Photoluminescence studies of nitrogen-doped TiO2 powders prepared by annealing with urea

Photoluminescence and excitation spectra have been investigated for undoped and nitrogen-doped TiO₂ powders at low temperatures. A broad luminescence band peaking at 2.25?eV is observed in the undoped TiO₂ powders. The 2.25?eV luminescence band exhibits a sharp rise from 3.34?eV in the excitation spectrum reflecting the fundamental absorption edge of anatase TiO₂. On the other hand, the N-doped TiO₂ powders obtained by annealing with urea at 350 and 500°C exhibit broad luminescence bands around 2.89 and 2.63?eV, respectively. The excitation spectra for these luminescence bands rise from the lower energy side of the fundamental absorption edge of anatase TiO₂. The origin of the luminescence bands and N-related energy levels formed in the band-gap of TiO₂ are discussed.     

Synthesis of Nanometer Glass and Crystal Particles by Excimer Laser Ablation

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Preparation of nanosized crystalline TiO2 particles at low temperature for photocatalysis

Nanocrystalline titanium dioxide (TiO₂) particles were prepared by a modified alkoxide method under acidic conditions at temperatures ranging from 60°C to 90°C. The reaction temperature was used to control the crystalline phase of the TiO₂ particles. At 60°C and 75°C rutile was formed whilst at 90°C anatase and brookite were formed.The photocatalytic activity of the prepared particles was tested for the degradation of sucrose. The photocatalytic activities of the prepared nanosized TiO₂ were compared to those obtained from Degussa P-25 TiO₂ as well as TiO₂ crystalline samples prepared using the conventional sol–gel/heat treatment method. At low organic concentrations, Degussa P-25 exhibited higher photocatalytic behaviour than all the prepared particles while, at high organic concentrations, the nanosized TiO₂ particles prepared at low temperature displayed an activity comparable to Degussa P-25 but much higher than the heat treated sample. The formation of excess intermediates during the degradation of higher sucrose loadings is believed to hinder the photoactivity of Degussa P-25, while the prepared TiO₂ particles are able to maintain their activity for the degradation of the intermediates of sucrose.     

Structural transformation study of TiO2 nanoparticles annealing at different temperatures and the photodegradation process of eosin-Y

Hydrothermal method was used to prepare TiO₂ nanoparticles with annealing temperature at 500 °C–700 °C. The mixture of anatase-rutile phase was investigated by powerful tool of X-ray diffraction (XRD). The structural parameters of anatase and rutile mixture phaseTiO₂ nanoparticles were calculated from the Rietveld refinement. The transformation rate of rutile was increased linearly with an annealing temperature of 500 °C–700 °C. The spherical morphology of the anatase and rutile mixed phase were obtained by scanning electron microscope and transmission electron microscope. The spherical particle of the anatase and rutile TiO₂ shows with great aggregation with different size and within the range of few tens nm. The EDAX study revealed the presence of titanium and oxygen. The best photocatalytic activity was identified as the 87.04% of anatase and 12.96% of rutile mixer phase of TiO₂. Various factors could be involved for a better photocatalytic activity.     

Femtosecond Diffuse-Reflectance Spectroscopy of Various Commercially Available TiO2 Powders

The transient absorption properties of several commercially available TiO₂ photocatalysts were investigated by femtosecond diffuse-reflectance spectroscopy. Using femtosecond diffuse-reflectance spectroscopy, the quantities and rates of the initial trapping processes of holes and electrons generated by the photoexcitation of TiO₂ photocatalysts were investigated. It was found that the total amounts of trapped electrons for the pure-anatase and pure-rutile TiO₂ became smaller with increasing particle size, but increased again when the particles’ diameters were larger than 50 nm. The anatase–rutile mixed TiO₂ photocatalysts were found to have smaller amounts of trapped electrons compared with pure-anatase and pure-rutile TiO₂ photocatalysts. The lifetimes of trapped holes of various TiO₂ photocatalysts were also investigated, and it was found that the lifetimes were proportional to the anatase–rutile mixed ratios.     

Cobalt-doped TiO2: a computational analysis of dopant placement and charge transfer direction on thin film anatase

ABSTRACT

Titanium dioxide (TiO₂) nanocrystals are promising materials for photo-electrochemical water splitting. This study focuses on how surface dopant placement can affect the electronic properties. TiO₂ anatase thin films are doped two ways: a cobalt ion replacing a surface titanium ion (surface ingrained) and a cobalt ion chemisorbed to two surface oxygen ions and two NH₃ ligands. Specifically, when studying the binding pattern, the cobalt ion dopant changes from an electron acceptor for the surface ingrained model to an electron donor for the chemisorbed model. The optical absorption peaks of the surface ingrained model are attributed to p→d transitions and are much stronger when compared to the d→d transitions for the chemisorbed model. It is the conclusion of this computational study that one can alter the cobalt dopant on the anatase thin film to focus a positive or negative charge at the surface by changing the surface dopant location.     

Molecular dynamics study of water in contact with the TiO2 rutile-110, 100, 101, 001 and anatase-101, 001 surface

We have carried out classical molecular dynamics of various surfaces of TiO₂ with its interface with water. We report the geometrical features of the first and second monolayers of water using a Matsui Akaogi (MA) force field for the TiO₂ surface and a flexible single point charge model for the water molecules. We show that the MA force field can be applied to surfaces other than rutile (110). It was found that water OH bond lengths, H–O–H bond angles and dipole moments do not vary due to the nature of the surface. However, their orientation within the first and second monolayers suggest that planar rutile (001) and anatase (001) surfaces may play an important role in not hindering removal of the products formed on these surfaces. Also, we discuss the effect of surface termination in order to explain the layering of water molecules throughout the simulation box.     

飞秒强激光对二氧化钛金红石晶体相变的影响

该文章报道了利用显微激光拉曼光谱仪研究近红外飞秒强激光脉冲诱导二氧化钛金红石单晶所引起的相变.实验辐照时间为60s,当激光辐照平均功率增加时,锐钛矿相的拉曼振动模式强度增强,金红石相的拉曼振动模式强度减弱.通过金红石相和锐钛矿相粉体等拉曼光谱的实验,肯定了随着辐照激光功率的增大,.可以通过拉曼光谱中锐钛矿A1g B1g(515 cm-1)振动模式标志峰和金红石相Eg(445 cm-1)振动标志峰分别对应面积的比判断其相变量.     

飞秒激光诱导二氧化钛金红石单晶相变的拉曼光谱研究

利用显微拉曼光谱仪研究了近红外飞秒激光脉冲诱导二氧化钛金红石单晶所引起的相变。实验发现当激光的平均功率为300 mW时,随着辐照时间的增加,金红石相的Eg模式强度增强,而A1g模式强度减弱,由此得出激光诱导晶体产生了色心;辐照时间为10 s时,锐钛矿相出现;并且随着辐照时间的增加,锐钛矿相的拉曼振动模式强度增强,金红石相的减弱。然而当辐照时间确定为1/63 s时,随着激光功率的增加,金红石Eg模式强度与A1g模式强度的比值增加,而没有锐钛矿相出现。     

气相爆炸流场中TiO_2纳米颗粒生长的数值分析初探

气相爆炸制备TiO2纳米颗粒的实验成果在近年来多有报道,但对颗粒成长的模拟尚不多见。引入一种气溶胶的单分散性物理模型(Kruis模型),将其应用于气相爆炸流场中TiO2纳米颗粒生长的数值模拟,结合气相爆炸制备实验进行对比分析。结果表明,通过控制前驱体反应组分,气相爆轰合成了直径范围为20~150nm的球形TiO2纳米颗粒。数值模拟得到的颗粒大小与实验观测结果基本一致。影响纳米颗粒生长的主要因素包括反应温度、颗粒浓度及反应时间。     

Evaluation of Morphology and Size Distribution of Silicon and Titanium Oxide Nanoparticles Generated by Laser Ablation

Nanometer-sized particles of silicon and titanium oxide were generated by irradiating solid targets using a nanosecond pulsed-Nd : YAG laser in a low pressure atmosphere. A low pressure differential mobility analyzer (LP-DMA) was used to classify the size of the generated particles. The LP-DMA and electron microscopes (SEM and TEM) were used to measure the change in the size distribution and morphology of the generated particles with laser power density and system pressure. The size distribution of both silicon and titanium oxide ranged from two to one hundred nanometers in diameter depending on the laser power density and pressure. From the high resolution TEM observation and electron diffraction, it was found that the generated titanium oxide nanoparticles were composed of a core of faceted metallic single crystals with an oxide layer 'shell.     

Photoluminescence from TiO2/PMMA Nanocomposite Prepared by γ Radiation

The surface of anatase TiO₂ nanocrystals with an average size of ~20 nm was modified by PMMA through γ radiation. The modified nanocrystals were investigated with photoluminescence (PL) and Fourier transform infrared (FTIR) spectra. A stable blue luminescence peak (~420 nm) can be observed for the modified anatase TiO₂ nanocrystal.     

Ultrafine anatase TiO2 nanoparticles produced in premixed ethylene stagnation flame at 1 atm

Nano-sized titanium oxide particles were synthesized in a stationary, laminar, premixed, stagnation flame burning an ethylene–oxygen–argon mixture at an equivalence ratio of 0.36 under the atmospheric pressure. The titanium precursor, titanium tetraisopropoxide (TTIP), was fed into the flame by a carrier argon flow through a heated TTIP bath. Particles synthesized in this flame were characterized for their size distribution, morphology, phase purity, and crystal structure, by scanning mobility particle sizer, transmission electron microscopy, and X-ray diffraction. It was found that the mean diameter of the particles was highly controllable and ranged from 3 to 6 nm depending on TTIP loading. The particle size was nearly uniform, and particles appeared to be single crystals without excessive aggregation. XRD analyses show that particles directly synthesized in the flame are pure anatase. Upon sintering and size growth on the flame stabilizer, a notable portion of particles transformed into rutile with much larger crystal sizes.     

飞秒激光烧蚀合成Y_2O_3∶Pr~(3+),Yb~(3+)上转换发光材料

利用飞秒激光烧蚀方法合成了Y2O3∶Pr3+,Yb3+纳米颗粒并对其上转换发光性质进行了研究。对合成产物的形貌分析显示,在一定的激光烧蚀功率密度下,即可制备出小尺寸的纳米颗粒,提高激光功率密度可以得到更高的纳米颗粒产量,所获得的纳米颗粒尺寸小于50 nm。荧光测试结果表明,Y2O3∶Pr3+,Yb3+纳米颗粒具有510 nm为中心的上转换发光带,上转换发光随纳米颗粒数量的增加而增强。     

Phase transition rate of anatase during detonation synthesis of TiO2

TiO₂ powders were synthesized by two types of mixed explosives in a sealed reaction kettle. The phase and morphology of TiO₂ powders were obtained by X-ray diffractometry and transmission electron microscopy. Results indicate that powders obtained from metatitanic acid contained mixed explosive are mixed crystal of anatase and rutile. The phase transition rate of anatase increases from 22.9% to 93.3% with the rise of mass ratio of hexogen, and the grain size also enlarges gradually. The powder obtained from anatase contained mixed explosive is rutile, and the phase transition rate of anatase is 100%. Compared with that before detonation, the grain size of anatase after detonation significantly changes, from nanoscale to micronscale. Based on the calculation of detonation parameters, the phase transition process and grain growth during the synthesis of TiO₂ by means of detonation method are analyzed, and the nucleating collision–growth model is proposed.     

N掺杂锐钛矿TiO2光学性能的第一性原理研究

用平面波赝势方法(PWP)计算了N掺杂锐钛矿型TiO₂前后的光学特性,即介电函数虚部ε₂(ω)，光学吸收系数I(ω)和反射率R(ω). 并从能带结构上解释了为什么掺N后锐钛矿型TiO₂的光学谱在2.93，3.56和3.97eV处相对掺杂前会出现3个峰值的原因. 从光谱图上分析得出，掺杂后TiO₂要发生红移现象，实验现象证实了这一结果. 关键词： N掺杂 2')" href="#">锐钛矿型TiO₂ 光学性能 第一性原理     

Preparation of synthetic rutile from high titanium slag using microwave heating

In this work, we demonstrate a novel synthesis of synthetic rutile from high titanium slag. This rutile TiO₂ was obtained by a simple one-step microwave roasting route. The influence of microwave roasting temperature and duration on the phase transformation of high titanium slag has been assessed. X-ray diffraction (XRD) results indicate that the intensity of anosovite (Fe₃Ti₃O₁₀) phase, which were the major phase of high titanium slag of carbon thermal reduction of ilmenite ores, decreased rapidly while the peaks for rutile TiO₂ phase increased with increase in the microwave roasting temperature. The scanning electron microscope (SEM) images revealed formation and the particle-size distribution of rutile TiO₂ phase. Based on XRD and SEM analysis, confirmed the dependence of phase structure, composition and crystallite size on the process conditions of microwave roasting.     

N掺杂锐钛矿TiO2电子结构的第一性原理研究

为了研究N掺杂对锐钛矿型TiO₂电子结构的影响，进而揭示N掺杂导致锐钛矿型TiO₂的禁带宽度变小的机理，对N掺杂TiO₂进行了基于密度泛函理论的第一性原理研究. 通过对能带、态密度及电子分布密度图的分析，发现在N掺杂后，N原子与Ti原子在导带区，发生了强烈的相互关联作用，致使Ti原子3d轨道上的电子向N原子2p轨道发生移动，使得导带降低了，从而使得TiO₂导带的禁带宽度变小.理论预测可以发生红移现象，与实验结果对比分析，理论与实验基本相符. 关键词： N掺杂 2')" href="#">锐钛矿型TiO₂ 电子结构     

Uniform thin films of TiO2 nanoparticles deposited by matrix-assisted pulsed laser evaporation

We report morphological and optical properties of a colloidal TiO₂ nanoparticle film, deposited on a quartz substrate by using the Matrix-Assisted Pulsed Laser Evaporation (MAPLE) technique. Atomic Force Microscopy demonstrated that a good uniformity of the deposition can be obtained. The presence of agglomerates with dimensions of about 1 μm in size was noticed. Form UV-vis transmission spectra, recorded in the 200-800 nm range, the optical constants and the energy gap were determined besides the film thickness. The optical constants resulted in agreement with the values reported in literature for TiO₂ nanoparticle thin films.     

DFT calculations for Au adsorption onto a reduced TiO2 (110) surface with the coexistence of Cl

Residual chlorines, which originate from HAuCl₄, enhance the aggregation of gold (Au) nanoparticles and clusters, preventing the generation of highly active supported Au catalysts. However, the detailed mechanism of residual-chlorine-promoted aggregation of Au is unknown. Herein to investigate this mechanism, density functional theory (DFT) calculations of Au and Cl adsorption onto a reduced rutile TiO₂ (110) surface were performed using a generalised gradient approximation Perdew, Burke, and Ernzerhof formula (GGA–PBE) functional and plane-wave basis. Although both Au and Cl atoms prefer to mono-absorb onto oxygen defect sites, Cl atoms have a stronger absorption onto a reduced TiO₂ (110) surface, abbreviated as rTiO₂ (110) in the following, than Au atoms. Additionally, co-adsorption of a Cl atom and a Au atom or Au nanorod onto a rTiO₂ surface was investigated; Cl adsorption onto an oxygen defect site weakens the interaction between a Au atom or Au nanorod and rTiO₂ (110) surface. The calculation results suggest that the depletion of interaction between Au and rTiO₂ surface is due to strong interaction between Cl atoms at oxygen defect sites and neighbouring bridging oxygen (O^B) atoms.