Synthesis and nanostructural investigation of TiO<Subscript>2</Subscript> nanorods doped by SiO<Subscript>2</Subscript>

TiO₂ Nano rods can be used as dye-sensitized solar cells, various sensors and photocatalysts. These nanorods are synthesized by a hydrothermal corrosion process in NaOH solution at 200°C using TiO₂ powder as the source material. In the present work, the synthesis of TiO₂ nanorods in anatase, rutile and Ti₇O₁₃ phases and synthesis of TiO₂ nanorods by incorporating SiO₂ dopant, using the sol–gel method and alkaline corrosion are reported. The morphologies and crystal structures of the TiO₂ nanorods are characterized using field emission scanning electron microscopy (FE-SEM), atomic force microscopy (AFM) and X-ray diffraction (XRD) study. The obtained results show not only an aggregation structure at high calcination temperatures with spherical particles but also Ti–O–Si bonds having four-fold coordination with oxygen in SiO^4 −.     

Effects of Gd<Superscript>3+</Superscript> modifications on the photoelectrochemical properties of TiO<Subscript>2</Subscript>-based dye-sensitized solar cells

In this paper, TiO₂ particles (~30 nm) modified with Gd₂O₃-coating layer (~2 nm) for dye-sensitized solar cells (DSSCs) were fabricated via the hydrothermal method. Among the solar cells based on the Gd³⁺-doped TiO₂ photoanodes, the optimal conversion efficiency was obtained from the 0.025Gd³⁺-modified TiO₂-based cell, with a 17.7% improvement in the efficiency as compared to the unmodified one (7.18%). This enhancement was probably due to the improved UV radiation harvesting via a down-conversion luminescence process by Gd³⁺ ions, enhancement of visible light absorption and improved dye loading capacity. In addition, after Gd modification, a thin coating could be formed on the TiO₂ nanoparticles, which worked as an energy barrier and resulted in a lower charge recombination.     

Sulfonated poly(phenylene oxide)/Ti<Superscript>3+</Superscript>/TiO<Subscript>2</Subscript> nanotube arrays membrane/electrode with high performances for lithium ion battery

Sulfonated poly(phenylene oxide) (SPPO) film was electrodeposited on Ti³⁺-doped TiO₂ nanotube arrays (Ti³⁺/TiO₂NT) electrode via the electropolymerization of sulfonated phenol. The as-synthesized SPPO/Ti³⁺/TiO₂NT membrane/electrode was investigated in terms of SEM, FESEM, EDX, FTIR, XPS, galvanostatic charge/discharge, and cycle voltammetry (CV). As expected, the porous SPPO film did form on the surface of Ti³⁺/TiO₂NT electrode; furthermore, the resultant SPPO/Ti³⁺/TiO₂NT membrane/electrode delivered higher electrochemical performances than PPO/Ti³⁺/TiO₂NT, mainly attributed to the contributions of the ionic conductivity induced by –SO₃H groups within SPPO.     

Effects of dopant on the electrochemical properties of Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> anode materials

The effects of dopant on the electrochemical properties of spinel-type Li_3.97M_0.1Ti_4.94O₁₂ (M = Mn, Ni, Co) and Li_(4-x/3)Cr_xTi_(5-2x/3)O₁₂(x = 0.1, 0.3, 0.6, 0.9, 1.5) were systematically investigated. Charge-discharge cycling were performed at a constant current density of 0.5 mA/cm² between the cut-off voltages of 3.0 and 1.0 V, the experimental results showed that Cr³⁺ dopant improved the reversible capacity and cycling stability over the pristine Li₄Ti₅O₁₂. The substitution of the Mn³⁺ and Ni³⁺ slightly decreased the capacity of the Li₄Ti₅O₁₂. Dopants such as Co³⁺ to some extent worsened the electrochemical performance of the Li₄Ti₅O₁₂.     

Tunable optical parametric oscillator based on a KTP crystal,pumped by a pulsed Ti<Superscript>3+</Superscript>:Al<Subscript>2</Subscript>O<Subscript>3</Subscript> laser

We present the characteristics of an optical parametric oscillator based on a KTP crystal, pumped with noncritical phase matching by a pulsed Ti³⁺:Al₂O₃ laser, tunable in the range 677–970 nm. Tunable generation of signal and idler waves is obtained in the ranges 1030–1390 nm and 2690–3050 nm respectively. The efficiency of conversion of the pump to the signal wave is ≈23%, which for pulses of duration ≈8 nsec ensures an energy in the range 1.0–11.5 mJ. The width of the emission spectrum for the signal wave is within the range 0.8–1.8 nm and is predominantly determined by the linewidth of the Ti³⁺:Al₂O₃ pump laser. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 3, pp. 351–356, May–June, 2007.     

Optical properties of pyridine funtionalized TbF<Subscript>3</Subscript> nanoparticles

The preparation of pyridine functionalized TbF₃ nanoparticles are described in this report. Synthesized nanoparticles were characterized using the TEM, UV/Vis, FTIR and photoluminescence spectroscopy. TEM micrograph reveals the nanorod shaped, uniform in size with a particles size in the range of 20–30 nm. FTIR spectrum shown characteristic absorption bands of pyridine and a small intensity band at 411 cm⁻¹ corresponding metal nitrogen ν(Tb–N) bonding. Uv-vis spectrum shown the characteristic absorption transitions of Tb³⁺ ion. A strong emission transition at 540 nm (⁵D₄ → ⁷F₅) was observed on excite by visible light at 414 nm.     

Ti<Superscript>3+</Superscript>-doped TiO<Subscript>2</Subscript> hollow sphere with mixed phases of anatase and rutile prepared by dual-frequency atmospheric pressure plasma jet

A novel method of synthesizing Ti³⁺-doped TiO₂ was proposed. Ti³⁺-doped TiO₂ hollow spheres were prepared with different thickness of carbon shell by using atmospheric pressure plasma jet generated by dual-frequency power sources. The as-synthesized Ti³⁺-doped TiO₂ hollow microspheres were characterized by X-ray diffraction (XRD) pattern, scanning electron microscope (SEM) images, high-resolution transmission electron microscopy (HRTEM) images, Raman spectra, X-ray photoelectron spectroscopy (XPS), and UV–vis spectra. These results indicated that these samples had mixed phases of anatase and rutile and the structure of hollow sphere varied with different thickness of carbon shell. The Ti-O-C chemical bond was the connection between the TiO₂ hollow sphere and carbon layer. Amount of Ti³⁺ ions were found, which were accompanied with the formation of oxygen vacancies. Meantime, the as-synthesized catalysts also display strong absorption in the visible light region and have a narrow band energy gap. Optical emission spectroscopy (OES) was used to observe different excited species in the discharge area. These results showed that the oxygen content had a significant impact on the number of oxygen vacancies. Finally, the photocatalytic activities of as-prepared samples were evaluated by decomposition of rhodamine B aqueous solution, which showed better photocatalytic activity under UV–vis light irradiation.     

Sensitizing of Sm<Superscript>3+</Superscript> fluorescence by silver dopant in the TiO<Subscript>2</Subscript> films

Composite material based on a TiO₂ matrix doped with Sm³⁺ ions and co-doped with silver was investigated. Samarium ions together with nano- and micro-aggregates of silver were incorporated into the titanium alkoxide during the sol-gel process. Samarium ions were excited either directly (λ _exc = 488 nm) or through the TiO₂ host (λ _exc = 355 nm). It was revealed that samarium fluorescence (λ _exc = 488 nm) in gelled TiO₂ films is enhanced by up to 20 times in the vicinity of silver inclusions. Sensitizing and plasmonic mechanisms of enhancement in Sm³⁺ fluorescence are discussed.     

On the Luminescence of Ce<Superscript>3+</Superscript>, Eu<Superscript>3+</Superscript>, and Tb<Superscript>3+</Superscript> in Novel Borate LiSr<Subscript>4</Subscript>(BO<Subscript>3</Subscript>)<Subscript>3</Subscript>

This paper reports on the photoluminescence (PL) and time-resolved properties of Ce³⁺, Eu³⁺, and Tb³⁺ in novel LiSr₄(BO₃)₃ powder phosphors. Ce³⁺ shows an emission band peaking at 420 nm under 350-nm UV excitation. Energy transfer from Ce³⁺ to Mn²⁺ takes place in the co-doped samples. Eu³⁺ shows red emission under near UV excitation. LiSr₄(BO₃)₃:Eu³⁺ phosphor could be a suitable candidate for phosphor-converted solid state lighting. The luminescence lifetime is 2.13 ms for Eu³⁺ in LiSr₄(BO₃)₃:0.001Eu³⁺. As Eu³⁺ concentration increasing, the decay curves deviate from exponential behavior. Tb³⁺ shows the strongest ⁵D₄→⁷ F₅ emission line at 540 nm. Decay curves of ⁵D₄→⁷ F₅ and ⁵D₃→⁷ F₅ emission with different Tb³⁺ concentrations were also measured. Cross-relaxation process is discussed based on the decay curves.     

Influence of carbon additive on the properties of spherical Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> and LiFePO<Subscript>4</Subscript> materials for lithium-ion batteries

Preparing spherical particles with carbon additive is considered as one effective way to improve both high rate performance and tap density of Li₄Ti₅O₁₂ and LiFePO₄ materials. Spherical Li₄Ti₅O₁₂/C and LiFePO₄/C composites are prepared by spray-drying–solid-state reaction method and controlled crystallization–carbothermal reduction method, respectively. The X-ray diffraction characterization, scanning electron microscope, Brunauer–Emmett–Teller, alternating current impedance analyzing, tap density testing, and electrochemical property measurements are investigated. After hybridizing carbon with a proper quantity, the crystal grain size of active materials is remarkably decreased and the electrochemical properties are obviously improved. The Li₄Ti₅O₁₂/C and LiFePO₄/C composites prepared in this work are spherical. The tap density and the specific surface area are as high as 1.71 g cm⁻³ and 8.26 m² g⁻¹ for spherical Li₄Ti₅O₁₂/C, which are 1.35 g cm⁻³ and 18.86 m² g⁻¹ for spherical LiFePO₄/C powders. Between 1.0 and 3.0 V versus Li, the reversible specific capacity of the Li₄Ti₅O₁₂/C is more than 150 mAh g⁻¹ at 1.0-C rate. Between 2.5 and 4.2 V versus Li, the reversible capacity of the LiFePO₄/C is close to 140 mAh g⁻¹ at 1.0-C rate.     

n/p-Type changeable semiconductor TiO<Subscript>2</Subscript> prepared from NTA

A novel kind of nano-sized TiO₂ (anatase) was obtained by high-temperature (400–700°C) dehydration of nanotube titanic acid (H₂Ti₂O₄(OH)₂, NTA). The high-temperature (400–700°C) dehydrated nanotube titanic acids (HD-NTAs) with a unique defect structure exhibited a p-type semiconductor behavior under visible-light irradiation ( nm, E _photon=2.95 eV), whereas exhibited an n-type semiconductor behavior irradiated with UV light ( nm, E _photon=3.40 eV).     

Synthesis and characterization of mono-dispersed Y<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript>:Er<Superscript>3+</Superscript>-coated SiO<Subscript>2</Subscript> nanoparticles by co-precipitation process

In this paper, a facile co-precipitation process for preparing mono-dispersed core–shell structure nanoparticles is reported. The 110 nm SiO₂ cores coated with an yttrium aluminum garnet (Y₃Al₅O₁₂) layer doped with Er³⁺ were synthesized and the influence of the concentration ratio of [urea]/[metal ions] on the final product was investigated. The structure and morphology of samples were characterized by the X-ray powder diffraction, Fourier transform IR spectroscopy and transmission electron microscopy, respectively. The results indicate that a layer of well-crystallized garnet Y₃Al₅O₁₂:Er³⁺ were successfully coated on the silica particles with the thickness of 20 nm. The near infrared and upconversion luminescent spectra of the SiO₂@Y₃Al₅O₁₂:Er³⁺ powders further confirm that a Y₃Al₅O₁₂:Er³⁺ coating layer has formed on the surface of silica spherical particles.     

Synthesis, structure and photocatalytic activity of nano TiO2 and nano Ti1-xMxO2-δ (M = Cu, Fe, Pt, Pd, V, W, Ce, Zr)

We have synthesized 5–7 nm size, highly crystalline TiO₂ which absorbs radiation in the visible region of solar spectrum. The material shows higher photocatalytic activity both in UV and visible region of the solar radiation compared to commercial Degussa P25 TiO₂. Transition metal ion substitution for Ti⁴⁺ creates mid-gap states which act as recombination centers for electron-hole induced by photons thus reducing photocatalytic activity. However, Pt, Pd and Cu ion substituted TiO₂ are excellent CO oxidation and NO reduction catalysts at temperatures less than 100° C.     

Spectroscopic Properties and Energy Transfer Analysis of Tm<Superscript>3+</Superscript>-Doped BaF<Subscript>2</Subscript>-Ga<Subscript>2</Subscript>O<Subscript>3</Subscript>-GeO<Subscript>2</Subscript>-La<Subscript>2</Subscript>O<Subscript>3</Subscript> Glass

This paper reports on the spectroscopic properties and energy transfer analysis of Tm³⁺-doped BaF₂-Ga₂O₃-GeO₂-La₂O₃ glasses with different Tm₂O₃ doping concentrations (0.2, 0.5, 2.0, 2.5, 3.0, 3.5, 3.5, 4.0 wt%). Mid-IR fluorescence intensities in the range of 1,300 nm−2,200 nm have been measured when excited under an 808 nm LD for all the samples with the same pump power. Energy level structure and Judd-Ofelt parameters have been calculated based on the absorption spectra of Tm³⁺, cross-relaxation rates and multi-phonon relaxation rates have been estimated with different Tm₂O₃ doping concentrations. The maximum fluorescence intensity at around 1.8 μm has been obtained in Tm₂O₃-3 wt% sample and the maximum value of calculated stimulated emission cross-section of Tm³⁺ in this sample is about 0.48 × 10⁻²⁰ cm² at 1,793 nm, and there is not any crystallization peak in the DSC curve of this sample, which indicate the potential utility of Tm³⁺-doped BaF₂-Ga₂O₃-GeO₂- La₂O₃ glass for 2.0-μm optical fiber laser.     

Evaluation of nanoparticle emission for TiO<Subscript>2</Subscript> nanopowder coating materials

In this study, nanoparticle emission of TiO₂ nanopowder coated on different substrates including wood, polymer, and tile, was evaluated in a simulation box and measured with a Scanning Mobility Particle Sizer (SMPS) for the first time. The coating process for the substrate followed the instructions given by the supply company. In the simulation box, UV light, a fan, and a rubber knife were used to simulate the sun light, wind, and human contacting conditions. Among the three selected substrates, tile coated with TiO₂ nanopowder was found to have the highest particle emission (22 #/cm³ at 55 nm) due to nanopowder separation during the simulation process. The UV light was shown to increase the release of particle below 200 nm from TiO₂ nanopowder coating materials. The results show that, under the conditions of UV lamps, a fan and scraping motion, particle number concentration or average emission rate decreases significantly after 60 and 90 min for TiO₂/polymer and TiO₂/wood, respectively. However, the emission rate continued to increase after 2 h of testing for TiO₂/tile. It is suggested that nanoparticle emission evaluation is necessary for products with nanopowder coating.     

Photocatalytic ability of Bi<Subscript>6</Subscript>Ti<Subscript>3</Subscript>WO<Subscript>18</Subscript> nanoparticles with a mix-layered Aurivillius structure

Aurivillius phase layered perovskites Bi₆Ti₃WO₁₈ was prepared by the sol-gel citrate-complexation synthesis. The sample developed into the plate-like nanoparticles with the exposed (001) facets. The phase formation and structure have been verified via X-ray polycrystalline powder diffraction (XRD) Rietveld refinements. The nanoparticles were investigated via the measurements such as FE-SEM, TEM, EDS, and the surface analyses. UV–Vis absorption data revealed that the Aurivillius compound has a direct band characteristic with the band energy of 2.214 eV. The band structure of Bi₆Ti₃WO₁₈ nanoparticles was discussed on the base of the experiments and theoretical calculation. Bi³⁺-containing Aurivillius Bi₆Ti₃WO₁₈ shows efficient photocatalytic degradation for rhodamine B dye (RhB) with the visible light irradiation (λ?>?420 nm). Dynamic characteristic of the light-created excitons was measured by the luminescence and decay lifetime. The multivalent properties of W and Ti ions in the Aurivillius-like lattices of Bi₆Ti₃WO₁₈ photocatalyst were discussed.     

Intense formation of intermetallic phases during implantation of aluminum ions in titanium

The results from microstructure and phase composition investigations of titanium in different structural states (with average grain sizes of 0.3 μm, 1.5 μm, and 17 μm) are presented following Al ion implantation using the Mevva-V.RU source (irradiating dose, 10¹⁸ ion/cm²). The implanted multiphase layers are found to form on the base of α-Ti grains. The size, shape, and localization of the formed phases (TiO₂, Ti₂O, TiC, Ti₃Al, Al₃Ti) depend strongly on the grain size of titanium target. It is shown that the nanostructural particles of TiO₂ phase are located mainly on dislocations in the body of target grains. A Ti₂O surface layer is found to arise in titanium with a grain size of 17 μm. It is established that an ordered Ti₃Al phase is located at a depth of more than 200 nm in the implanted layer along the bounaries of the titanium grains.     

Structural and optical properties of Bi<Subscript>3.25</Subscript>La<Subscript>0.75</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> ferroelectric thin films prepared by chemical solution methods

Ferroelectric Bi_3.25La_0.75Ti₃O₁₂ (BLT) thin films have been grown on Pt/Ti/SiO₂/Si substrates by chemical solution methods. X-ray diffraction analysis shows that BLT thin films are polycrystalline with (171)-preferential orientation. Atomic force microscopy investigation shows that they have large grains about 120 nm in size. A Pt/BLT/Pt capacitor has been fabricated and showed excellent ferroelectricity, with a remnant polarization and coercive field of 24 μC/cm² and 116 kV/cm, respectively. The capacitor shows no polarization fatigue up to 10⁹ switching cycles. The optical constants (n,k) of the BLT thin films in the wavelength range 0.35–1.7 μm were obtained by spectroscopic ellipsometry measurements, and the band-gap energy was found to be about 3.25 eV. Received: 16 October 2001 / Accepted: 6 January 2002 / Published online: 3 June 2002 RID="*" ID="*"Corresponding author. Fax: +86-21/65830-734, E-mail: gswang@mail.sitp.ac.cn     

Titanium-modified Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> with a synergistic effect of surface modifying,bulk doping,and size reducing

In this work, a one-step solid-phase sintering process via TiO₂ and Li₂CO₃ under an argon atmosphere, with ultra-fine titanium powder as the modifying agent, was used to prepare a nano-sized Li₄Ti₅O₁₂/Ti composite (denoted as LTO–Ti) at 800 °C. The introduction of ultra-fine metal titanium powder played an important role. First, X-ray photoelectron spectroscopy demonstrates that Ti⁴⁺ was partially changed into Ti³⁺, through the reduction of the ultra-fine metal titanium powder. Second, X-ray diffraction revealed that the ultra-fine metal titanium powder did not react with the bulk structure of Li₄Ti₅O₁₂, while some pure titanium peaks could be seen. Additionally, the size of LTO–Ti particles could be significantly reduced from micro-scale to nano-scale. The structure and morphology of LTO–Ti were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy, scanning electron microscopy, and transmission electron microscopy. Electrochemical tests showed a charge/discharge current of 0.5, 1, 5, and 10 C; the discharge capacity of the LTO–Ti electrode was 170, 161, 140, and 111 mAh g^?1. It is believed that the designed LTO–Ti composite makes full use of both components, thus offering a large contact area between the electrolyte and electrode, high electrical conductivity, and lithium-ion diffusion coefficient during electrochemical processes. Furthermore, ultra-fine titanium powder, as the modifying agent, is amenable to large-scale production.     

Spectroscopic properties of Er<Superscript>3+</Superscript> ions in LiNbO<Subscript>3</Subscript> crystals codoped with HfO<Subscript>2</Subscript>

The results of the spectroscopic analysis of transition strengths for Er³⁺ ions in a series of Hf:Er:LiNbO₃ crystals with variable Hf content and fixed Er content are reported. Unpolarized UV-VIS-NIR absorption spectra, upconversion fluorescence spectra excited at 800 nm, and microsecond time-resolved spectra excited at 400 nm and 800 nm by 800 nm femtosecond laser were measured at room temperature. The HfO₂ incorporation has influence on Er³⁺ radiative lifetimes, and fluorescence branching ratios. For Hf(4 mol %):Er(1 mol %):LiNbO₃, Ω₂=2.63×10^-20 cm², Ω₄=2.86×10^-20 cm², and Ω₆=0.72×10^-20 cm². Ω₂<Ω₄ is contrary to the Er³⁺ general trend of Ω₂>Ω₄>Ω₆ when the Hf content is below its threshold concentration. In addition, the sum of Ω increases with the Hf content when the HfO₂ content below 6 mol % is unfamiliar. The upconversion mechanism is discussed in this work. PACS 71.20.Eh; 77.84.Dy; 42.62.Fi; 42.65.Ky