion. It was shown that the sorbent can be used to purify low-salt technological solutions of liquid radioactive wastes.     

Morphological behavior of spherically granulated hydrated zirconium dioxide during its chemical and hydrothermal treatments

Hydrated zirconium dioxide samples were synthesized via original sol–gel route by two-step neutralization of zirconium oxychloride. Spherical granules of zirconia materials were prepared using a well-known “oil-drop” method. By the use of low temperature nitrogen adsorption, it is shown that surface fractal dimension of synthesized xerogels strongly depends on synthesis conditions, chemical and hydrothermal treatments. It is established that the change of synthesis conditions allows to obtain zirconium containing materials with developed porous structure: BET surface area—250–450 m²/g, pore diameter—2.0–4.2 nm, surface fractal dimension—2.28–2.63. It is shown that surface fractal dimension is an important parameter allowing to control the final properties of synthesized material and to determine the reasons of non-reproducibility of adsorptive, catalytic and other physical and chemical properties of zirconium containing oxides from synthesis to synthesis.     

Ion exchange of some transition metal cations on hydrated titanium dioxide in aqueous ammonia solutions

The adsorption of transition metal cations on hydrated titanium dioxide in complexing ammonia and amine solutions has been studied as a function of ammonia (amine) concentration. The relationships between the distribution coefficients and ammonia concentration as well as the effects of various amines on sorption of transition metals indicate that a coordinate bond is formed between the metal ions and the hydroxy groups of the sorbent. The distribution coefficients of silver(I) and cobalt(III), which form strong ammonia complexes in aqueous solutions, decrease with increasing concentration of ammonia already at concentrations exceeding 10^–3. mol·dm^–3. Cations of zinc, manganese and mercury which form much weakerammonia complexes do not exhibit any effect of ammonia concentration in the whole range investigated. In the case of sorption of macroamounts of ammonia or amine complexes of silver, the molecular sieve effect plays an important role. The differences in the affinity of hydrated titanium dioxide for ammonia solvates of various transition metal ions can serve as a tool for effective separation of these ions in ammonia solutions.     

Sorption rate of uranyl ions by Hyphan cellulose exchangers and by hydrated titanium dioxide

Summary Sorption of uranyl ions by the cellulose exchanger Hyphan proceeds rather fast. Two steps are observed with half-times of the order of 10 s and 2 min. The majority of the uranyl ions is bound in 1 min. Sorption of uranyl ions by titanium dioxide is a very slow process. For particle sizes between 0,1 and 0.5 mm the half-time is about 3 h and equilibrium is attained in about 1 day. The effect of stirring suspensions of inorganic sorbents like titanium dioxide in solution is investigated in detail. Sorption of uranyl ions by titanium dioxide and change in pH in solution are measured simultaneously as a function of time.Alexander von Humboldt fellow     

Transformations of P-chalcogenide precursors with a hydrated metal salt

The preparation, characterisation and X-ray structures of the three Ni(II) salts [Ni{ArP(OH)S₂}₂(thf)₂] (1) (Ar = 4-anisyl), [Ni{PhP(OH)Se₂}₂(thf)₂] (2) and [Ni{P(OH)₂S₂}₂(thf)₄] (3) are reported.     

Antibacterial inactivation of spiramycin after titanium dioxide photocatalytic treatment

The photocatalytic degradation of an antibiotic (spiramycin) has been studied using immobilized titanium dioxide (TiO₂) as a photocatalyst in a laboratory reactor under ultraviolet illumination (365 nm). The degradation of the antibiotic was monitored by ultraviolet spectrophotometry and high-pressure liquid chromatography and confirmed by an antibacterial activity evaluation. Two types of TiO₂ (P25 and PC500) immobilized on glass plates were compared. For TiO₂ PC500 immobilization on glass and paper was also studied. A slightly better degradation was obtained with TiO₂ P25 for which the degradation kinetics were investigated. The Langmuir–Hinshelwood kinetic model is satisfactorily obeyed at initial time and in the course of the reaction. Adsorption and apparent rate constants were determined. These results show a complete degradation of spiramycin, which was confirmed by the inhibition of the antibacterial activity of Staphylococcus xylosus, when exposed to spiramycin solutions treated with photocatalyst for a short time. In addition, the codegradation of spiramycin and tylosin was investigated and showed that tylosin had a higher affinity to the catalyst TiO₂ P25 than spiramycin. The complete degradation of spiramycin confirms the feasibility of such a photocatalytic treatment process for spiramycin elimination from contaminated water.     

Structural and morphological transformations of mesostructured titanium phosphate through hydrothermal treatment

The phase transformation of mesostructured titanium phosphate (TiPO) from hexagonal to lamellar structure was observed in a simply hydrothermal treatment, accompanied by drastically morphological changes in the micrometer-sized particles. XRD pattern revealed that different mesostructures were obtained by simply varying hydrothermal temperature or treatment duration. SEM and TEM observations showed the morphological evolution from individual particles to interconnected nanoplatelets. A significant blue shift in UV-vis spectra was observed for lamellar mesostructured material, which may be associated with the different coordinated Ti-sites in the hexagonal and lamellar mesostructures. FT-IR spectra and detailed (31)P MAS NMR studies indicated that additional POH groups were presented in the lamellar structure, which might play a key role in the structural and morphological transformations of mesostructures.     

Nanotubes in Si-doped titanium dioxide

Silicon-doped metal oxide nanotubes are formed in Si-doped titanium dioxide prepared by a sol-gel technique.     

Photoelectron imaging of hydrated carbon dioxide cluster anions

The effects of homogeneous and heterogeneous solvation on the electronic structure and photodetachment dynamics of hydrated carbon dioxide cluster anions are investigated using negative-ion photoelectron imaging spectroscopy. The experiments are conducted on mass-selected [(CO(2))(n)()(H(2)O)(m)()](-) cluster anions with n and m ranging up to 12 and 6, respectively, for selected clusters. Homogeneous solvation in (CO(2))(n)()(-) has minimal effect on the photoelectron angular distributions, despite dimer-to-monomer anion core switching. Heterogeneous hydration, on the other hand, is found to have the marked effect of decreasing the photodetachment anisotropy. For example, in the [CO(2)(H(2)O)(m)()](-) cluster anion series, the photoelectron anisotropy parameter falls to essentially zero with as few as 5-6 water molecules. The analysis of the data, supported by theoretical modeling, reveals that in the ground electronic state of the hydrated clusters the excess electron is localized on CO(2), corresponding to a (CO(2))(n)()(-).(H(2)O)(m)() configuration for all cluster anions studied. The diminishing anisotropy in the photoelectron images of hydrated cluster anions is proposed to be attributable to photoinduced charge transfer to solvent, creating transient (CO(2))(n)().(H(2)O)(m)()(-) states that subsequently decay via autodetachment.     

Characteristics of the hydrous titanium dioxide-anatase phase transformation during hydrothermal treatment in aqueous solutions

The transformations of hydrous titanium dioxide, prepared by thermal hydrolysis of titanium(IV) compounds in sulfuric acid solutions, during hydrothermal treatment (150–240°C) in water were studied. The dispersivity and the chemical compositions of the samples obtained determined depending on the synthesis conditions (the composition) of hydrous titanium dioxide and the heat treatment temperature.     

Visible spectrum of titanium dioxide

The electronic spectrum in the region 17?500 cm(-1) to 18?850 cm(-1) of a cold molecular beam of TiO(2) has been investigated using laser induced fluorescence (LIF) and mass-resolved resonance enhanced multi-photoionization (REMPI) spectroscopy. Bands at 18?412 cm(-1), 18?470 cm(-1) and 18?655 cm(-1) were recorded at a resolution of 35 MHz, rotationally analyzed, and assigned as the ?(1)B(2) (0,1,2) ←X[combining tilde](1)A(1) (0,0,0), ?(1)B(2) (1,0,0) ←X[combining tilde](1)A(1) (0,0,0) and ?(1)B(2) (1,1,0) ←X[combining tilde](1)A(1) (0,0,0) transitions. The dispersed fluorescence from the ?(1)B(2) (0,1,2) and ?(1)B(2) (1,0,0) levels were combined with previous results to produce an improved set of vibrational parameters for the X[combining tilde](1)A(1) state. The optical Stark effect in the ?(1)B(2) (0,1,2) ←X[combining tilde](1)A(1) (0,0,0) and ?(1)B(2) (1,0,0) ←X[combining tilde](1)A(1) (0,0,0) bands were recorded and combined with earlier results for ?(1)B(2) (1,1,0) ←X[combining tilde](1)A(1) (0,0,0) to determine the permanent electric dipole moment for these states. The origin and harmonic vibrational constants for the ?(1)B(2) state are determined to be: T(000) = 17?593(5) cm(-1), ω(1) = 876(3) cm(-1), ω(2) = 184(1) cm(-1), and ω(3) = 316(2) cm(-1). A normal coordinate analysis was performed and Franck-Condon factors calculated.     

Raman spectra of titanium dioxide

First-order Raman spectra have been recorded at room temperature for the anatase and rutile phases of polycrystalline titanium dioxide using an argon ion laser as exciter. The high-temperature rutile phase was found to be stabilized at temperatures below 450°C. Anatase transforms to rutile phase at ～750°C. All the Raman active fundamentals predicted by group theory are observed.     

Defect disorder of titanium dioxide

The present work derived defect disorder diagram representing the effect of oxygen activity on the concentration of both ionic and electronic defects for undoped TiO2. This diagram was determined using the equilibrium constants derived in the present work, including (i) the intrinsic electronic equilibrium constant, (ii) the equilibrium constant for the formation of oxygen vacancies, and (iii) equilibrium constant for the formation of titanium vacancies. These equilibrium constants are consistent with three properties determined independently, including: electrical conductivity, thermoelectric power and change of mass determined by thermogravimetry. The derived defect disorder diagram may be used for tailoring semiconducting properties of TiO2 that are desired for specific applications through the selection of optimized processing conditions.     

Niobium diffusion in niobium-doped titanium dioxide

The present work studied the self-diffusion coefficient of ⁹³Nb in Nb-doped TiO₂ single crystal (4.3 at.% Nb) at high oxygen activity [p(O₂) = 21 kPa] over the temperature range 1,073 to 1,573 K. The diffusion-induced ⁹³Nb concentration profile was determined by using secondary ion mass spectrometry (SIMS). The subsequently determined self-diffusion coefficient of ⁹³Nb exhibits the following temperature dependence:. This study builds upon a similar study performed previously for ⁹³Nb tracer diffusion in undoped TiO₂, and identifies the effect of compositional change on self-diffusion behaviour. The obtained activation energy has been considered in terms of migration and formation enthalpies of titanium vacancies. The present work is dedicated to Professor John Bockris on the occasion of his 85th birthday. His contribution to the progress of modern electrochemistry is well-known to several generations of students and researchers who have been using his textbooks. His specific contribution to the theory of photoelectrochemical water splitting is known to all working in this fascinating area.