纳米二氧化钛粉体晶相控制实验研究

在水解－沉淀法制备纳米TiO2粉体的过程中，使用不同的沉淀剂获得了晶相不同的纳米TiO2粉体，使用混合沉淀剂，通过控制沉淀剂的比例，制备了晶相组成（金红石与锐钛矿比例）不同的纳米TiO2多晶粉体，采用相同的粉体制备工艺，不同的后续处理工艺，探讨了锐钛矿向金红石转变的相变温度，经分析研究后认为，水解－沉淀法制备的纳米粉体中的锐钛矿向金红石红转变的温度为500－800℃，完全转变的温度在800℃以上；纳米TiO2多晶粉体的晶相组成不仅与沉淀剂的种类，混合沉淀剂中沉淀剂的比例和粉体的煅烧温度有关，而且与粉体的后续处理工艺和粉体表面界面相的稳定性有关。     

控制中和水解法制备纳米TiO2及其光催化性能的研究

用四氯化钛为原料,氨水为水解沉淀剂,采用控制中和水解的方法制备出了锐钛矿型纳米TiO2粉体.采用XRD和TEM手段对产品进行了表征分析,考察了中和水解过程中pH值、温度和浓度因素的影响.结果表明,pH值是影响产品前驱体组成的重要因素,当控制pH值在2～4的酸性条件下反应时,能得到团聚少的含有一定晶型的H2 TiO3前驱体,易于分离,收率可达97%以上,前驱体在600～800℃焙烧2h得到的是单一相锐钛矿TiO2纳米晶,平均粒径为15nm左右,高温焙烧时粒径生长缓慢,表现出很好的热稳定性.以甲基橙为目标降解物,测试了纳米TiO2样品的光催化性能.光催化降解反应60min时,甲基橙的去除率可达95.5%.     

不同水解抑制剂制备纳米TiO_2薄膜及其性能

本文以钛酸丁酯、三乙醇胺、冰醋酸、盐酸等为主要原料,采用溶胶-凝胶(sol-gel)法和旋转涂膜工艺在玻璃衬底上制备均匀、透明的纳米TiO2薄膜。利用X射线衍射(XRD)、紫外-可见光谱(UV/vis)和原子力显微镜(AFM)对纳米TiO2进行表征,结果显示:经500℃退火后,三乙醇胺、冰醋酸作水解抑制剂制备的TiO2粉体为锐钛矿晶相,而盐酸作水解抑制剂制备的TiO2粉体为锐钛矿、金红石和板钛矿的混合晶相;纳米TiO2薄膜存在光催化活性和吸收带边不同程度的蓝移,且用三乙醇胺制备的TiO2薄膜的蓝移最大,光催化活性最强。     

（TiO2-CdS）／SiO2复合粉体的溶胶一凝胶法合成及晶相转变

以钛酸丁脂为原料，CdS纳米晶为掺杂相，通过正硅酸乙脂水解，用溶胶-凝胶法制备(TiO2-CdS)／SiO2复合粉体。用DTA-TG、XRD和TEM对复合粉体进行表征。发现复合粉体中TiO2从无定型向锐钛矿型的相变温度大约为810℃，从锐钛矿型向金红石型的相变温度为900℃；添加少量的二氧化硅明显地抑制二氧化钛晶粒粒径的增大和相变。     

Ce/ TiO2纳米复合粉体的制备及其性能评价

以锐钛矿型纳米TiO2和硫酸铈为主要原料，采用浸渍法制备了Ce／TiO2纳米复合材料。采用滴定法研究TiO2对Ce^4＋的吸附，结果表明，在pH值为2-7的范围内TiO2对铈离子的吸附量接近100％。采用X射线衍射（XRD）进行物相结构分析，发现在700℃下焙烧仍保持锐钛型结构，而在800℃下焙烧出现了金红石型TiO2和CeO2，说明铈离子的存在减缓了TiO2的晶型转变。最后以甲基橙为目标降解物评价了Ce^4＋／TiO2复合粉体的光催化反应活性。     

(TiO2-CdS)/SiO2复合粉体的溶胶-凝胶法合成及晶相转变

以钛酸丁脂为原料,CdS纳米晶为掺杂相,通过正硅酸乙脂水解,用溶胶-凝胶法制备(TiO 2-CdS)/SiO2复合粉体.用DTA-TG、XRD和TEM对复合粉体进行表征.发现复合粉体中TiO2从无定型向锐钛矿型的相变温度大约为810C,从锐钛矿型向金红石型的相变温度为900℃;添加少量的二氧化硅明显地抑制二氧化钛晶粒粒径的增大和相变.     

纳米TiO2的原位包覆及分散性研究

采用水热合成法制备纳米TiO2粉体,以自制的1100分散剂对粉体进行原位包覆和后包覆,考察了分散剂用量、pH值对包覆体系分散性的影响,利用XRD和TEM进行结构表征和形貌观测,并采用分光光度法对纳米TiO2粉体水分散体系稳定性进行了检测,在此基础上制备了纳米TiO2／有机复合涂膜．研究表明：原位包覆制备的纳米TiO2中,锐铁矿相的质量分数为100％,分散较均匀,纳米TiO2粉体的平均粒径约为20nm;分散剂用量为8．0％、pH值为3和10时,其水溶液分散稳定性较高;后包覆制备的纳米TiO2粉体由锐钛矿相（73％）和金红石相（27％）构成,纳米TiO2粒子处于团聚状态,无明显颗粒形态;涂膜经自然光照射24h后,对大肠杆菌的杀灭率为99．8％;良好的分散工艺和有效的分散剂可充分发挥纳米TiO2的光催化功能．     

金红石生长用TiO2纳米晶粉体制备及表征

针对金红石晶体生长所需,我们人工合成了硫酸氧钛铵（ATS）晶体。并以其为原料,采用高温焙烧法制备了TiO2纳米晶粉体,用XRD、SEM和TEM分析了纳米晶的物相和形貌。结果表明所得TiO2纳米晶粉体分散性好、流动性好、纯度高且颗粒细小均匀。此外,研究了焙烧温度、保温时间和急烧、缓烧等工艺参数对其形貌、物相的影响,给出了大批是生产TiO2纳米晶粉体的最佳工艺条件。     

pH值对溶液燃烧法制备纳米LaFeO3的影响

以硝酸镧和硝酸铁为氧化剂,柠檬酸为燃料,采用溶液燃烧法制备了钙钛矿型LaFeO3.通过XRD和SEM研究了分别以氨水和NaOH溶液为pH调节剂,前驱物溶液pH值对制备的纳米LaFe03粉体的晶相组成和微观形貌的影响.结果表明不同的pH调节剂和前驱物溶液pH值对燃烧产物的晶相组成、晶粒大小和微观相貌都有显著的影响.氨水调...     

溶胶-凝胶法制备TiO2粉体及其光催化性能研究

以钛酸丁酯为前驱物,无水乙醇为溶剂,采用溶胶-凝胶法制备了TiO2粉体,并采用紫外分光光度计、XRD等表征手段对TiO2的粒度、晶型结构进行了表征,分析了煅烧温度、TiO2晶型比例、溶液初始pH值等因素对TiO2结构性能及光催化活性的影响.结果表明:TiO2的锐钛矿晶型与金红石晶型的转相温度为700 ℃左右;采用溶胶-凝胶法制备TiO2时,控制溶液的pH值为4,煅烧温度为600 ℃,所得产物晶型全部为锐钛矿;当无水乙醇与钛酸丁酯的体积比为10:1时,产物的粒径为617 nm;且当配制溶液pH值为4,煅烧温度为600℃条件下,煅烧时间为40~60 min时,所制备TiO2的光催化效果较好,降解率较高;当光催化体系的pH值为9、以质量浓度为10 mg/L的亚甲基兰溶液浸泡2 h,TiO2的用量为0.25 g/L时,产物的降解率高达95.3%.     

煅烧温度对二氧化钛纳米晶性能的影响

研究了不同煅烧温度下,锐钛矿相、混晶和金红石相二氧化钛纳米晶的 粒径、比表面积和吸收光谱的变化。经相同的温度煅烧后,金红石相二氧化钛纳米晶的生长速率和比表面积下降速率均大大高于锐钛矿相,表明高温反应或煅烧难以获得金红石相纳米晶,真空热处理的金红石相二氧化钛纳米晶可以保持较高的比表面积和较小的粒径,但易导致非化学配比、晶格缺陷并降低了粉体的性能。     

Reaction mechanism and kinetics analysis of the phase transformation of TiO2 from the anatase phase to the rutile phase

The kinetic mechanism of the phase transformation of TiO₂ from the anatase phase to the rutile phase was investigated. TiO₂ powders were prepared with different pH value of the starting solution via the thermal hydrolysis method in this study. The pH values of the starting solutions have significant effects on the phase transformation temperatures of the thermal hydrolysis reaction. As the reaction temperatures were raised, the conversion from the anatase phase to the rutile phase was increased. A core–shell morphology of the prepared TiO₂ samples was suggested via the signals of the anatase phase and the rutile phase in UV–vis spectrum analysis. Through the isothermal heating process of the reaction kinetics, the controlling reaction in the phase transformation process from the anatase phase to the rutile phase was determined to be the three-dimensional phase boundary controlled process. The activation energy of the phase transformation was increased with an increase in the pH value of the starting solution.     

铝硅酸盐中间体对TiO2纳米粒子团聚及相转变的抑制

以粉煤灰为原料, 通过与NaOH煅烧、水解合成铝硅酸盐中间体(ASI), 向sol-gel法制备的TiO₂溶胶中加入ASI, 经处理得到钛铝硅酸盐复合材料(TiO₂/ASI). X射线衍射分析(XRD)和紫外-可见漫反射光谱(DRS)研究ASI对sol-gel方法制备TiO₂纳米晶形成过程和相转变的影响. 研究结果表明: 铝硅酸盐中间体不但能抑制TiO₂纳米粒子的团聚, 而且能够有效地抑制TiO₂由锐钛矿型向金红石型的相转变, 由此所制备TiO₂与ASI的钛铝硅酸盐复合材料(TiO₂/ASI)对溶液中亚甲基蓝的吸附性能高于单一的TiO₂或铝硅酸盐中间体.     

Synthesis of nano titania particles embedded in mesoporous SBA-15: characterization and photocatalytic activity

Supported nanocrystalline titanium dioxide (TiO2) has been prepared by a post-synthesis step via Ti-alkoxide hydrolysis through the use of mesoporous SBA-15 silica. TiO2/SBA-15 composites with various TiO2 loading have been prepared and characterized by X-ray diffraction, nitrogen adsorption, Fourier transform infrared spectroscopy and diffusive reflective UV-vis spectroscopy. The addition of mesoporous SBA-15 prevents the anatase to rutile phase transformation and the growth of crystal grain. TiO2 did not block the SBA-15 pores, and their surface was fully accessible for nitrogen adsorption. Calcination in air of the composites up to 800 degrees C did not change the nanocrystal phase and slightly increased the domain size from 5.0 to 7.5 nm, indicating that the anatase TiO2 grains in the mesostructures have a relatively high thermal stability and proper pore diameter allows controlling the size of obtained titania particles. The TiO2/SBA-15 composites prepared by this study showed much higher photodegradation ability for methylene blue (MB) than commercial pure TiO2 nanoparticles P-25. Experimental results indicate that the photocatalytic activity of titania/silica mixed materials depends on the adsorption ability of composite and the photocatalytic activity of the titania, and there is an optimal ratio of Ti:Si, too high or low Ti:Si ratio will lower the photodegradation ability of the composites.     

板钛矿纳米TiO2微晶的热分析特性研究

对板钛纳米ＴｉＯ２微晶样品（ｎ－ＴｉＯ２）进行了差热分析（ＤＴＡ），发现其ＤＴＡ曲线上出现了Ａ、Ｂ两上吸热峰。通过对原始样品及其系列热处理样品进行Ｘ射线衍射（ＸＲＤ）实验，证实Ａ峰对应于物理或化学吸附的脱附过程，Ｂ峰完全对应于ｎ－ＴｉＯ２原始样品结构从板钛矿经锐钛矿向着金红石的一级相变；这一结构相变促成了纳米晶粒的生长。     

Effect of Flame Conditions on Crystalline Structure of TiO2 in Liquid Flame Spraying

Nanostructured TiO2 is a most promising functional ceramic owing to its potential utilization in photocatalytical, optical and electrical applications. Nanostructured TiO2 coating was deposited through thermal spraying with liquid feedstock. Two types of crystalline structures were present in the synthesized TiO2 coating including anatase phase and rutile phase.The effect of spray flame conditions on the crystalline structure was investigated in order to control the crystalline structure of the coating. The results showed that spray distance, flame power and precursor concentration in the liquid feedstock significantly influenced phase constitutions and grain size in the coating. Anatase phase was formed at spray distance from 150 to 250mm, while rutile phase was evidently observed in the coating deposited at 100 mm. The results suggested that anatase phase was firstly formed in the coating, and rutile phase resulted from the transformation of the deposited anatase phase. The phase transformation from anatase to rutile occurred through the annealing effect of spraying flame. The control of the phase formation can be realized through flame condition and spray distance.     

One step synthesis of rutile TiO2 nanoparticles at low temperature

Sphere-like rutile TiO2 nanocrystals have been synthesized by sol-gel method followed by hydrolysis of titanium tetrachloride in deionized water in the presence of ammonium hydroxide as hydrolysis catalyst. The as-prepared TiO2 nanoparticles have single rutile phase with average diameter approximately 26.4 nm. The results show that the temperature has a great influence on the particle size distribution and also crystalline phase (rutile) of TiO2 nanoparticles is consistent with the temperature. Characterization of the as-prepared nanocrystalline powder was carried out by different techniques such as powder X-ray diffraction (XRD), field emission transmission electron microscopy (FE-TEM) and Raman spectroscopy.     

Structural Characteristics of TiO2 Ceramic Coating by Micro-Plasma Oxidation

TiO2 ceramic coatings with thickness of 20 μm were formed on the surface of pure titanium by micro-plasma oxidation. Their micro-structures were investigated by by using X-ray diffraction and their surface images were detected by using scan electronic microscope. There were three kinds of TiO2 coatings, pure anatase type TiO2 phase, mixed phases consisted of rutile type TiO2 phase and anatase type TiO2 phase, pure rutile type TiO2 phase. The coating surface with the pure anatase type TiO2 phase is rough, while the coating surface with the pure rutile type TiO2phase is smooth. The upper coating surface with the mixed type TiO2 phases is anatase type TiO2 structure and the subsurface of the TiO2 coating is rutile type TiO2structure.     

Photoluminescence of dense nanocrystalline titanium dioxide thin films: effect of doping and thickness and relation to gas sensing

The photoluminescence (PL) of dense nanocrystalline (anatase) TiO(2) thin films is reported as a function of calcination temperature, thickness, and tungsten and nickel doping. The dependence of the optical absorption, Raman spectra, and PL spectra on heat treatment and dopants reveals the role of oxygen vacancies, crystallinity, and phase transformation in the performance of TiO(2) films used as gas sensors. The broad visible PL from defect states of compact and undoped TiO(2) films is found to be much brighter and less sensitive to the presence of oxygen than that of mesoporous films. The dense nanocrystalline grains and the nanoparticles comprising the mesoporous film are comparable in size, demonstrating the importance of film morphology and carrier transport in determining the intensity of defect photoluminescence. At higher calcination temperatures, the transformation to rutile results in the appearance of a dominant near-infrared peak. This characteristic change in the shape of the PL spectra demonstrates efficient capture of conduction band electrons by the emerging rutile phase. The W-doped samples show diminished PL with quenching on the red side of the emission spectrum occurring at lower concentration and eventual disappearance of the PL at higher W concentration. The results are discussed within the context of the performance of the TiO(2) thin films as CO gas sensors and the chemical nature of luminescent defects.     

Rietveld analysis of the effect of annealing atmosphere on phase evolution of nanocrystalline TiO2 powders

The structural evolution of nanocrystalline TiO2 was studied by X-ray diffraction (XRD) and the Rietveld refinement method (RRM). TiO2 powders were prepared by the sol-gel technique. Post annealing of as-synthesized powders in the temperature range from 500 degrees C to 800 degrees C under air and argon atmospheres led to the formation of TiO2 nanoparticles with mean crystallite size in the range of 37-165 nm, based on the Rietveld refinement results. It was found that the phase structure, composition, and crystallite size of the resulting particles were dependent on not only the annealing temperature, but also the annealing atmosphere. Rietveld refinement of the XRD data showed that annealing the powders under argon atmosphere promoted the polymorphic phase transformation from anatase to rutile. Field emission scanning electron microscopy (FESEM) was employed to investigate the morphology and size of the annealed powders.