Cr掺杂锐钛矿型TiO_2(001)薄膜中Cr原子的直接观测（英文）

掺杂元素的成像对于理解TiO_2掺杂薄膜的光催化活性是至关重要的.然而,如何在原子尺度上表征掺杂原子与TiO_2晶格之间的相互关联性仍然是一项挑战性工作.本文利用高角环形暗场像/环形明场像扫描透射电镜(HA ADF/ABF-STEM)结合电子能量损失谱(EELS)从[100]晶向上对锐钛矿型Ti02(001)薄膜中掺杂的单个铬原子进行了直接成像.结果表明,Cr掺杂原子同时占据TiO_2晶格中的取代位和填隙位,而其可以用具有原子级分辨的电子能量损失谱元素面分布图(EELS mapping)来成像识别,但在HAADF/ABFSTEM图像中未能被看到.大部分的Cr掺杂原子更倾向于取代TiO_2晶格中的Ti原子.这些结果在原子尺度上为Cr掺杂TiO_2薄膜的掺杂构型提供了直接的证据,同时也表明电子能量损失谱元素面分布图在对掺杂材料的结构表征是个非常出色的技术.     

离子注入掺杂锐钛矿TiO2薄膜的光学性能

 在玻璃基体上,采用射频磁控溅射方法在不同的基体温度下制备了TiO₂薄膜,然后在薄膜中注入注量分别为5×1016, 1×1017和5×1017/cm2的N离子以制备N掺杂的TiO₂薄膜。X射线衍射结果表明：制备出的TiO₂薄膜为锐钛矿型。X射线光电子能谱研究结果表明：注入的N离子与TiO₂晶粒相互作用,形成了含氮的TiO_xN_2-x化合物,从而改变了TiO₂薄膜的吸收边;随N离子注量增加,吸收边移动更明显;同时,由于氮离子注入产生的辐照缺陷使TiO₂薄膜在紫外和可见光区的吸收也明显增强。     

离子注入掺杂锐钛矿TiO2薄膜的光学性能

在玻璃基体上,采用射频磁控溅射方法在不同的基体温度下制备了TiO2薄膜,然后在薄膜中注入注量分别为5×1016, 1×1017和5×1017/cm2的N离子以制备N掺杂的TiO2薄膜。X射线衍射结果表明：制备出的TiO2薄膜为锐钛矿型。X射线光电子能谱研究结果表明：注入的N离子与TiO2晶粒相互作用,形成了含氮的TiOxN2-x化合物,从而改变了TiO2薄膜的吸收边;随N离子注量增加,吸收边移动更明显;同时,由于氮离子注入产生的辐照缺陷使TiO2薄膜在紫外和可见光区的吸收也明显增强。     

N/Cu共掺杂锐钛矿型TiO2第一性原理研究

基于密度泛函理论的第一性原理平面波超软赝势法, 采用局域自旋密度近似加Hubbard U值方法研究了纯锐钛矿型TiO₂, N, Cu单掺杂TiO₂及N/Cu共掺杂TiO₂ 的晶体结构、电子结构和光学性质. 研究结果表明, 掺杂后晶格发生相应畸变, 晶格常数变大. N 和Cu的掺杂在TiO₂禁带中引入杂质能级, 禁带宽度发生相应改变. 对于N掺杂TiO₂禁带宽度减小较弱, 而Cu掺杂和N/Cu共掺TiO₂禁带宽度显著降低, 导致吸收光谱明显红移, 光学催化性增强, 有利于实际应用.     

P掺杂锐钛矿相TiO2的第一性原理计算

利用基于密度泛函理论的第一性原理对不同P掺杂形式(P替位Ti, P替位O, 间隙P)的锐钛矿相TiO₂的晶格常数、电荷布居、能带结构、分态密度和吸收光谱进行了计算. 结果表明, P替位Ti时, TiO₂体积减小, P替位O和间隙P的存在使TiO₂的体积膨胀; 替位Ti的P和间隙P均有不同程度的氧化, 而替位O的P带有负电荷. 三种P掺杂形式均导致锐钛矿相TiO₂禁带宽度的增大, 并在TiO₂禁带之内引入了掺杂局域能级. P掺杂导致TiO₂禁带宽度增大的程度依次为: 间隙P>P替位Ti>P替位O. 吸收光谱的计算结果表明, P替位Ti并不能增强TiO₂的可见光吸收能力, 但间隙P的存在大幅提高了TiO₂的可见光光吸收能力, 间隙P有可能是造成实验上P掺杂增强锐钛矿相TiO₂光催化活性的重要原因. 关键词： P掺杂 2')" href="#">锐钛矿相TiO₂ 第一性原理     

Surface reconstruction on stishovite SiO2,HfO2 and rutile TiO2 （001）

This paper systematically investigates the surface reconstruction processes and patterns on stishovite SiO 2,HfO 2 and rutile TiO 2 (001) by using classical molecular dynamics.It is found that these three surfaces relax instead of reconstruction at 0 K,and have little possibility to reconstruct below 40 K.Above 40 K,surface reconstructions take place as collective atomic motion which can be speeded by higher temperature or compressed strain.Several reconstruction patterns with approximate surface energies are found,and electrostatic potentials on them are also provided in comparison with possible microscopic results.     

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     

C掺杂锐钛矿相TiO2吸收光谱的第一性原理研究

运用第一性原理,对C掺杂锐钛矿相TiO₂的电子结构进行了研究,从能带结构理论解释了C掺杂TiO₂吸收光谱的一些实验现象.发现在C掺杂后的锐钛矿相TiO₂的禁带宽度增大,并且在带隙中出现了杂质能级,这些杂质能级主要是由C 2p轨道上的电子构成的,它们之间是独立的,正是这些独立的杂质能级使TiO₂掺杂后可以发生可见光响应.价带上的电子可以吸收一定能量的光子跃迁到杂质能级,而杂质能级上的电子也可以吸收一定能量的光子跃迁到导带,所以从理论上可以计算出掺杂后的TiO₂在可见光范围内存在两个吸收边,与实验中所得到的现象相一致.     

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     

C掺杂锐钛矿相TiO2吸收光谱的第一性原理研究

运用第一性原理,对C掺杂锐钛矿相TiO₂的电子结构进行了研究,从能带结构理论解释了C掺杂TiO₂吸收光谱的一些实验现象.发现在C掺杂后的锐钛矿相TiO₂的禁带宽度增大,并且在带隙中出现了杂质能级,这些杂质能级主要是由C 2p轨道上的电子构成的,它们之间是独立的,正是这些独立的杂质能级使TiO₂掺杂后可以发生可见光响应.价带上的电子可以吸收一定能量的光子跃迁到杂质能级,而杂质能级上的电子也可以吸收一定能量的光子跃迁到导带,所以从理论上可以计算出掺杂后的TiO₂在可见光范围内存在两个吸收边,与实验中所得到的现象相一致. 关键词： C掺杂 2')" href="#">锐钛矿TiO₂ 能带结构 吸收光谱     

甲醇分子在金红石TiO2(110)和锐钛矿TiO2(001)表面吸附和反应的活性位点

通过高分辨的扫描隧道显微术研究并比较了金红石型TiO₂(110)-(1×1)和锐钛矿型TiO₂(001)-(1×4)两种表面的活性位点． 在金红石型TiO₂(110)-(1×1)表面, 观察到氧空位缺陷是O₂和CO₂分子的活性吸附位点,而五配位的Ti原子是水分子和甲醇分子的光催化反应活性位点．在锐钛矿型TiO₂(001)-(1×4)表面,观察到完全氧化的表面,Ti原子更可能是六配位的,H₂O和O₂分子均不易在这些Ti原子上吸附．经还原后表面出现富Ti的缺陷位点, 这些缺陷位点对H₂O和O₂分子表现出明显的活性． 锐钛矿型TiO₂(001)-(1×4)表面的吸附和反应活性并不具有很高的活性,某种程度上其表现出的活性似乎低于金红石型TiO₂(110)-(1×1)表面．     

锐钛矿二氧化钛体相缺陷的准粒子能带结构

Quasiparticle band structures of the defective anatase TiO₂ bulk with O vacancy, Ti interstitial and H interstitial are investigated by the GW method within many-body Green''s function theory. The computed direct band gap of the perfect anatase bulk is 4.3 eV, far larger than the experimental optical absorption edge (3.2 eV). We found that this can be ascribed to the inherent defects in anatase which drag the conduction band (CB) edge down. The occupied band-gap states induced by these defects locate close to the CB edge, excluding the possible contribution of these bulk defects to the deep band-gap state below CB as observed in experiments.     

Optical and hydrophilic properties of Cr doped TiO2-SiO2 nanostructure thin film

Cr doped TiO₂-SiO₂ nanostructure thin film on glass substrates was prepared by a sol-gel dip coating process. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) were used to characterize the structural and chemical properties of the films. A UV-vis spectrophotometer was used to measure the transmittance spectra of the thin film. The hydrophilicity of the thin film during irradiation and storage in a dark place was measured by a contact angle analyzer. The results indicated that Cr doping has a significant effect on the transmittance and super-hydrophilicity of TiO₂-SiO₂ thin film.     

Crystallisation of TiO2 thin films induced by excimer laser irradiation

Titanium dioxide thin films have been deposited by reactive magnetron sputtering on glass substrate and subsequently irradiated by UV radiation using a KrF excimer laser. In this work, we have study the influence of the laser fluence (F) ranging between 0.05 and 0.40 mJ/cm² on the constitution and microstructure of the deposited films. Irradiated thin films are characterized by profilometry, scanning electron microscopy and X-ray diffraction. As deposited films are amorphous, while irradiated films present an anatase structure. The crystallinity of the films strongly varies as a function of F with maximum for F = 0.125 J/cm². In addition to the modification of their constitution, the irradiated areas present a strongly modified microstructure with appearance of nanoscale features. The physico-chemical mechanisms of these structural modifications are discussed based on the theory of nucleation.     

光沉积Ru和RuO2的锐钛矿TiO2纳米片的光解水产氧

采用水热法以HF作为结构调控剂合成了主要暴露（001）面的锐钛矿TiO₂纳米片,通过光沉积方法分别合成了负载Ru和RuO₂物种的光催化剂。利用X射线衍射、透射电镜和氢气程序升温还原等分析表征了催化剂的结构性质。通过光解水产氧反应来研究催化剂的催化性能,详细考察了Ru含量、负载方式以及氧化和还原处理等因素的影响,光解水产氧速率的差异证明了Ru物种在不同晶面的电荷-空穴分离效应。与负载单一助催化剂的Ru/TiO₂和RuO₂/TiO₂样品相比,活性最优的0.5%Ru-1.0%RuO₂/TiO₂样品由于负载了双助催化剂,其催化活性得到更大的提高,证实了在锐钛矿TiO₂上的晶面电荷-空穴分离效应.     

氧空位对共掺型锐钛矿TiO2能带结构的影响

基于电子密度泛函理论计算,系统研究了氧空位对V-C(p型)、Cr-N(n型)、V-N和Cr-C(电中性)四种共掺型锐钛矿TiO₂的几何和电子结构的影响．结果表明在最稳定构型中氧空位处在与金属杂质原子相连的位置．由于氧空位的出现,共掺TiO₂禁带中一些未占据的杂质态被填充满电子,掺杂体系的导带带边位置几乎不变,这有利于减少光生载流子复合,且不影响光解水过程中的产氢反应,在厌氧条件下很容易在V-N共掺TiO₂中引入氧空位．     

CH3OH/TiO2(110)界面的光电子能谱研究

Methanol/TiO₂(110) is a model system in the surface science study of photocatalysis where methanol is taken as a hole capture. However, the highest occupied molecular orbital of adsorbed methanol lies below the valence band maximum of TiO₂, preventing the hole transfer. To study the level alignment of this system, electronic structure of methanol covered TiO₂(110) surface has been measured by ultraviolet photoelectron spectroscopy and the molecular orbitals of adsorbed methanol have been clearly identified. The results indicate the weak interaction between methanol and TiO₂ substrate. The static electronic structure also suggests the mismatch of the energy levels. These static experiments have been performed without band gap excitation which is the prerequisite of a photocatalytic process. Future study of the transient electronic structure using time-resolved UPS has also been discussed.     

Theoretical study of CO adsorption on the illuminated TiO2 (0 0 1) surface

A quantum modeling of the CO adsorption on illuminated anatase TiO₂ (0 0 1) is presented. The calculated adsorption energy and geometries of illuminated case are compared with the ground state case. The calculations were achieved by using DFT formalism and the BH and HLYP. Upon photoexcitation, an electron-hole pair is generated. Comparing of natural population in the ground state and the exited state, shows that an electron is trapped in a Ti⁴⁺ ion and a hole is localized in an oxygen ion. The photoelectron helps generation of a CO₂ molecule on the TiO₂ surface. As shown by optimization of these systems, the CO molecule adsorbed vertically on the TiO₂ (0 0 1) surface in the ground state case while the CO molecule made an angle of 134.3° to this surface at the excited state case. Based on the here used model the obtained adsorption energy was 0.36 eV which is in excellent agreement with the reported experimental value. In the present work the C-O stretch IR frequencies are calculated which are 1366.53 and 1423.16 cm⁻¹. These results are in good agreement with the earlier reported works for the surface carbonaceous compounds, and oxygenated carbon species.     

From anodic TiO2 nanotubes to hexagonally ordered TiO2 nanocolumns

We report on the formation of hexagonally ordered TiO₂ nanocolumnar layers by electrochemical oxidation in a fluoride containing electrolyte, using self-organizing nanotube formation conditions at elevated potentials and low temperatures. The influence of the substrate temperature on the nanocolumn morphology and composition is investigated and characterized by FE-SEM and EDX. The origin of these nanocolumns can be attributed to a thickening of the inner tube wall of the double wall structure of self-organized TiO₂ nanotubes. Furthermore, a transition from nanocolumnar to nanotubular structure can be established by changing the applied voltage or applying a post-immersion treatment.     

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.