镧掺杂介孔TiO2光催化剂的制备、表征及其光催化性能

以钛酸四正丁酯和硝酸镧为原料, 以P123为模板剂,采用模板法合成了La掺杂型介孔TiO₂光催化剂, 借助TGA-DSC、BET、XRD及UV-Vis等测试手段对样品进行了表征,并以苯酚为模型污染物考察了镧掺杂量对样品光催化活性的影响．结果表明: La掺杂介孔TiO₂光催化剂孔径分布较均匀(～10 nm),比表面积可达165 m²/g．与纯介孔TiO₂相比,经掺杂改性后的样品在紫外光区及可见光区的吸收显著增强,对光具有更高的利用率,La掺杂可显著提高介孔TiO₂的光催化活性.     

铁和镧共掺杂纳米二氧化钛光催化剂的制备、表征及其光催化活性

以葡聚糖为模板,钛酸四正丁酯、硝酸铁和硝酸镧为前驱体采用模板法制备了一系列铁、镧单掺杂及共掺杂纳米TiO₂光催化剂. 利用SEM、XRD、BET比表面积测定和UV-Vis等技术对其形貌、晶体结构及表面结构、光吸收特性等进行了表征. 以甲基橙溶液的光催化降解为模型反应,考察了不同掺杂的样品在紫外和可见光下的光催化性能. TiO₂材料具有较大的比表面积(约150 m²/g),铁和镧共掺杂纳米TiO₂在可见光区域有较强的吸收,在紫外和可见光条件下较纯TiO₂和单掺杂TiO₂对甲基橙溶液具有更好的光催化降解效果,且铁和镧的掺杂量显著影响该材料的催化性能. 当铁掺杂量为0.5mol%、镧掺杂量为0.3mol%,在500 ℃焙烧2 h所得光催化材料的催化性能最佳,焙烧4 h即可使甲基橙的降解率达98.8%,且该复合材料有较高的循环回收利用率,重复使用4次仍可使甲基橙的降解率保持在88%以上.     

爆轰法制备纳米TiO2及其参数控制

 采用偏钛酸与炸药混合进行爆轰合成，制备出晶粒尺寸在10 nm到60 nm之间的纳米TiO₂粉末。结合XRD、TEM、BET等表征手段，研究了纳米TiO₂的制备参数与其晶粒尺寸和晶相结构之间的关系。发现当炸药含量增加时，产物晶粒尺寸增大，同时晶相结构随炸药量的增加逐渐由低温的锐钛矿型和板钛矿型向高温的金红石型转变，爆轰温度在这种转变过程中起着极为重要的作用。     

Photocatalytic Activities of Boron Doped Titanium Dioxide Nanoparticles and its Composite with Polyaniline

Abstract

Titanium dioxide (TiO₂) was doped with a nonmetalic element, boron (B), and the boron doped TiO₂ (B-TiO₂) was combined with polyaniline (Pani) through an in-situ polymerization technique. The photocatalytic activity of the prepared samples was monitored by the degradation of methylene blue under UV light irradiation. X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy were used to reveal the effect of boron doping on the crystalline and chemical structure of the photocatalyst, respectively. The morphological and elemental compositional characteristics of the samples were evaluated using field emission scaning electron microscopy (FE-SEM) and energy dispersive x-ray analysis. The optical band gap energy of the prepared samples was obtained by UV-Visible (UV-Vis) spectroscopy. B-TiO₂ exhibited enhanced photocatalytic performance compared to the undoped photocatalyst. Furthermore, compared with TiO₂ and B-TiO₂, Pani/B-TiO₂ displayed superior photocatalytic activity. The composite achieved almost 26% methylene blue degradation within 150?minutes. Although the boron doping enhanced the crystallinity of TiO₂ slightly, it did not affect the morphology. FTIR confirmed the presence of tri-coordinated interstitial boron in the Ti–O–B bonds. The UV-Vis spectra displayed a red shift with the incorporation of the boron atoms. The incorporation of the boron atoms in the TiO₂ crystal structure are suggested to promote the separation of the photoinduced electron-hole pairs, a possible reason for the enhanced photocatalytic activity. B-TiO₂ and its composite with polyaniline could be considered as a promising photocatalyst to remove organic dyes from the wastewater.     

Studies on the Chemical Synthesis of Nanosized Nickel Powder and its Stability

The synthesis of nanosized nickel colloids is investigated by using nickel chloride as the precursor, hydrazine as the reducing agent and palladium as the nucleation agent. High purity nickel can be obtained when the reaction temperature is above 80^°C. At a lower reaction temperature, nickel hydroxide is also present in the precipitate form. Starting concentration of nickel ion is a dominant factor in affecting colloidal sizes, while other parameters such as reaction temperature and quantity of poly(vinyl pyrrolidone) (PVP) exhibit only minor effects. Although PVP has some dispersion power, it is not capable of preventing nickel colloids from gradual agglomeration. Our study shows that the subsequent addition of poly(acrylic acid) (PAA) after synthesis can help to stabilize the nickel suspension. This stabilized suspension can then be de-stabilized by changing pH to lower than 4 and vice versa. This reversible stabilization–de-stabilization process is likely due to the behaviour of PVP–PAA complex in the aqueous solutions.     

TiO2及其掺Fe材料的制备和EPR谱的研究

以钛酸四丁酯、无水乙醇、冰醋酸为原料,在室温下用溶胶-凝胶法制备得到二氧化钛及其掺Fe样品的湿凝胶,室温放置2天后,100 ℃干燥得到干凝胶,在500 ℃下焙烧得到二氧化钛及其掺Fe的粉末状样品. 利用X射线衍射、电子顺磁共振等测试手段对样品进行分析,结果显示所得样品均为锐钛矿,Fe被引入了二氧化钛晶格中,Ti³⁺氧化中心信号强度随Fe掺杂量的增加而增强,峰值向磁场减小方向小幅偏移. 在不同测试温度下, 含Fe量为0.1%的Fe-TiO₂样品中Ti³⁺氧化中心信号强度随温度升高而增强,峰值也向磁场减小方向小幅偏移. 根据电子顺磁共振理论以及二氧化钛在空气中与O₂的反应解释了这些现象.     

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。     

Effect of Particle Size and Phase Composition of Titanium Dioxide Nanoparticles on the Photocatalytic Properties

Titanium dioxide (TiO₂) nanoparticles were prepared by the oxidation of titanium tetrachloride (TiCl₄) in a diffusion flame reactor. The average diameter of particles was 15–30 nm and mass fraction of anatase ranged from 40% to 80%. Effects of particle size and phase composition of those TiO₂ nanoparticles on photocatalytic properties such as decomposition of methylene blue, bacteria and ammonia gas were investigated. The degree of decomposition of methylene blue by the TiO₂ nanoparticles under the illumination of the black light was directly proportional to the anatase mass fraction, but inversely to the particle size. The decomposition of bacteria and ammonia gas by the TiO₂ nanoparticles under the illumination of the fluorescent light showed the same trend as in the case of the methylene blue.     

纳米二氧化钛介孔微球光催化降解水中BPA的机理

描述了两种不同三维二氧化钛介孔球对水悬浮液中BPA的光降解效果,结果发现紫外线照射下两种三维二氧化钛介孔球的光催化效果要优于P25型二氧化钛,且微球孔隙越小,对BPA的降解效果越好;运用HPLC-MS以及HPLC-MS-MS联用技术对降解中间产物进行定性分析,并且对BPA光催化降解机理进行分析。发现在光催化降解过程中形成5种主要的中间产物并对它们的演变过程进行了讨论。根据分析测定得到的降解中间产物,提出了一个关于两种二氧化钛介孔球光催化剂对BPA降解的详细路径。     

纳米TiO_2用于甲基橙溶液的光催化氧化研究

本实验采用纳米级的二氧化钛,对甲基橙溶液进行了紫外光催化氧化处理,探讨了pH的影响和添加Fe3+的效果及反应动力学方程,结果表明,采用UV/O3/TiO2工艺对其进行处理,pH4-5时,10W紫外灯光照60min,CODcr去除率达84%,脱色率达96%以上。添加Fe3+,对溶液的催化降解速度提高不明显。动力学研究表明,CODcr降解速度对CODcr的浓度为一级反应。     

PbMoO4微晶的水热合成及光催化性能

以钼酸铵、硝酸铅为原料,采用水热法合成了纳米PbMoO₄光催化剂,并采用光还原处理对其进行表面载Ag修饰。借助X-射线粉末衍射（XRD）、扫描电镜（FE-SEM）和紫外-可见吸收光谱（UV-Vis）等测试手段对样品进行表征,并以罗丹明B为模型污染物,考察了纳米PbMoO₄光催化剂的催化活性,研究了样品的制备条件和表面载银对催化剂活性的影响。XRD分析结果表明,所得样品为四方晶系结构,且产物纯度高;样品的形貌分析和光催化活性实验结果表明,水热体系的pH值对产物的形貌和活性影响显著,且表面载银可显著提高催化剂的可见光催化活性。     

光催化二氧化钛(TiO2)活性炭再生控制系统

对光催化二氧化钛(TiO2)活性炭进行了分析,利用光催化二氧化钛(TiO2)活性炭的再生机理,提出了光催化二氧化钛(TiO2)活性炭的制备方法及光催化二氧化钛(TiO2)活性炭再生控制系统的设计实现过程,论述了控制系统硬件原理,对TGS2600空气质量传感器电路、活性炭换层控制单元、再生用TL-D 15W/10紫外灯控制单元进行了描述和方案设计,对软件设计流程进行了讨论和说明; 在光催化二氧化钛(TiO2)活性炭再生控制系统,利用再生过程紫外灯光照强度连续监测及动态在线调整,结合程序计算反馈调整,运用碳层连续换层设计,使得 光催化二氧化钛(TiO2)活性炭的再生效率好,光催化二氧化钛(TiO2)活性炭再生控制系统对其它的类似设计提供了借鉴。     

单原子层FeS半导体纳米片及其光催化还原二氧化碳应用

采用简单的溶剂热法制备了厚度约为1.16 nm单层超薄FeS纳米片,其具有涵盖从近紫外至近红外的太阳光谱波段的优异光学吸收性能和干净均一的表面,显微图像显示其具有超薄的片状结构,晶面结构清晰,物相测定证实合成的超薄FeS纳米片为单硫铁矿相,物性测定及理论计算显示超薄FeS纳米片具有半导体的电子能带结构,电子迁移率高,全光谱光催化CO₂还原到CO的产率约为260μmol·g^-1·h^-1,且具有很好的光催化稳定性,该研究为地球储量丰富的铁基材料应用于能源转化领域提供了可行的方向.     

氮掺杂TiO2的冲击合成及可见光催化活性研究

 冲击相变及冲击诱导化学反应可导致材料的物理、化学性能发生显著改变。采用炸药爆轰驱动飞片高速碰撞产生冲击波的方法,对富氮掺杂物双氰胺（C₂N₄H₄）与P25 TiO₂或偏钛酸（H₂TiO₃）的粉末混合物进行冲击加载,对回收产物进行X射线粉末衍射、透射电子显微镜、X光电子能谱、比表面积及紫外-可见漫反射光谱表征,通过亚甲基蓝和罗丹明B评价了回收产物的可见光催化降解活性。结果表明：以P25 TiO₂为原料的冲击氮掺杂浓度可达8.88%,掺杂样品具有明显的可见光吸收,能带宽度减小到1.75 eV,样品中形成了少量Srilankite高压相;而以偏钛酸为原料的冲击氮掺杂浓度为3%～4%,能带宽度变化较小,但是由于其独特的冲击脱水膨胀机理,比表面积剧增。冲击氮掺杂样品对亚甲基蓝和罗丹明B染料有较好的吸附和可见光催化降解作用,其中高飞片速度处理的样品有更高的光催化降解活性。     

Gas-phase Crystallization of Titanium Dioxide Nanoparticles

We have investigated the development of crystal morphology and phase in ultrafine titanium dioxide particles. The particles were produced by a droplet-to-particle method starting from propanolic titanium tetraisopropoxide solution, and calcined in a vertical aerosol reactor in air. Mobility size classified 40-nm diameter particles were conveyed to the aerosol reactor to investigate particle size changes at 20–1200°C with 5–1-s residence time. In addition, polydisperse particles were used to study morphology and phase formation by electron microscopy. According to differential mobility analysis, the particle diameter was reduced to 21–23-nm at 600°C and above. Precursor decomposition occurred between 20°C and 500°C. The increased mobility particle size at 700°C and above was observed to coincide with irregular particles at 700°C and 800°C and faceted particles between 900°C and 1200°C, according to transmission electron microscopy. The faceted anatase particles were observed to approach a minimized surface energy by forming {101} and {001} crystallographic surfaces. Anatase phase was observed at 500–1200°C and above 600°C the particles were single crystals. Indications of minor rutile formation were observed at 1200°C. The relatively stable anatase phase vs. temperature is attributed to the defect free structure of the observed particles and a lack of crystal–crystal attachment points.     

High-Pressure Behavior of Nano Titanium Dioxide

Nanocrystalline rutile Titanium dioxide has been studied by X-ray diffraction at ambient temperature up to 47.4 GPa. The material is found to transform to the monoclinic baddeleyite structure between 20 and 30 GPa, which is higher than the corresponding pressure range for bulk material. Upon decompression, the baddeleyite phase transforms to the f -PbO 2 phase at about 4-2 GPa. The experimental bulk moduli are 211(7) GPa for the rutile phase, 235(16) for the baddeleyite type and 212(25) GPa for the f -PbO 2 type phase. The results are compared with previous measurements of bulk rutile Titanium dioxide.     

中空TiO2纳米球的制备

报道了一种新的无机模板法合成中空的TiO₂纳米球,该法以TiCl₄为钛源,中空Sb₂S₃微球为模板,利用TiCl₄水解产生的TiO₂沉积在模板的表面,同时产生的HCl消蚀Sb₂S₃,一步制备中空纳米材料。     

Facile Synthesis of Au Nanocube-CdS Core-Shell Nanocomposites with Enhanced Photocatalytic Activity

Au nanocube-CdS core-shell nanocomposites are prepared by using a one-pot method in aqueous phase with cetyltrimethylammonium bromide as the surfactant. The extinction properties and photocatalytic activity of Au-CdS nanocomposites are investigated. Compared with the pure Au nanocubes, the Au-CdS nanocomposites exhibit enhanced extinction intensity. Compared with CdS nanoparticles, the Au-CdS nanocomposites exhibit improved photocatalytic activity. Furthermore, the photocatalytic et~ciency is even better with the increase in the core size of the Au-CdS nanocomposites. Typically, the photocatalytic efficiency of the Au-CdS with 62 nm sized Au nanocubes is about two times higher than that of the pure CdS. It is believed that the Au-CdS nanocomposites may find potential applications in environmental fields, and this synthesis method can be extended to prepare a wide variety of functional composites with Au cores.     

二氧化锡气敏纳米粉体的红外光谱研究

采用溶胶-凝胶法制备了纳米级SnO2,利用XRD和IR光谱对其晶化过程进行了详细研究。结果表明,硝酸胶溶有利于SnO2纳米晶的生成,676和545cm-1处的红外吸收分别为二氧化锡中Eu型对称的Sn-O的伸缩振动和A2u型对称的O-Sn-O变角振动,且随着纳米粉体热处理温度的升高,峰形窄化,A2u型的变角振动峰强度降低。