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。     

热处理对爆轰合成的纳米TiO_2混晶的结构相变的影响

采用爆轰法制备了纳米TiO2混晶体,初步研究了不同煅烧温度(600℃和720℃)和不同煅烧时间(1 h,2 h,3.5 h和5 h)对其微结构和结构相变行为的影响,并应用热动力学理论讨论了从锐钛矿相到金红石相的结构相变过程和相变机理.研究表明:随着煅烧温度的升高和煅烧时间的增加,纳米TiO2的粒径逐渐增大,混晶中金红石相的含量逐渐提高.与常规方法制备的纳米TiO2不同的是,在相同煅烧温度和煅烧时间下金红石相的平均生长速率明显低于锐钛矿相.锐钛矿相完全相变为金红石的温度也明显低于常规方法报道的相变温度.该研究会对控制纳米TiO2晶体尺寸和批量合成提供一定的理论和实验指导.     

平面冲击波作用下TiO_2晶粒的相变纳米化

利用平面冲击波技术,对溶胶-凝胶法制备的锐钛矿型TiO2粉体和干凝胶进行冲击实验,采用X射线衍射(XRD)、透射电镜(SEM)和激光粒度分析仪(LPSA)等手段对冲击前后的TiO2粉体和干凝胶进行表征。结果表明:冲击波的高温作用能够实现亚稳态的锐钛矿型TiO2向稳定态的金红石型TiO2转变,并且冲击波直接作用于干凝胶时更容易获得稳定态的金红石型TiO2;冲击波的瞬时性可以抑制TiO2晶粒的长大,实现晶粒纳米化;冲击波的高压作用可以有效控制由于溶胶-凝胶法导致的粉体团聚现象。     

重氧空位对金红石型和锐钛矿型TiO2导电性能影响的模拟计算

基于密度泛函理论框架下的第一性原理平面波超软赝势方法,构建了未掺杂与相同重氧空位金红石型和锐钛矿型TiO_1.9375超胞模型,分别对模型进行了几何结构优化、能带结构分布和态密度分布的计算. 结果表明,氧空位后金红石型和锐钛矿型TiO₂体系体积均变大,同时,锐钛矿型TiO_1.9375超胞的稳定性、迁移率以及电导率均高于金红石型TiO_1.9375超胞. 计算结果和实验结果相一致. 关键词： 重氧空位 2')" href="#">金红石型和锐钛矿型TiO₂ 导电性能 第一性原理     

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。     

锐钛矿相和金红石相Nb:TiO_2电学性质的GGA(+U)法研究

采用基于密度泛函理论第一性原理GGA和GGA+U相结合的方法研究了不同掺杂浓度下锐钛矿相和金红石相Nb:TiO2的晶体结构、电子结构以及稳定性.结果表明:锐钛矿相Nb:TiO2能带结构与简并半导体类似,呈类金属导电机理.金红石相Nb:TiO2呈半导体导电机理.Nb原子比Ti原子电离产生出更多的电子.锐钛矿相Nb:TiO2中Nb原子的电离率比金红石相Nb:TiO2的大.以上结果说明锐钛矿相Nb:TiO2比金红石相Nb:TiO2更适宜用作TCO材料;掺杂浓度对其杂质能级,费米能级和有效质量都有影响.Nb原子掺杂浓度越高,材料电离率呈降低趋势;形成能计算结果显示:在富钛条件下不利于Nb原子的掺杂,而在富氧条件下有利于Nb原子的掺杂.对于金红石相和锐钛矿相Nb:TiO2,不论是在贫氧或富氧条件下,随着Nb原子掺杂浓度的提高,形成能均增大.     

二氧化钛薄膜的制备及退火对其形貌、结构的影响

利用磁控溅射技术,在石英基片上沉积Ti膜,分别在400、600、700、900℃的大气中退火获得TiO2薄膜。采用这种制备方式获得的TiO2薄膜呈现不同的颜色,退火温度为400℃的样品为暗紫红色,600℃时为黑色,而在700℃和900℃时均为黄色。采用X射线衍射、扫描电子显微镜（SEM）以及Raman光谱等手段研究了退火温度对TiO2薄膜的结构和形貌的影响。结果表明：退火温度为400℃时,TiO2薄膜为锐钛矿相,温度升高至600℃时,几乎转变为金红石晶相,但仍存在微量锐钛矿相,温度升高至700℃以上,则完全转变为金红石晶相。由XRD衍射图可知退火温度为700℃和900℃时,薄膜的金红石相沿（101）晶面择优取向。     

二氧化钛薄膜的结构和光催化活性关系

用化学气相沉积法合成了具有不同晶体结构的二氧化钛薄膜，研究了二氧化钛薄膜的结构和光催化活性的关系．用XRD、AFM研究了薄膜的晶体组成和形貌，用亚硝酸根研究了薄膜的光催化活性．结果表明在制备温度低于573 K或高于773 K时，薄膜的结构分别为锐钛矿型或金红石型．而在上述温度之间生成的薄膜具有混合的晶型结构，特别是在623 K附近，制备的薄膜具有最高的光催化活性．进一步研究表明，当金红石与锐钛矿微晶体的比例在0.5?0.7时，催化剂薄膜具有高活性．     

(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.     

TiO2混晶光催化性能的第一性原理研究

本文采用第一性原理平面波超软赝势方法,通过搭建混晶界面的方式计算并分析了TiO2混晶的光催化性能.从光的吸收能力、光生电子-空穴对的分离效率以及载流子的转移效率三方面,与锐铁矿相和金红石相TiO2单晶进行对比分析.结果显示TiO2混晶的电子-空穴对分离率高于锐钛矿相TiO2、金红石相TiO2单晶,TiO2混晶中吸收峰明...     

Observation of carbon‐facilitated phase transformation of titanium dioxide forming mixed‐phase titania by confocal Raman microscopy

Confocal Raman microscopy, a relatively new and advanced technique, is found to be suitable for imaging the chemical morphology below the submicrometer scale. It has been employed to probe the phase transformation of carbon‐containing titania (TiO₂) nanopowder and titania thin film subjected to laser annealing. The observation of phase transformation from the anatase phase to the rutile phase at high laser power annealing is attributed to carbon inclusion inside or on the surface of titania. Upon annealing, carbon could react with the oxygen of titania and create oxygen vacancies favoring the transformation from the anatase to the rutile phase. This study provides evidence for the carbon‐assisted phase transformation for creating carbon‐containing mixed‐phase titanium dioxide by laser annealing. We explicitly focus on the presence of carbon in the phase transformation of TiO₂ using confocal Raman microscopy. In all of the investigated samples, mixed anatase/rutile phases with carbon specifically was found at the rutile site. X‐ray diffraction (XRD), scanning electron microscopy (SEM) and energy‐dispersive spectroscopy (EDS) studies have been performed in addition to Raman mapping to verify the mixed‐phase titania formation. Copyright © 2010 John Wiley & Sons, Ltd.     

Preparation of F-doped titania nanoparticles with a highly thermally stable anatase phase by alcoholysis of TiCl4

Pure anatase is a metastable phase and inclined to (transform) be transformed into rutile structure under heating over than 500 °C, which limits its suitability for high-temperature applications. Hitherto much research efforts have been made to increase the stability temperature of anatase structure. However, metallic doping usually introduced metallic oxides into titania at high temperature, and many nonmetallic doping are not competent for increasing the stability temperature of anatase structure up to 900 °C. In this study, F-doped anatase TiO₂ nanoparticles were conveniently prepared via the alcoholysis of TiCl₄ and the as-prepared product shows very high stability temperature up to 1000 °C before being transformed into rutile structure phase. On the basis of XPS results of F-doped titania annealed at different temperature, it is learned that the F atoms were anchored on the crystal planes of anatase in favor of decreasing the energy faces of anatase and stabilizing the anatase structure till annealed at 1300 °C all the anatase were transformed into rutile phase.     

Raman study of phase transformation of TiO2 rutile single crystal irradiated by infrared femtosecond laser

Titanium dioxide (TiO₂) rutile single crystal was irradiated by infrared femtosecond (fs) laser pulses with repetition rate of 250 kHz and phase transformation of rutile TiO₂ was observed. Micro-Raman spectra show that the intensity of E_g Raman vibrating mode of rutile phase increases and that of A_1g Raman vibrating mode decreases apparently within the ablation crater after fs laser irradiation. With increasing of irradiation time, the Raman vibrating modes of anatase phase emerged. Rutile phase of TiO₂ single crystal is partly transformed into anatase phase. The anatase phase content transformed from rutile phase increased to a constant with increasing of fs pulse laser irradiation time. The study indicates the more stable rutile phase is transformed into anatase phase by the high pressure produced by fs pulse laser irradiation.     

不锈钢丝网上薄膜TiO2光催化剂的Raman光谱研究

用Raman光谱方法来研究用Sol Gel法负载于金属丝网的薄膜TiO2 光催化剂的物相结构、厚度以及粒径大小。研究结果显示 ,薄膜达到一定厚度能够阻止基底Fe元素向薄膜表层的扩散 ;在 4 0 0℃下灼烧制得的薄膜TiO2 光催化剂具有锐钛矿晶型 ,而高于 4 0 0℃时 ,将出现金红石相TiO2 ;锐钛矿晶型TiO2 的Raman特征峰产生偏移 ,表明薄膜粒径的变化 ,通过计算表明 ,薄膜TiO2 的粒径为 10nm左右 ,TEM的分析结果也与之一致。     

Phase transformation at the surface of TiO<Subscript>2</Subscript> single crystal irradiated by femtosecond laser pulse

Phase transformation of a titanium oxide crystal irradiated by a femtosecond laser from rutile to anatase was studied by Raman spectroscopy. In the case of the high temperature phase of TiO₂ single crystal rutile, irradiated by the 120 fs, 800 nm, 250 kHz femtosecond laser with an average power of 300 mW for a short time, the intensity of Raman active mode E_g (446 cm^-1) of TiO₂ would decrease, while that of A_1g (611 cm^-1) increased, which indicated the color-center-defect-cluster was formed. After the longer irradiation time (less than 600 s), four new Raman active modes would occur, so a part of rutile in the irradiated region was transformed into anatase phase. As the irradiation time increased, the component of anatase increased to a constant, while that of rutile decreased. By this means, we can selectively induce anatase on the rutile surface through controlling the femtosecond laser exposure region. We suggest that this technique can be applied to fabricate micro patterns of anatase. PACS 52.38.Dx; 36.20.Ng; 36.40.Ei; 42.62.-b; 42.65.Dr     

N掺杂TiO_2纳米管阵列的制备与性质研究

本文采用阳极氧化法制备了孔径为60-80nm,孔壁厚约为20-30nm的高有序度TiO2纳米管。将制备的TiO2纳米管经表面酸化后在浓氨水中浸泡,并于氮气气氛中进行退火处理,以实现TiO2纳米管的N掺杂。利用SEM、XRD、Raman和XPS对样品的形貌与结构进行了研究。结果显示,掺N后不会破坏阳极氧化形成的高有序纳度米管阵列,而且N的引入促进了TiO2纳米管在低温下由锐钛矿相向金红石相的转变。N掺杂样品的XPS中出现了结合能位于399.7 eV的峰,该峰来源于TiO2的间隙氮杂质,显示此方法在TiO2纳米管中实现了有效的N的掺杂。     

溶胶-凝胶法制备的纳米TiO2结构相变及晶体生长动力学

讨论了采用溶胶-凝胶法经由先驱物钛酸四异丙脂水解而制备的纳米TiO₂粉末的 结构相变 ，并讨论了该纳米粉末的生长动力学机理.结果表明，水解pH值为0.9，当高压釜热处理温度 ＜503K时，粉末晶粒度增长较为缓慢，而当热处理温度＞503K时，粉末粒度明显长大.应用 相变理论计算出了纳米TiO₂颗粒的两阶段的生长激活能，分别是18.5kJ/mol和5 9.7kJ/mol .XRD物相分析表明，高压釜热处理温度达到503K时，样品就开始发生锐钛矿到金红石相的结 构相变，到543K就基本实现了这一结构相变，使得这一相变温度比其他文献中报道的又降低 了许多. 关键词： 2')" href="#">纳米TiO₂ 溶胶_凝胶法 结构相变 晶粒生长动力学     

Dynamic nucleation and growth of Ni nanoparticles on high-surface area titania

Nucleation and growth mechanisms of Ni nanoparticles synthesized via an incipient wetness technique on a high-surface area titania support (i.e., a mixture of anatase and rutile) are studied using environmental transmission electron microscope (ETEM). Most Ni nanoparticles are found to nucleate from the Ni precursor coated on the surface of the titania support. Even though both anatase and rutile supports are the nucleation sites for Ni nanoparticles, it was observed that the particles have different morphologies on the supports, i.e., a non-wetting morphology on the anatase support versus a wetting morphology on the rutile {1 0 1}. This is because the interfacial energy of Ni/rutile is lower than that of Ni/anatase. Titania clusters are found to nucleate on the surface of the Ni particles during in situ ETEM reduction, indicating that the presence of partial titania overlayers is directly related to the synthesis of the Ni/TiO₂ catalysts. The growth mode of the Ni nanoparticles on the titania support is three-dimensional, while that of the rutile cluster on the surface of the Ni is two-dimensional layer-by-layer.     

TiO_2纳米粒子的Ram an光谱表征和紫外可见光吸收特性

用 Sol- Gel方法制备粒径约 1 0 - 50 nm的 Ti O2 微粒。Raman光谱测量显示 ,水解时 p H值不同 ,在同样热处理温度下得到的 Ti O2 微粒的晶体结构不尽相同。在低于 673K热处理温度下得到的 Ti O2 微粒是板钛矿和锐钛矿的混合晶体。用谱峰拟合技术可以将样品 A1的1 57cm-1 Raman谱峰分解成分属于板钛矿和锐钛矿的两个振动峰。 UV- Vis测量表明 ,锐钛矿型 Ti O2 微粒的紫外光吸收性能最好。而粒度约 2 0 μm的市售锐钛矿型 Ti O2 的紫外光吸收性能甚至比板钛矿型和金红石型 Ti O2 纳米粒子的还略低些 ,表明小尺寸效应和表面缺陷对紫外光吸收亦有贡献     

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.