锐钛矿型二氧化钛纳米粉体的IR光谱与光催化性能研究

采用溶胶-凝胶法制备了TiO2光催化剂,研究了不同温度下焙烧TiO2粉体的XRD和FT-IR光谱。400℃焙烧后,相应有机物的红外吸收峰消失,随着焙烧温度的升高,粉体粒径变大,800-420cm-1之间的吸收峰逐渐锐化,700℃焙烧的FT-IR谱的423cm-1为金红石型TiO2的特征Ti-O键振动。500℃焙烧的锐钛矿型TiO2粉体对水杨酸具有较好的光催化活性。     

锐钛矿相纳米TiO2晶体生长动力学及生长过程控制

研究了采用溶胶-凝胶法经由前驱物钛酸四异丙酯水解制备纳米TiO2结构相变及锐钛矿晶体生长动力学过程. 研究结果表明,在酸性条件下水解,由于高压热处理温度的变化导致锐钛矿向金红石相的结构相变,锐钛矿相纳米TiO2生长活化能在250℃以下和以上分别为(15.8±4.5) kJ/mol和(80.2±1.0) kJ/mol;而在碱性条件下水解的活化能值为(3.5±0.4 kJ/mol. 在不发生结构相变的条件下,酸性水解条件下锐钛矿相纳米TiO2生长速率相比没有碱性条件下快,即表明在酸性条件下提高锐钛矿生长速率主要依靠提高温度来实现,而在碱性条件下,可以通过延长高压热处理时间使得晶体生长速率加快,该研究成果对实现锐钛矿相纳米TiO2晶体尺寸控制和将来批量化制备提供了理论和实验指导.     

纳米二氧化钛的红外辐照相变

以四氯化钛为原料 ,采用溶胶凝胶法技术合成路线 ,可以获得平均粒径在 30到 4 0纳米的二氧化钛粉末。在X—射线衍射 (XRD)和拉曼散射 (Raman)测试技术下 ,分析得到红外干燥方式下可使锐钛矿向金红石相转化 ,同时由于TiO2 纳米晶粒的尺寸效应以及弱的结晶性和局部格点不完善 ,使得Raman光谱特征峰向低波数移动。此外 ,随着反应温度的提高 ,逐步有金红石相产生 ,而 4 48cm- 1Eg 活性模对温度的依赖性体现了反斯托克斯现象。     

纳米TiO_2-活性炭的制备及光催化脱汞初探

采用溶胶凝胶法以活性炭(AC)为载体,制备纳米TiO_(2-)活性炭复合物(TiO_(2-)AC).采用X射线衍射仪(XRD),场发射扫描电镜结合X射线能谱分析仪(FSEM-EDX)对TiO_(2-)AC复合物进行表征。在波长为253.7 nm的紫外光照射下进行TiO_(2-)AC光催化氧化脱除单质汞试验。结果表明,复合物表面TiO_2纳米粒子尺寸可控制在30 nm左右;热处理温度的升高促进TiO_2晶粒的生长及相变,复合物中TiO_2锐钛矿相向金红石相转变的温度在500～700℃之间;负载锐钛矿型TiO_2的复合物较金红石型复合物显示出更强的光催化脱汞效果。TiO_(2-)AC能够达到预期的结合TiO_2光催化氧化性能与活性炭强吸附能力的效果,脱汞性能显著,具有广阔的应用前景。     

掺钴氧化钛电极的制备、表征及其光电性能

采用溶胶 凝胶法在纯钛片上制备了掺Co氧化钛薄膜光电极 ,运用扫描电子显微镜 (SEM )、X射线衍射 (XRD)等分析手段对其进行表征 ,并对其结构和性能的相互关系进行了研究 .结果表明 ,掺 5 %Co ,5 0 0℃热处理的TiO2 电极具有最大的可见光响应 .过量的Co掺入将析出新相CoTiO3 ,并促使TiO2 由锐钛矿型转变为金红石型 ,使电极光电效应减低 .而高温处理的掺钴TiO2 也将析出CoTiO3 ,对电极光电性能有阻碍作用     

负载型纳米TiO2-Al2O3载体的液相合成及表征

采用沉淀法、共沉淀法、溶胶-凝胶法和改进的溶胶-凝胶法制备出TiO2-Al2O3复合载体,并用XRD、TEM、FT-IR等手段对其进行了表征。XRD结果表明,复合载体经550℃焙烧后,TiO2和Al2O3分别以锐钛矿和γ-Al2O3晶型存在,其中沉淀法和改进的溶胶-凝胶法制得载体的锐钛矿特征峰宽而尖锐;共沉淀法和溶胶-凝胶法制得的载体的锐钛矿特征峰表现不明显。TEM结果表明,TiO2为纳米粒子且均匀分布在Al2O3表面上,共沉淀法制备出的复合载体的粒子形貌表现为锐钛型TiO2粒子在γ-Al2O3上以单层或亚单层分散形式存在,而改进的溶胶-凝胶法制备出的复合载体中锐钛型TiO2和γ-Al2O3粒子形貌以更为清晰的橄榄状和絮状形式存在。FT-IR结果表明,4种方法制备出的复合载体酸性均主要表现为以L酸形式存在,仅含微量B酸。     

锐钛矿相纳米TiO2晶体生长动力学及生长过程控制

研究了采用溶胶-凝胶法经由前驱物钛酸四异丙酯水解制备纳米TiO₂结构相变及锐钛矿晶体生长动力学过程. 研究结果表明,在酸性条件下水解,由于高压热处理温度的变化导致锐钛矿向金红石相的结构相变,锐钛矿相纳米TiO₂生长活化能在250℃以下和以上分别为(15.8±4.5)kJ/mol和(80.2±1.0)kJ/mol;而在碱性条件下水解的活化能值为(3.5±0.4)kJ/mol. 在不发生结构相变的条件下,酸性水解条件下锐钛矿相纳米TiO₂生长速 关键词： 2')" href="#">纳米TiO₂ 锐钛矿 生长动力学 溶胶-凝胶法     

(Fe,N)共掺杂TiO2红外光谱的电负性原理研究

采用电负性原理,构建合理的红外光谱模型,对TiO2红外光谱的振动频率与元素电负性之间的各种经验关系进行探究.采用溶胶-凝胶法制备(Fe,N)共掺杂TiO2,利用X-射线衍射(XRD)、傅里叶红外光谱(FTIR)对样品的物相和红外光谱进行了表征.XRD物相分析表明当煅烧温度为600 ℃时,TiO2样品中的无定形结构己基本转化为锐钛矿型结构.随着煅烧温度升高,TiO2的X射线衍射峰逐渐由宽变窄,衍射强度由弱变强.当煅烧温度为700 ℃时,锐钛矿型的衍射峰基本消失,取而代之的是金红石相的衍射峰,但TiO2的主晶相并没有发生改变.红外光谱分析表明(Fe,N)共掺杂TiO2在650~500 cm-1区间有一个较宽的吸收峰.电负性模拟计算了(Fe,N)共掺杂TiO2红外光谱的伸缩振动频率,获得了Fe、N掺杂的位置、分子结构和键价特征:首先计算出约化质量μ,然后按照经典力学伸缩力常数k与频率V之间满足的关系,结合力常数与电负性关系、键级的计算方法,计算了基本单元都是氧八面体的掺杂金红石、锐钛矿TiO2的分子振动频率.结果表明:通过电负性理论计算的(Fe,N)共掺杂的TiO2的红外光谱与实验测量的红外光谱的伸缩振动频率比较吻合.     

TiO_2晶型及其相变的高温拉曼光谱研究

本文测量了锐钛矿型和金红石型TiO2常温至1923K的高温拉曼光谱,观察了锐钛矿型TiO2在1373K～1473K间发生相变,不可逆转化为金红石型TiO2,分析了特征峰随温度变化的规律以及两种结构相的温度依赖性。并为不同晶型TiO2的研究、生产和应用提供重要的实验依据。     

Sn掺杂的纳米TiO_2的拉曼散射

本文主要利用拉曼光谱研究一组在合成过程中掺入了不同浓度锡的纳米二氧化钛样品,确定其从锐钛矿结构到金红石型结构的转变,进而分析其金红石型结构的形成。拉曼光谱测试表明,晶型导向剂SnO2的引入促使金红石型TiO2在较低的反应温度下形成,高温合成条件的免除使我们获得了很好的纳米级的金红石型TiO2晶体。此晶体具有有趣的包覆型结构,金红石型TiO2纳米晶体内包含着同结构的SnO2籽晶。分析其成因,在结晶过程中,掺入的杂质原子Sn4+与O2-结合,先沉积出金红石型结构的SnO2作籽晶,金红石型结构的SnO2和同样结构的TiO2晶格常数十分接近,促使了TiO2在它表面外延生长,形成金红石结构的包覆纳米晶。     

冲击波温度和压力对二氧化钛相变的影响

 介绍了一种简便易行的降低疏松固体物质冲击波温度的方法，其要点是用液体石蜡充填样品的空隙。以用粉末锐钛矿压装成型的样品为例，对比了不充填和充填液态石蜡时冲击波作用的结果。在同样的冲击加载条件下（均为钢飞片，撞击速度为3.16 km/s），估算两种样品中达到的压力分别为36.3 GPa和46.8 GPa，平均温度分别约为4.7×10³ ℃和2.0×10³ ℃，即：充填液态石蜡的样品中压力增加了约10 GPa，但平均温度降低了近3×10³ ℃。对冲击后回收样品的分析结果表明，不充填石蜡样品的主要产物为金红石，即冲击波产生的高温起了主要作用。而充填液态石蜡时，主要生成β-TiO₂高压相，即高压起了主要作用。     

BaCO3和TiO2粉末混合物冲击压缩性和BaTiO3冲击合成的实验研究

 利用高能炸药爆轰驱动冲击波、狭缝扫描闪光隙高速照相技术和阻抗匹配解原理，在10~100 GPa压力范围内，测量了BaCO₃和TiO₂粉末混合物的冲击绝热数据。同时，利用轴对称柱面和平面爆轰装置，进行了该混合物样品的冲击后回收实验和回收样品的X射线衍射分析，考察BaTiO₃的冲击合成。测量出的冲击绝热数据，以冲击波压力和比容平面上的结果为例，在约30和45 GPa两个压力值时，比容发生明显跃变。冲击绝热数据与回收样品X射线衍射分析结果相结合，判断出，这两个跃变分别对应于TiO₂从锐钛矿相转变到高压β-TiO₂相，BaCO₃与TiO₂开始急剧化学反应合成出BaTiO₃并放出CO₂。此外，在压力为10 GPa左右作回收实验，其回收样品的X射线衍射分析表明TiO₂由锐钛矿相完全转变为金红石相。     

Structural and thermoluminescence properties of undoped and Fe-doped-TiO<Subscript>2</Subscript> nanopowders processed by sol–gel method

In this study, we report on the nanocrystalline powders of TiO₂ and Fe-doped TiO₂ (anatase and rutile phases) prepared by sol–gel method. The X-ray diffraction and Raman spectroscopy measurements indicated the presence of anatase or rutile phase in nanopowders. TEM micrographs showed 10 and 112 nm average particle sizes for anatase and rutile, respectively. Furthermore, their thermoluminescence properties were analyzed.     

Silver-Doping Induced Lattice Distortion in TiO2 Nanoparticles

The Ag-doping effects on Ti02 nanoparticles are investigated by means of x-ray diffraction （XRD） and Raman scattering spectroscopy. XRD and Raman results indicate that Ag-doping stabilizes the rutile phase in TiO2. We find an Ag-doping induced lattice expansion in both anatase and rutile phases. The Ag-doping has different influences on the lattice distortion for anatase and rutile phases, that is, the e/a-value for the anatase phase decreases with 0.5% Ag-doping and then increases with 1~ Ag-doping while that for the rutile phase shows a gradual increase with increasing Ag-doping. We have ascribed the different variations of lattice distortion due to Ag-doping to the change of interracial interaction between the anatase and rutile phases induced by different Ag concentrations.     

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.     

The effect of different ambient gases, pressures, and substrate temperatures on TiO2 thin films grown on Si(100) by laser ablation technique

Pure titanium dioxide (TiO₂) thin films were deposited on single-crystal Si(100) substrates by laser ablation. We investigated the effects of ambient gas (O₂ or Ar), pressures, and substrate temperatures on film quality. From the annealing experiment of the deposited TiO₂ thin film under Ar or O₂ ambient gas, we see the chemical effect of ambient gas on film quality. The crystallinity of the deposited TiO₂ thin film is best at 700 °C in the substrate temperature range attempted, 400-700 °C, and at pressures of 0.1 Torr and below. The rutile phase is dominant under most experimental conditions. Only under very extreme conditions did we obtain a thin film of the anatase phase.     

The effects of activated carbon supports on the structure and properties of TiO2 nanoparticles prepared by a sol-gel method

TiO₂-coated activated carbon (TiO₂/AC) composites and pure TiO₂ powders were prepared by a sol-gel method using tetrabutylorthotitanate as a precursor. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), differential thermal analysis (DTA), X-ray photoelectron spectrum (XPS) and nitrogen absorption. The photoactivity of samples was evaluated by methylene blue (MB) degradation. The analysis results show that compared with pure TiO₂ powders, the spherical-shaped TiO₂ particles are well-dispersed in the AC matrix and the size of the resulting TiO₂ crystallites decreases to below 40 nm with increasing phase transformation temperature. The AC matrix creates anti-calcination effects and shows interfacial energy effects that control the growth of the TiO₂ particles, baffle the anatase to rutile phase transition, and cumber the TiO₂ particles to agglomerate. Compared with the surface areas of TiO₂ powders, the combination of TiO₂ and AC forms composites with high surface areas which are slightly affected by calcination temperature. By AC support, the photoactivity of TiO₂ is increased in MB photocatalytic course, possible because active carbon increases photocatalytic activity of TiO₂ particles by producing high concentration of organic compound near TiO₂, and small-size TiO₂ particles are well-dispersed on the surface of AC.     

Characterization and antibacterial functions of Ag–TiO<Subscript>2</Subscript> and W–TiO<Subscript>2</Subscript> nanostructured thin films prepared by sol-gel/laser-induced technique

A novel sol-gel/laser-induced technique (SGLIT) has been developed to form nanocrystalline titanium dioxide (TiO₂) based thin films with an improved antibacterial performance. TiO₂ precursor films loaded with W⁺⁶ and Ag⁺² ions (W–TiO₂, Ag–TiO₂) were prepared separately by sol-gel method and spin-coated on microscopic glass slides. As-dried films were subjected to KrF excimer laser pulses at optimized parameters to generate mesoporous anatase and rutile phases at room temperature. The anatase phase was obtained after irradiation with 10 laser pulses only at 75–85 mJ/cm² fluence in W–TiO₂ films. However, higher number of laser pulses and higher W⁺⁶ content favored the formation of rutile. Whereas Ag–TiO₂ films exhibited anatase up to 200 laser pulses at the same fluence. The films were characterized by using XRD, FEG-SEM, TEM and UV-Vis spectrophotometer to investigate the crystallographic structure, phase transformation, surface morphology, film thickness and the optical properties. A crystallite size of approximately 20 nm was achieved from the anatase prepared by SGLIT. The films exhibited an enhanced antibacterial function against E-Coli cells under the UV excitation.     

Oxygen defect dependent variation of band gap,Urbach energy and luminescence property of anatase,anatase–rutile mixed phase and of rutile phases of TiO2 nanoparticles

TiO₂ nanoparticles are prepared by a sol–gel method and annealed both in air and vacuum at different temperatures to obtain anatase, anatase–rutile mixed phase and rutile TiO₂ nanoparticles. The phase conversion from anatase to anatase–rutile mixed phase and to rutile phase takes place via interface nucleation between adjoint anatase nanocrystallites and annealing temperature and defects take the initiate in this phase transformation. The samples are characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), UV–vis and photoluminescence spectroscopy (PL). Anatase TiO₂ exhibits a defect related absorption hump in the visible region, which is otherwise absent in the air annealed samples. The Urbach energy is very high in the vacuum annealed and in the anatase–rutile mixed phase TiO₂. Vacuum annealed anatase TiO₂ has the lowest emission intensity, whereas an intense emission is seen in its air annealed counterpart. The oxygen vacancies in the vacuum annealed samples act as non-radiative recombination centers and quench the emission intensity. Oxygen deficient anatase TiO₂ has the longest carrier lifetime. Time resolved spectroscopy measurement shows that the oxygen vacancies act as efficient trap centers of electrons and reduce the recombination time of the charge carriers.     

Enhanced photocatalytic performance of TiO2 particles via effect of anatase–rutile ratio

In the present work anatase–rutile transformation temperature and its effect on physical/chemical properties as well as photocatalytic activity of TiO₂ particles were investigated. The characterisation of the synthesised and annealed TiO₂ particles were determined by X-Ray Powder Diffraction (XRD), scanning electron microscope (SEM), dynamic light scattering (DLS) and Brunauer–Emmett–Teller surface area analysis (BET). The refraction in the ultraviolet–visible (UV–vis) range was assessed using a dual-beam spectrophotometer. The photocatalytic performance of the particles was tested on methylene blue solution. The XRD data indicated that the percentage of rutile increased with the annealing temperature and almost 100% of anatase transformed to rutile at 1000 °C. In addition, the phase transformation was a linear function of annealing temperature so phase composition of TiO₂ can be controlled by changing the annealing temperature. The SEM and BET results presented the increase of agglomerate size and the decrease of specific surface area with the increasing annealing temperature. This proved that anatase has smaller particle size and higher surface area than rutile. The photocatalytic activity of the annealed TiO₂ powders reduced with the increase of annealing temperature. The samples annealed at 900 °C and 925 °C with anatase: rutile ratio of 92:8 and 77:23, respectively, showed the best activity. These results suggested that the photocatalytic activity of TiO₂ particles is a function of phase composition. Thus it can be enhanced by changing its phase composition which can be controlled by annealing temperature.