Aerosol-assisted flow synthesis of WxTi1−xO2 solid solution spheres with enhanced photocatalytic activity

In this paper, W_xTi_1−xO₂ solid solutions (x = 0.000, 0.005, 0.010, 0.015, and 0.020) microspheres were synthesized with an aerosol-assisted flow synthesis method. The resulting samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), nitrogen sorption, UV-vis diffuse reflectance spectrum (DRS) and X-ray photoelectron spectroscopy (XPS). The photocatalytic activities of the as-prepared catalysts were measured by the degradation of rhodamine B (RhB) under visible light irradiation (λ ≥ 420 nm). All the solid solutions exhibited higher photocatalytic activities than pure TiO₂ and the W_0.015Ti_0.985O₂ solid solution possessed the highest photocatalytic activity. The degradation constant of RhB on W_0.015Ti_0.985O₂ solid solution catalyst was about 15 times of that of the pure TiO₂ and 25 times of that of Degussa P25, respectively. This study provides an effective method to prepare visible light photocatalysts on a large scale.     

(Mo + N) codoped TiO2 for enhanced visible-light photoactivity

A series of Ti_1−xMo_xO_2−yN_y samples were prepared by using sol-gel method and characterized by X-ray diffraction, transmission electron microscopy and UV-vis absorption spectroscopy. All Ti_1−xMo_xO_2−yN_y samples are anatase phase. It is found that Mo, N mono-doping can increase visible light absorption, while (Mo + N) co-doping can greatly enhance absorption in whole visible region. Results of our first-principles band structure calculations reveal that (Mo + N)-doping, especially passivated co-doping can increase the up-limit of dopant concentration and create more impurity bands in the band gap of TiO₂, which leads to a greatly increase of its visible-light absorption without a decrease of its redox potential. It reveals that (Mo + N) co-doped TiO₂ is promising for a photocatalyst with high photocalystic activity under visible light.     

Superhydrophilic stability enhancement of RF co-sputtered TixSi1−xO2 thin films in dark

Ti_xSi_1−xO₂ compound thin-film systems were deposited by reactive RF magnetron co-sputtering technique. The effect of Ti concentration on the hydrophilicity of Ti_xSi_1−xO₂ compound thin films was studied and it was shown that the films with Ti_0.6Si_0.4O₂ composition possess the best hydrophilic property among all the grown samples. Surface ratio and average roughness of the thin films were measured by atomic force microscopy (AFM). Surface chemical states and stoichiometry of the films were determined by X-ray photoelectron spectroscopy (XPS). In addition, XPS revealed that the amount of Ti-O-Si bonds in nanometer depth from the surface of the Ti_0.6Si_0.4O₂ films was the maximum, which resulted in the most stable superhydrophilic property. According to XRD data analysis for the pure TiO₂ films, the polycrystalline anatase phase was formed with an average grain size of about 15 nm. Moreover, amorphous phase was also formed for the Ti_xSi_1−xO₂ compound systems due to presence of silicon in the films. Finally, optical properties of the films such as transmission, reflection and band gap energy were investigated using UV-vis spectrophotometry. It was found that the transmittance of the films was decreased with increasing Ti concentration in the films.     

IR and XPS investigation of visible-light photocatalysis—Nitrogen-carbon-doped TiO2 film

To use solar irradiation or interior lighting efficiently, we sought a photocatalyst with high reactivity under visible light. Nitrogen and carbon doping TiO_2−x−yN_xC_y films were obtained by heating the TiO₂ gel in an ionized N₂ gas and then were calcined at 500 °C. The TiO_2−x−yN_xC_y films have revealed an improvement over the TiO₂ films under visible light (wavelength, 500 nm) in optical absorption and photocatalytic activity such as photodegradation of methyl orange. X-ray photoemission spectroscopy, infrared spectrum and UV-visible (UV-vis) spectroscopy were used to find the difference of two kinds of films. Nitrogen and carbon doped into substitutional sites of TiO₂ has been proven to be indispensable for band-gap narrowing and photocatalytic activity.     

The influence of hydrogen annealing on magnetism of Co-doped TiO2 films prepared by sol–gel method

Co-doped TiO₂ (Co_xTi_1−xO₂, 0.05?x?0.2) films have been prepared on Si (0 0 1) substrates by sol–gel method. When heat treated in air, Co_xTi_1−xO₂ films are non-ferromagnetic at room temperature. However, after further annealed in a flowing hydrogen atmosphere, Co_xTi_1−xO₂ films show room-temperature ferromagnetism (RTFM). Measurements of magnetization (M) vs. temperature (T), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) fail to detect Co clusters in the hydrogenated Co_0.1Ti_0.9O₂ films, suggesting that RTFM in the hydrogenated Co_0.1Ti_0.9O₂ films may be intrinsic. But, metal Co appears in the hydrogenated Co_0.2Ti_0.8O₂ films, showing that RTFM in the hydrogenated Co_0.2Ti_0.8O₂ films is as least partly due to metal Co. These results indicate that hydrogen annealing can produce room-temperature ferromagnetism in Co_xTi_1−xO₂ films, but it should be carefully designed to avoid the formation of metal Co in the hydrogenated Co_xTi_1−xO₂ films.     

2-Propanol photodegradation over nitrogen-doped NaNbO3 powders under visible-light irradiation

Nitrogen-doped perovskite-type materials, yellowish NaNbO_3−xN_x powders, had been developed as visible-light-sensitive photocatalysts for decomposition of gaseous 2-propanol. The NaNbO_3−xN_x samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), ultraviolet-visible (UV-vis) light diffuse reflectance spectroscopy, Brunauer-Emmett-Teller (BET) measurement, and scanning electron microscopy (SEM). The UV-vis spectra confirmed that the spectral response of the NaNbO₃ powders could be tuned to visible-light region by nitrogen doping technique. The photocatalytic activities of NaNbO_3−xN_x samples were evaluated by decomposing gaseous 2-propanol into acetone and CO₂ under visible-light irradiation (400 nm<λ<520 nm). The NaNbO_3−xN_x sample annealed at 833 K showed the highest visible-light photocatalytic activity among all the nitrogen-doped samples. The relationship between nitrogen doping amount and photocatalytic activity of NaNbO_3−xN_x samples was also investigated and discussed.     

Preparation and characterization of cerium oxide doped TiO2 nanoparticles

A mixed oxide consisting of TiO₂ as the major phase and CeO_2−y (0<y<0.5) as the dopant phase was prepared via the sol-gel reaction of Ti(i-OC₃H₇)₃ in an aqueous solution of Ce(NO₃)₃. The resulting oxide powders with different CeO_2−y contents were all composed of nano-sized spheres. The CeO_2−y phase was identified to have retarding effect on the phase transition from anatase TiO₂ to rutile TiO₂ at calcinations temperature as high as 800 °C, which would otherwise be a thorough conversion. The CeO_2−y-TiO₂ powders could apparently shift the UV-absorption band of TiO₂ toward visible range, and there was an optimal CeO_2−y content in association with the maximum absorbance. This effect is interpreted as the existence of an n-type impurity band, due to the substitution of Ti⁴⁺ for Ce^3+/4+ at the interface between the two oxides, in the gap of TiO₂. According to X-ray photoelectron spectroscopy (XPS) investigation, the Ti element mainly existed as the chemical state of Ti⁴⁺ and the Ce oxide doping did not affect the peak position of Ti 2p. The Ce 3d spectrum of CeO_2−y-doped TiO₂ sample basically denotes a mixture of Ce^3+/4+ oxidation states giving rise to a myriad of peaks.     

Boron and nitrogen co-doped titania with enhanced visible-light photocatalytic activity for hydrogen evolution

A visible-light boron and nitrogen co-doped titania (B-N-TiO₂) photocatalyst was prepared by sol-gel method with titanium tetra-n-butyl oxide, urea and boric acid as precursors. The photocatalyst was characterized by Fourier Transform Infrared (FT-IR), UV-vis diffusive reflectance spectroscopy (DRS), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), BET and electrochemistry method. Photocatalytic activity for hydrogen production over platinized B-N-TiO₂ under visible-light (λ ≥ 420 nm) irradiation was investigated. In nitrogen doped titania (N-TiO₂) NTiO bond is formed, which extends the absorption edge to the visible-light region. A part of doping boron enters into titania lattice and most of the boron exists at the surface of the catalyst. The crystallite size of B-N-TiO₂ decreases compared to N-TiO₂, while its photocurrent and the surface hydroxyl group increase. Furthermore, doping boron could act as shallow traps for photoinduced electrons to prolong the life of the electrons and holes. Therefore, the visible-light activity of B-N-iO₂ increases greatly compared with that of N-TiO₂.     

The role of oxygen vacancies in magnetism of CoxTi1−xO2−δ films on Si(001) prepared by sol-gel method

Co_xTi_1−xO_2−δ films have been prepared on Si(001) substrates by sol-gel method. When heat treated in air, Co_xTi_1−xO_2−δ films are non-ferromagnetic at room temperature. However, after further vacuum annealing or hydrogenation, Co_xTi_1−xO_2−δ films show room-temperature ferromagnetism (RTFM). When the vacuum annealed Co_xTi_1−xO_2−δ films are reheated in air, the magnetic moments of the films strongly reduce. After these films are vacuum annealed once again, the magnetic moments are greatly enhanced, confirming the role of vacuum annealing in ferromagnetism of Co_xTi_1−xO_2−δ films. The x-ray diffraction (XRD), x-ray photoelectron spectroscopy (XPS) and measurements of magnetization (M) vs temperature (T) fail to detect Co clusters in the vacuum annealed and the hydrogenated Co_xTi_1−xO_2−δ films. Oxygen vacancies are formed in Co_xTi_1−xO_2−δ films after vacuum annealing and hydrogenation, determined by XRD and XPS measurements. These results indicate that oxygen vacancies created by vacuum annealing and hydrogenation play an important role in the generation of RTFM in Co_xTi_1−xO_2−δ films.     

Effect of N2 ion flux on the photocatalysis of nitrogen-doped titanium oxide films by electron-beam evaporation

Nitrogen-doped titanium oxide (TiO_xN_y) films were prepared with ion-assisted electron-beam evaporation. The nitrogen (N) incorporated in the film is influenced by the N₂ flux modulated by the N₂ flow rate through an ion gun. The TiO_xN_y films have the absorption edge of TiO₂ red-shifted to 500 nm and exhibit visible light-induced photocatalytic properties in the surface hydrophilicity and the degradation of methylene blue. The structures and states of nitrogen in the films are investigated by X-ray diffraction patterns (XRD), and X-ray photoelectron spectroscopy (XPS) and related to their visible light-induced photocatalytic properties. The results indicate that the substitutional N in anatase TiO₂ can induce visible light photocatalysis. The substitutional N is readily doped by the energetic nitrogen ions from the ion gun. The best photocatalytic activity is obtained at the largest N loading about 5.6 at.%, corresponding to the most substitutional N in anatase TiO₂. The film exhibits the degradation of methylene blue with a rate-constant (k) about 0.065 h⁻¹ and retaining 7° water contact angle on the surface under visible light illumination.     

The preparation of nitrogen-doped TiO2−xNx photocatalyst coated on hollow glass microbeads

In this paper, the effective method for nitrogen-doped TiO_2−xN_x photocatalyst coated on hollow glass microbeads is described, which uses titanium tetraisopropoxide [Ti(iso-OC₃H₇)₄] as the raw materials and gaseous ammonia as a heat treatment atmosphere. The effects of heat treatment temperature and time on the photocatalytic activity of TiO_2−xN_x/beads are studied. The photocatalyst is characterized by the UV-vis diffuse reflection spectroscopy, X-ray photoelectron spectroscopy (XPS), X-ray powder diffraction (XRD), Brunauer-Emmett-Teller (BET) analysis and scanning electron microscopy (SEM). The results show that when the TiO_2−xN_x/beads is heated at 650 °C for 5 h, the photocatalytic activity of the TiO_2−xN_x/beads is the best. Compared with TiO₂, the photoabsorption wavelength range of nitrogen-doped TiO_2−xN_x red shifts of about 60 nm, and the photoabsorption intensity increases as well. The photocatalytic activity of the TiO_2−xN_x/beads is higher than that of the TiO₂/beads under visible light irradiation. The presence of nitrogen neither influences on the transformation of anatase to rutile, nor creates new crystal phases. When the TiO_2−xN_x/beads is heated at 650 °C for 5 h, the amount of nitrogen-doped is 0.53 wt.% in the TiO_2−xN_x. As the density of TiO_2−xN_x/beads prepared is lower than 1.0 g/cm³, it may float on water surface and use broader sunlight spectrum directly.     

Photooxidation of different organic dyes (RB, MO, TB, and BG) using Fe(III)-doped TiO2 nanophotocatalyst prepared by novel chemical method

The nano-structured Fe(III)-doped TiO₂ photocatalysts with anatase phase have been developed for the oxidation of non-biodegradable different organic dyes like methyl orange (MO), rhodamine B (RB), thymol blue (TB) and bromocresol green (BG) using UV-Hg-lamp. The different compositions of Fe_xTi_1−xO₂ (x = 0.005, 0.01, 0.05, and 0.1) nanocatalysts synthesized by chemical method (CM), have been characterized by X-ray diffraction (XRD), UV-vis diffuse reflectance spectra, specific surface area (BET), transmission electronic microscopy (TEM) analysis, XPS, ESR and zeta potential. From XRD analysis, the results indicate that all the compositions of Fe(III) doped in TiO₂ catalysts gives only anatase phase not rutile phase. For complete degradation of all the solutions of the dyes (MO, RB, TB, and BG), the composition with x = 0.005 is more photoactive compared all other compositions of Fe_xTi_1−xO₂, and degussa P25. The decolorization rate of different dyes decreases as Fe(III) concentration in TiO₂ increases. The energy band gap of Fe(III)-doped TiO₂ is found to be 2.38 eV. The oxidation state of iron has been found to be 3+ from XPS and ESR show that Fe³⁺ is in low spin state.     

Sputter deposition of high transparent TiO2−xNx/TiO2/ZnO layers on glass for development of photocatalytic self-cleaning application

In this study, TiO_2−xN_x/TiO₂ double layers thin film was deposited on ZnO (80 nm thickness)/soda-lime glass substrate by a dc reactive magnetron sputtering. The TiO₂ film was deposited under different total gas pressures of 1 Pa, 2 Pa, and 4 Pa with constant oxygen flow rate of 0.8 sccm. Then, the deposition was continued with various nitrogen flow rates of 0.4, 0.8, and 1.2 sccm in constant total gas pressure of 4 Pa. Post annealing was performed on as-deposited films at various annealing temperatures of 400, 500, and 600 °C in air atmosphere to achieve films crystallinity. The structure and morphology of deposited films were evaluated by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and atomic force microscopy (AFM). The chemical composition of top layer doped by nitrogen was evaluated by X-ray photoelectron spectroscopy (XPS). Photocatalytic activity of samples was measured by degradation of Methylene Blue (MB) dye. The optical transmittance of the multilayer film was also measured using ultraviolet-visible light (UV-vis) spectrophotometer. The results showed that by nitrogen doping of a fraction (∼1/5) of TiO₂ film thickness, the optical transmittance of TiO_2−xN_x/TiO₂ film was compared with TiO₂ thin film. Deposited films showed also good photocatalytic and hydrophilicity activity at visible light.     

Electrical and electrochemical properties of molten salt-synthesized Li4Ti5−xSnxO12 (x=0.0, 0.05 and 0.1) as anodes for Li-ion batteries

Submicron-sized polyhedral Li₄Ti_5−xSn_xO₁₂ (x=0.0, 0.05, and 0.1) materials were successfully prepared by a single-step molten salt method. The structural, morphological, transport and electrochemical properties of the Li₄Ti_5−xSn_xO₁₂ were studied. X-ray diffraction patterns showed the formation of a cubic structure with a lattice constant of 8.31 Å, and the addition of dopants follows Vegard's law. Furthermore, FT-IR spectra revealed symmetric stretching vibrations of octahedral groups of MO₆ lattice in Li₄Ti₅O₁₂. The formation of polyhedral submicron Li₄Ti_5−xSn_xO₁₂ particles was inferred from FE-SEM images, and a particle size reduction was observed for Sn-doped Li₄Ti₅O₁₂. The chemical composition of Ti, O and Sn was verified by EDAX. The DC electrical conductivity was found to increase with increasing temperature, and a maximum conductivity of 8.96×10⁻⁶ S cm⁻¹ was observed at 200 °C for Li₄Ti₅O₁₂. The galvanostatic charge–discharge behavior indicates that the Sn-doped Li₄Ti₅O₁₂ could be used as an anode for Li-ion batteries due to its enhanced electrochemical properties.     

Properties of high-k Ti1−xSixO2 gate dielectric layers prepared at room temperature

High-k Ti_1−xSi_xO₂ gate dielectric layers were prepared at room temperature by RF magnetron sputtering using SiO₂ and TiO₂ targets to investigate their applicability to transparent thin-film transistors as well as metal-oxide-semiconductor field-effect transistors. Based on XRD and XPS analyses, it was found that, regardless of the deposition time, the Ti_1−xSi_xO₂ gate dielectric layers had more stable Si-based phases with stronger Si-O bonds with increasing SiO₂ RF power. As SiO₂ RF power increased, the capacitance of the dielectric layers decreased due to the higher fraction of the Si-based phases, and the leakage current decreased, dominantly because of the decrease in oxygen vacancies due to the formation of stoichiometric SiO₂. The Ti_1−xSi_xO₂ gate dielectric layers exhibited high transparency above 80% and moderate bandgap of 4.1-4.2 eV, which can be applied to transparent thin-film transistors.     

Structural characterization and ferromagnetic behavior of Fe-doped TiO2 powder by high-energy ball milling

Fe-doped TiO₂ powder was prepared by high-energy ball milling, using TiO₂ Degussa P-25 and α-Fe powders as the starting materials. The structure and magnetic properties of the Fe-doped TiO₂ powder were studied by X-ray diffraction, ⁵⁷Fe Mossbauer spectroscopy and vibrating sample magnetometer. The Reitveld refinement of XRD revealed that ball milling not only triggered incorporation of Fe in TiO₂ lattice but also induced the phase transformation from anatase to rutile in TiO₂ and consequently the milled Fe-doped TiO₂ powder contained only rutile.⁵⁷Fe Mössbauer effect measure showed that Fe atoms existed in Fe²⁺ and Fe³⁺ state, which were assigned to the solid solution Fe_xTi_1−xO₂. The magnetization measurements indicated that the milled Fe-doped TiO₂ powder was ferromagnetic above room temperature. The ferromagnetism in our milled Fe-doped TiO₂ powder seemingly does not come from Fe and iron oxides particles/clusters but from the Fe-doped TiO₂ powder matrices.     

Visible-light photocatalytic activity of nitrogen-doped TiO2 thin film prepared by pulsed laser deposition

Nitrogen-doped titanium dioxide (TiO_2−xN_x) thin films have been prepared by pulse laser deposition on quartz glass substrates by ablated titanium dioxide (rutile) target in nitrogen atmosphere. The x value (nitrogen concentration) is 0.567 as determined by X-ray photoelectron spectroscopy measurements. UV-vis spectroscopy measurements revealed two characteristic deep levels located at 1.0 and 2.5 eV below the conduction band. The 1.0 eV level is attributable to the O vacancy state and the 2.5 eV level is introduced by N doping, which contributes to narrowing the band-gap by mixing with the O2p valence band. The enhanced degradation efficiency in a broad visible-light range was observed from the degradation of methylene blue and methylene orange by the TiO_2−xN_x film.     

Preparation and photocatalytic activity of nitrogen-doped TiO2 hollow nanospheres

TiO₂ hollow nanospheres were prepared using silicon oxide as a template. N-doped titanium oxide hollow spheres, TiO_2−xN_x were synthesized by reacting TiO₂ hollow spheres with thiourea at 500 °C. XRD and XPS data showed that oxygen was successfully substituted by nitrogen through the nitrogen-doping reaction, and finally N-doped TiO₂ hollow spheres were formed. The N-doped TiO₂ hollow spheres showed new absorption shoulder in visible light region so that they were expected to exhibit photocatalytic activity in the visible light. The photocatalytic activity of N-doped TiO₂ hollow spheres under visible light was similar to that of normal spherical TiO_2−xN_x in spite of the structural difference.     

Control of luminescence and conductivity of delafossite-type CuYO2 by substitution of rare earth cation (Eu, Tb) and/or Ca cation for Y cation

Delafossite-type oxides of CuTb_yY_1−yO₂, CuEu_yY_1−yO₂, CuCa_xTb_yY_1−x−yO₂ and CuCa_xEu_yY_1−x−yO₂ have been prepared by solid state reactions. The lattice-parameter dependence on the composition implies substitution of the Tb³⁺, Eu³⁺ and Ca²⁺ cations for the Y³⁺ site. Noticeable sharp emission lines due to the f-f transitions (⁵D₄→⁷F_J, J=3-6) of Tb³⁺ or due to the f-f transitions (⁵D₀→⁷F_J, J=0-4) of Eu³⁺ are observed at room temperature. Electrical conductivities of CuCa_xTb_yY_1−x−yO₂ and CuCa_xEu_yY_1−x−yO₂ are larger than those of CuTb_yY_1−yO₂ and CuEu_yY_1−yO₂, indicating the increase of the hole concentration caused by the substitution of Ca²⁺ for the Y³⁺ site. These results indicate the controllability of the luminescence and conductivity in CuCa_xTb_yY_1−x−yO₂ and CuCa_xEu_yY_1−x−yO₂ delafossite-type oxides by simultaneous substitution of the rare earth Tb³⁺ or Eu³⁺ cation and the Ca²⁺ cation for the Y³⁺ site.     

Stress induced preferred orientation and phase transition for ternary WCxNy thin films

We deposit ternary WC_xN_y thin films on Si (1 0 0) substrates at 500 °C using direct current (DC) reactive magnetron sputtering in a mixture of CH₄/N₂/Ar discharge, and explore the effects of substrate bias (V_b) on the intrinsic stress, preferred orientation and phase transition for the obtained films by virtue of X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and selective area electron diffraction (SAED). We find that with increasing the absolute value of V_b up to 200 V the carbon (x) and nitrogen (y) atom concentrations of WC_xN_y films keep almost constant with the values of 0.75 and 0.25, respectively. The XPS and SAED results, combined with the density-functional theory (DFT) calculations on the electronic structure of WC_0.75N_0.25, show our obtained WC_xN_y films are single-phase of carbonitrides. Furthermore, we find that the compressive stress sharply increases with increasing the absolute value of V_b, which leads to a pronounced change in the preferred orientation and phase structure for the film, in which a phase transition from cubic β-WC_xN_y to hexagonal α-WC_xN_y occurs as V_b is in the range of −40 to −120 V. In order to reveal the relationship between the stress and phase transition as well as preferred orientation, the DFT calculations are used to obtain the elastic constants for β-WC_xN_y and α-WC_xN_y. The calculated results show that the preferred orientation is dependent on the competition between strain energy and surface energy, and the phase transition can be attributed to a decrease in the strain energy.