Effect of annealing on UV-visible absorption and photoluminescence behavior of liquid phase deposited TiO2 nanorods

In this work, anatase and rutile TiO₂ nanorods were fabricated using one-step liquid phase deposition process, followed by heat treatment in the range 300-800°C. The direct and indirect band gap of the TiO₂ nanorods was estimated form optical absorption data which illustrated a red shift at higher temperatures owing to the different nature of excitons in anatase and rutile phases. The photoluminescence (PL) spectra revealed the presence of two main emission bands consisting of four peaks. It was found that two high-energy peaks located at 2.95-3.30 eV could be generated from exciton transitions from the conduction band to the valence band of TiO₂ nanorods, while two low-energy peaks located at 2.43-2.64 eV may arise from surface state transitions. The PL intensity firstly increased with temperature and at 500°C reached a maximum value, then decreased through increasing temperature up to 800°C. These variations in the intensity of PL emission could be explained in terms of changes in phase structure, crystallinity, and amount of the oxygen vacancies, which are all dependent to the annealing temperature based on X-ray diffractometer and X-ray photoelectron spectrometer studies. These results indicated that annealing temperature allows to manipulate the properties of TiO₂ nanorods for opto-electronic applications.     

An Amalgam of Mg-Doped TiO2 Nanoparticles Prepared by Sol–Gel Method for Effective Antimicrobial and Photocatalytic Activity

In this study, undoped and Magnesium doped TiO₂ nanoparticles (Mg-TiO₂ NPs) are successfully synthesized via a simple sol–gel method cost-effectively. The prepared Mg- TiO₂ NPs is characterized by UV–Vis, FTIR, PL, XRD, FESEM, TEM, and EDAX. UV–Visible Spectroscopy showed that an increase in the optical bandgap concerning the concentration of dopant Mg increases. The bandgap values were found to be 3.57–3.54 eV. FTIR spectra shows that the presence of the characteristic stretching and bending vibrational band of Ti–O bonding at 468 cm^?1 and shifts in vibrational bands were observed for Mg-TiO₂ NPs. PL spectra of Mg- TiO₂ NPs at different concentrations exhibit a strong UV emission band. X-ray diffraction confirmed the formation of the tetragonal anatase phase. The average crystallite size of synthesized samples was found to be 22–19 nm. The average crystallite size of Mg- TiO₂ NPs decreases with increasing the concentration of dopant Mg. The FESEM and TEM analysis confirmed that the spherical morphology for both TiO₂ and Mg-TiO₂ NPs. SAED pattern confirms the crystalline nature of prepared samples. EDAX spectra confirm the presence of Ti, O, and Mg and confirm that Mg²⁺ ions are present in the TiO₂ lattices. The prepared samples were investigated against gram-positive and gram-negative bacteria. The prepared samples exhibit potent antibacterial activity against gram-negative bacteria than the gram-positive bacteria. The prepared samples exhibit significant photocatalytic degradation for Methylene blue (MB).

     

Synthesis of Ti1−xSnxO2 nanosized photocatalysts in reverse microemulsions

The preparation of Ti_1−xSn_xO₂ nanocrystalline photocatalysts in reverse microemulsions is reported in this work. The obtained materials have been characterised by total reflection X-ray fluorescence (TXRF), X-ray diffraction (XRD) and Raman and UV–vis spectroscopies. Very good accordance between calculated and obtained compositions is observed. Undoped TiO₂ prepared in this way crystallises in the anatase phase. Tin-doped anatase is formed with x < 0.05, while both anatase and rutile phases crystallise when x ≥ 0.05. When both phases coexist, a preferential doping of rutile seems to occur. When x = 0.10, a multiphase mixture containing TiO₂(anatase), TiO₂(rutile) and SnO₂ was formed. No significant modification of the band gap is found in any case. The photocatalytic activity of the obtained catalysts is compared employing the trichloroethylene photocatalytic degradation as a test reaction. The beneficial effect of Sn⁴⁺ in the activity of TiO₂ appears to be related to the formation of anatase–rutile mixtures, leading to the highest specific photocatalytic activity in the sample of composition Ti_0.93Sn_0.07O₂, with anatase:rutile ratio close to 3.     

Kinetics of anatase transition to rutile TiO2 from titanium dioxide precursor powders synthesized by a sol-gel process

Kinetics of anatase transition to rutile TiO₂ from titanium dioxide precursor powders synthesized by a sol-gel process have been studied using differential thermal analysis (DTA), X-ray diffraction, transmission electron microscopy (TEM), selected area electron diffraction (SAED), nano beam electron diffraction (NBED) and high resolution TEM (HRTEM). The DTA result shows residual organic matter decomposed at 436 K. The transition temperature for amorphous precursor powders converted to anatase TiO₂ occurred at 739 K. Moreover, the full anatase transition to rutile TiO₂ occurred at 1001 K. The activation energy of anatase TiO₂ formation was 128.9 kJ/mol. On the other hand, the activation energy of anatase transition to rutile TiO₂ was 328.4 kJ/mol. Mesoporous structures can be observed in the TEM image.     

Suspension high velocity oxy-fuel spraying of a rutile TiO2 feedstock: Microstructure,phase evolution and photocatalytic behaviour

Nano-structured TiO₂ coatings were produced by suspension high velocity oxy fuel (SHVOF) thermal spraying using water-based suspensions containing 30 wt% of submicron rutile powders (~180 nm). By changing the flame heat powers from 40 kW to 101 kW, TiO₂ coatings were obtained with distinctive microstructures, phases and photocatalytic behaviour. Spraying with low power (40 kW) resulted in a more porous microstructure with the presence of un-melted nano-particles and a lower content of the anatase phase; meanwhile, high powers (72/101 kW) resulted in denser coatings and rougher surfaces with distinctive humps but not necessarily with a higher content of anatase. Linear sweep voltammetry (LSV) was used to evaluate the photocatalytic performance. Surprisingly, coatings with the lowest anatase content (~20%) using 40 kW showed the best photocatalytic behaviour with the highest photo-conversion efficiency. It was suggested that this was partially owing to the increased specific surface area of the un-melted nano-particles. More importantly, the structural arrangement of the similarly sized TiO₂ nano-crystallites between rutile and antase phases also created catalytic “hot spots” at the rutile−anatase interface and greatly improved the photo-activity.     

Synthesis of phase- and shape-controlled TiO2 nanoparticles via hydrothermal process

The TiO₂ nanoparticles with anatase (5.7–12.7 nm), rutile (5.4–8.8 nm), mixed (4.4–8.6 nm) phase were individually prepared using the hydrothermal method. The structure and shape of the particles could be controlled by careful alterations of the hydrothermal conditions. Herein, the TiO₂ nanoparticles were successfully synthesized by employing Ti-isopropoxide as the titanium source into hydrochloric acid solution at mild conditions. The crystal structures such as anatase, rutile and mixed phase of TiO₂ nanoparticles were determined by means of concentration of hydrochloride. Especially, we observed that the rutile TiO₂ crystallites were grown into one-dimensional nanostructures, especially, nanowires, with increasing reaction time. The mechanism of the crystallization of the nanoparticles and the growth habit of TiO₂-rutile structure were discussed.     

Anatase–rutile transformation of TiO2 sol–gel coatings deposited on different substrates

Titanium dioxide is widely used in a lot of applications. The properties of TiO₂ strongly depend on its phase composition. The transformation temperature between phases is influenced by a lot of factors. One of them is a type of substrate under the TiO₂ film. In presented work, thin films of TiO₂ were deposited by the sol–gel method on silicon, stainless steel (304 L) and Co–Cr–Mo alloy (Vitallium). The process of anatase–rutile phase transformation was investigated by Scanning Electron Microscopy (SEM) and X-Ray Diffraction (XRD) studies of deposited coatings. The results were compared with anatase–rutile transformations temperature of TiO₂ powders obtained by analogous sol–gel process. The temperature of anatase–rutile phase transformation changed in the range of 700–1000 °C and strongly depends on a kind of substrate. It was found that anatase–rutile transformation of TiO₂ coating proceeded at a higher temperature than rutilization of titania powders.     

Boron-doped rutile TiO2/ anatase TiO2/ ZrTiO4 ternary heterojunction photocatalyst with optimized phase interface and band structure

To improve the photocatalytic performance of TiO₂-based heterostructures, Z-scheme/Ⅱ-type rutile TiO₂ (R)/anatase TiO₂ (A)/ZrTiO₄ ternary heterojunction photocatalyst was designed and prepared via a facile one-step calcining strategy. Phase interface and band structure of the materials were controlled and optimized by regulating R–TiO₂/A–TiO₂ mass ratio in the TiO₂ (A, R)/ZrTiO₄ structures using boron doping. The highest photocatalytic performance and excellent catalytic stability of Rhodamine B removal was observed from the heterojunction with a low R–TiO₂/A–TiO₂ mass ratio of 0.066, even after five testing cycles, accompanying with low photoluminescence intensity and electrochemical impedance, high photocurrent and charge carrier density (5.12 × 10²² cm⁻³), and a positive shift of valence band position (from +2.06 to + 2.16 eV). The increased photodegradation behaviour was due to the remarkably enhanced separation efficiency and improved redox ability of the photo-induced charge carriers as a result of the high content of oxygen vacancies and the formed anatase TiO₂/rutile TiO₂ Z-scheme heterojunction.     

Photocatalytic partial oxidation of methylpyridine isomers on TiO2 particles under an anaerobic condition

Photocatalytic oxidation of methylpyridine isomers (2-methylpyridine, 3-methylpyridine, and 4-methylpyridine) was investigated in a mixed solution of acetonitrile and water or acetonitrile using various kinds of TiO₂ powders as photocatalysts. The main products from methylpyridine isomers were pyridinecarboxaldehyde isomers (2-pyridinecarboxaldehyde, 3-pyridinecarboxaldehyde, and 4-pyridinecarboxaldehyde). Rutile large TiO₂ particles showed the highest level of activity for oxidation of 2-methylpyridine probably because band bending was necessary for the oxidation of 2-methylpyridine. On the other hand, a fine particle having an anatase or rutile phase showed a higher level of activity than large TiO₂ particles for oxidation of 3-methylpyridine. A rutile fine particle showed the highest level of activity for the reaction. It was found that pure rutile or pure anatase particles were inactive for oxidation of 4-mathylpyridine. If the particles are not extremely small, pure rutile and pure anatase powders show fairly high levels of activity, and those containing both anatase and rutile phases show the highest level of activity. The activity of pure rutile particles was also enhanced by physically mixing them with a small amount of small anatase particles, which were inactive for this reaction. These results can be explained by the synergism between rutile and anatase particles. All of these reactions effectively proceeded even under anaerobic conditions. Photocatalytic reduction of methylpyridine isomers concomitantly proceeded on TiO₂ particles under the conditions used. These results suggest that the activities of TiO₂ photocatalysts for oxidation of methylpyridine isomers are dominated by the oxidation potential of alkylpiridine and band bending of TiO₂ particles.     

Photocatalytic mineralization of phenol catalyzed by pure and mixed phase hydrothermal titanium dioxide

The photocatalytic mineralization of phenol catalyzed by pure (anatase, rutile) and mixed phase hydrothermal TiO₂ was studied in aqueous solution employing different oxidative agents, H₂O₂ and O₂. In the case of H₂O₂, rutile particles, having large dimensions and high aspect ratio (size: 30–70 nm × 150–350 nm), display the highest catalytic activity due to their low tendency to recombine electrons and holes generated by UV irradiation. By using water dissolved gaseous O₂, the catalytic TiO₂ activity generally decreases and rutile displays the lowest efficacy. In fact, oxygen preferentially chemisorbs at the surface of the nanosized particles of anatase (5–15 nm) and acts as effective electron scavenger, inhibiting the electron-hole recombination. The number of electron and hole traps (Ti³⁺, O₂⁻ and O⁻) and the rate of formation of the short-lived hydroxyl radicals OH under UV irradiation, were evaluated by electron paramagnetic resonance (EPR). A correlation was suggested among the amount of the charge carrier centers, the rate of formation of OH radicals and the catalyst photoactivity. This confirms that the photocatalytic properties depend on the possibility that electrons and holes separately interact with the oxidative agents at the TiO₂ surface, inducing the formation of OH radicals.     

Different Effects of Fluoride Surface Modification on the Photocatalytic Oxidation of Phenol in Anatase and Rutile TiO2 Suspensions

The effect of calcination temperature on the photocatalytic degradation of phenol with aqueous suspensions of synthetic anatase and rutile TiO₂ under UV light irradiation (λ > 320 nm), was studied in the absence and presence of NaF. The presence of fluoride accelerates the degradation of phenol in anatase TiO₂, with this positive effect increasing at first, before declining with increasing calcined temperature. A negative effect of fluoride was observed for all the rutile TiO₂ suspensions. The selectivity of catechol increased in the presence of fluoride in both anatase and rutile TiO₂ suspensions.     

A glass-ceramic approach to prepare porous TiO2 with self-supported nano-flakes: The phase evolution and the thermal stability of the product

A porous TiO₂ material consisting of self-supported nano-flakes with mixed anatase/rutile phases was prepared by acid-etching of a glass-ceramic derived from 20MgO?24CuO?32TiO₂?24P₂O₅ phosphate glass frit. The analysis showed that selective dissolution of components of CuO, Mg₃(PO₄)₂, MgTi₄(PO₄)₆ in the crystallized sample first occurred, followed by the growth of TiO₂ nano-flakes and the formation of Ti(HPO₄)₂?2H₂O phase due to the supply of Ti⁴⁺ and [PO4]^3- released form the dissolved crystallites. The sample acid-treated for 17 h had the best crystallization of anatase and rutile phases, and the smallest band gap. In addition, the porous skeleton showed excellent thermal stability and a large surface area. The present study provided a new method which could be used for the scale-up production of porous TiO₂.     

Green synthesis of TiO2 nanospheres from isolated Aspergillus eucalypticola SLF1 and its multifunctionality in nanobioremediation of C. I. Reactive Blue 194 with antimicrobial and antioxidant activity

For synthesis of titanium dioxide (TiO₂) nanoparticles (NPs), Green methods have been proven to be more efficient than several physiochemical methods. This article presents a non-toxic, ecofriendly, cost-effective and a facile route of green synthesis of TiO₂ NPs by an isolated fungus Aspergillus eucalypticola SLF1, which exhibits excellent photocatalytic, antimicrobial and antioxidant activity without structural modification done by physicochemical methods. The TiO₂ NPs are characterized by UV–Visible spectroscopy, XRD, FTIR, FE-SEM, DLS, TEM, BET, Raman spectroscopy and PL. The mesoporous, anatase phase, with a band gap 3.49 eV observed by BET, XRD. UV–Visible spectral analysis displayed sunlight driven photocatalytic performance against C. I. Reactive Blue 194 by advanced oxidation process. Decolourization and 99.70% degradation within 30 min exhibited pseudo first order kinetic with reaction rate constant 0.1935 min⁻¹ by linear method. These findings are superior physicochemical methods. Ecofriendly degradation was confirmed by UV–Vis. HPLC and LCMS etc and phytotoxic studies.     

Size and Shape Tailoring of Titania Nanoparticles Synthesized by Solvothermal Route in Different Solvents

A simple solvothermal low‐temperature synthesis process of TiO₂ nanoparticles was investigated in different solvents [Octanol (Oc), Ethanolamine (Am) and Terathane (Tr)] with titanium (IV) chloride (TiCl₄) as precursor. The samples were characterized by X‐Ray Diffraction (XRD) and Transmission Electron Microscopy (TEM). XRD showed the crystallite size ranging from 4 to 12 nm, which were calculated using Debye–Scherrer's equation. The existence of poor or high crystalline anatase phases and high crystalline anatase/rutile mixture was also shown. TEM images displayed variations in the morphological behavior depending on the synthesis condition. Particles of irregular morphology with high irregular agglomeration up to well‐defined particles can be observed, which are self‐assembled by oriented attachment (OA). This self‐assembly led to TiO₂ microparticles with 3‐D Wulff shape for anatase and 1‐D shape for rutile. The results showed that the TiO₂ nanopowder could be easily engineered and adapted by the solvent type, the TiCl₄ concentration and the synthesis time.     

Visible light-active sub-5 nm anatase TiO2 for photocatalytic organic pollutant degradation in water and air,and for bacterial disinfection

Visible-light-sensitive sub-5 nm anatase titanium dioxide (TiO₂) nanoparticles (NPs) were fabricated without any doping and calcination treatments. The energy band gap was effectively narrowed to ~ 2.98 eV. The surface and subsurface hydroxyl defects were ascertained as the origin for the band gap narrowing and for the efficient azo-based dye degradation in water and formaldehyde decomposition in air, as well as disinfection of Staphylococcus aureus bacteria, under visible light irradiation.     

Stable anatase phase with a bandgap in visible light region by a charge compensated Ga–V (1:1) co-doping in TiO2

A series of charge compensated Ga–V co-doped TiO₂ samples (Ti_(1-x)(Ga_0.5V_0.5)_xO₂) have been synthesized by a modified sol-gel process. X-ray diffraction pattern shows that the anatase to rutile (A→R) onset temperature (T_O) shifts to a higher temperature, whereas the complete phase transformation temperature (T_C) shifts to a low-temperature region as compared to pure TiO₂, due to Ga–V incorporation. Ga–V co-doping helps in the transformation of some smaller sized Ti⁴⁺ to a relatively larger Ti³⁺. In the anatase phase, oxygen content also increases with increasing doping concentration, which along with the larger size of Ti³⁺ results in lattice expansion and thereby delays the T_O. In the rutile phase, oxygen vacancy increases with increasing doping concentration, which results in lattice contraction and accelerates phase transition. Grain growth process is hindered in the anatase phase (crystallites size reduces from ~15 nm (x = 0.00) to 8 nm (0.10)), whereas it is accelerated in the rutile phase as compared to pure TiO₂. In both phases bandgap (E_g) reduces to the visible light region (anatase: E_g = 3.16 eV (x = 0.00) to 2.19 eV (x = 0.10) and rutile: 3.08 eV (x = 0.00) to 2.18 eV (x = 0.10)) in all co-doped samples. The tail of the absorption edge reveals lattice distortion and increase of Urbach energy proofs the same due to co-doping. All these changes (grain growth, phase transition, and optical properties) are due to lattice distortion created by the combined effect of substitution, interstitials, and oxygen vacancies due to Ga–V incorporation in TiO₂.     

Effect of TiO2 on UV stability of polymeric binder films used in waterborne facade paints

The effect of two TiO₂ polymorphs with different optical activity (rutile and anatase) on UV-stability of four polymeric binders used in water-borne paints is described. The latexes employed in this study are based on acrylic, styrene–acrylic, vinyl acetate and vinyl acetate–butyl acrylate (co)polymers. Thin films obtained from the respective latexes doped with 1% TiO₂ were exposed to accelerated weathering by irradiation with UV light (λ ≥ 275 nm) and analysed using electrokinetic potential (ζ-potential), FTIR ATR spectroscopy, SEM microscopy and contact angle. The study shows that while rutile particles dispersed evenly in all the polymer matrices, the anatase remained partly aggregated. Despite markedly different optical properties, both titania polymorphs showed similar and minor effects on accelerated weathering of all the polymeric binders. The trends in surface charge and wettability remained the same as for the undoped films. More pronounced changes were observed in spectroscopic measurements, which probe the films deeper into the bulk. For the styrene-based films a photochemical interaction between TiO₂ and the styrene chromophore resulted in quenching the absorption band of the titania's photogenerated surface-trapped holes.     

Sonosynthesis of nanostructured TiO2 doped with transition metals having variable bandgap

Here is described a sonosynthesis method to produce nanostructured TiO₂ pure and doped (Al, C, Co, Fe and Rh). The synthesized TiO₂ is amorphous and is transformed to anatase, brookite or rutile by heat treatments at temperatures between 100 and 300 °C. Pure TiO₂ can be partially transformed to brookite between 100 and 300 °C. The band gap in all heat treated samples from 100–600 °C is relatively constant, 3.2 eV, except for those doped with Fe. This effect on the band gap is the results of a bi/tri-crystal (anatase:brookite:rutile) framework. Rhodium is the most effective dopant to narrow the band gap, the opposite effect is observed with C. In single phase frameworks the bandgap can be modified ranges from 2.38 to 4.10 eV depending on the dopant. TiO₂ lattices are rigid enough to promote an outwards diffusion of the dopants to the surface of the particles forming nanostructured precipitates. The precipitates develop a network of quantum-dots with sizes between 5 and 10 nm.     

Direct multipulse laser processing of titanium oxide–graphene oxide nanocomposite thin films

Nanocomposite thin films consisting of titanium oxide (TiO₂) nanoparticles (NPs) and graphene oxide (GO) platelets were deposited by a spin-coating technique. The obtained films were submitted to direct laser irradiation using a frequency quadrupled Nd:YAG (λ=266 nm, τ_FWHM≅3 ns, ν=10 Hz) laser source. The effect of the laser processing conditions, as laser fluence value and number of subsequent laser pulses incident onto the same target location, on the surface morphology, crystalline structure, and chemical composition of the TiO₂/GO nanocomposite thin films was systematically investigated. The laser fluence values were maintained below the vaporization threshold of the irradiated composite material. With the increase of the laser fluence and number of incident laser pulses melting and coalescence of the TiO₂ NPs into inter-connected aggregates as well as rippling of the GO platelets take place. The gradual reduction of GO platelets and the onset of anatase to rutile phase transition were observed at high laser fluence values.     

Tunable TiO2 (anatase and rutile) materials manufactured by mechanical means

Anatase and rutile are two naturally found titanium dioxide phases with attractive dielectric, catalytic, and photo-catalytic characteristics. Anatase and rutile are photo-catalytically active in the UV region, since their band gaps are 3.2 eV and 3.75 eV, respectively. In this work is proposed a cost-effective, easy to launch methodology for modification of the TiO₂ bandgap. Such modifications will make the oxides photo-catalytically active in a wider optical range from the visible wavelengths to an extended UV spectrum. The proposed methodology is based on mechanical means such as mixing and milling. Various ratios of anatase:rutile were investigated and milled from 0 (mixing only) to 50 h using high energy mills. The results on mixing and milling show that it is possible to modify the bandgap of the TiO₂ from 2.53 eV to 4.04 eV. The characterization was conducted by means of X-ray diffraction, Raman spectroscopy, Scanning electron microscopy, and optical spectroscopy.