Zn2+掺杂对TiO2相变温度和晶粒尺寸的影响

采用溶胶-凝胶法制备了不同含量Zn2 掺杂的氧化钛粉体,利用TG-DTA、XRD测试技术检测了锌离子掺杂对锐钛矿和金红石相变及其晶体尺度的影响。试验结果表明,锌离子的掺入抑制了锐钛矿和金红石的相变,使相变温度提高,而且显著阻碍晶体的生长,从而获得纳米晶体。     

锡掺杂二氧化钛相变过程和微结构分析

本文采用溶胶凝胶法制备了锡掺杂纳米二氧化钛,通过高分辨透射电镜法(HRTEM),X-射线衍射法(XRD)等分析手段对样品的相变过程进行了表征.XRD和HRTEM测试表明纯二氧化钛在烧结温度高于500℃时出现金红石相,而25mol; Sn2+掺杂二氧化钛凝胶在300℃烧结2h后少量锐钛矿相析出的同时结晶出金红石相.实验结果表明Sn2掺杂抑制了锐钛矿和金红石相的晶粒长大;Sn2+掺杂明显地促进了锐钛矿向金红石的转变.Sn2氧化后形成Sn4+,Sn4+置换Ti4+而引起二氧化钛晶格膨胀的同时晶格畸变应力增加.     

高热稳定性锐钛矿型Nd掺杂纳米TiO2的制备与表征

以钛酸丁酯为原料,采用溶胶凝胶法合成了纯TiO2与Nd掺杂TiO2纳米粉体,对其进行了350℃至850℃的热处理.利用XRD、SEM、和EDS对粉体的晶型结构,微观形貌和元素成分进行表征,研究了Nd掺杂对TiO2晶粒尺寸以及晶型转变的影响.结果表明:样品晶粒尺寸达到纳米级别,Nd掺杂后TiO2晶粒尺寸减小.纯TiO2在550℃时已经有金红石生成,750℃完成锐钛矿向金红石的转变;Nd掺杂TiO2在750℃时仍然是锐钛矿,850℃时有少许金红石生成,Nd掺杂提高了TiO2锐钛矿结构的热稳定性.     

稀土掺杂氧化钛基材料的相变及其湿度-电阻关系

本工作采用溶胶-凝胶工艺制备了La3 和Ce4 掺杂的TiO2-SnO2复合粉体,利用X-衍射仪对该粉体的相组成进行了分析,并对组装的湿敏薄膜元件进行了湿度-电阻关系的测试。结果表明,在500℃烧结,La3 和Ce4 掺杂对锐钛矿向金红石的转变起到先促进后阻碍的作用;600℃烧结,La3 和Ce4 掺杂抑制了锐钛矿向金红石的转变,La3 、Ce4 的加入降低了锐钛矿和金红石的晶体尺寸,同时降低了薄膜材料的电阻,使湿度-电阻关系呈现较好的线性度。La3 的作用最强,且促进了SnO2晶体的形成。     

Ce掺杂TiO2纳米粉体的制备及其光催化性能研究

以钛酸丁酯为前驱体,冰醋酸为螫合剂,以硝酸铈为掺杂剂,采用溶胶.凝胶法制备了铈掺杂TiO2纳米粉体.研究了铈掺杂对TiO2相组成和晶粒尺寸的影响及不同掺杂量对TiO2光催化活性的影响,确定了Ce的最佳掺杂量.结果表明:Ce掺杂缩小了TiO2的锐钛矿相→金红石相(A→R)的相变温区范围,抑制了TiO2的晶粒增长.热处理温度升高,二氧化钛的比表面积下降.掺杂适量的铈提高了TiO2的光催化活性,Ce掺杂为0.05;摩尔分数时Ce-TiO2的光催化活性达到最佳,甲基橙降解率可达90;左右.     

氮掺杂TiO2优势晶面及晶型的调控研究

以氮化钛为前驱体,氢氟酸、盐酸为晶面和晶型调控剂,采用一步水热法成功法制备了氮掺杂TiO2单晶,对样品进行了SEM、XRD和TEM分析,结果表明:在氟离子单独调控下,TiN优先生成具有(001)优势晶面的锐钛矿型片状TiO2单晶;在氯离子单独调控下,TiN优先生成具有(110)优势晶面的金红石型棒状TiO2单晶;在氟离子和氯离子协同调控下,TiN优先生成具有(001)优势晶面的锐钛矿型片状TiO2单晶,且在(001)晶面正方形的四个直角处均生成两个较小的新晶面.     

掺锗提高VO2薄膜的相变温度机理研究

二氧化钒(VO₂)作为一种长久以来备受关注的新型可逆相变材料,发展潜力巨大,其相变温度(T_MIT)的调控一直是研究热点。本文主要利用锗离子作为掺杂离子探索其对VO₂薄膜T_MIT的影响,并尝试解释其内部作用机理。在约1 cm²大小抛光的氧化铝薄片上沉积了一系列含不同比例锗离子VO₂薄膜。研究发现锗离子作为掺杂离子确实有利于T_MIT的提高(本课题T_MIT最大可达84.7 ℃)。T_MIT提高的主要原因是锗离子的引入能够强化单斜态V-V二聚体的稳定性,进而增强单斜态的稳定性,使得低温单斜态向四方金红石态转变更加困难。     

热处理过程对纳米TiO2结构和性能的影响

以钛酸丁酯为钛源,采用溶胶-凝胶法制备纳米TiO2,结合TG-DTA,XRD,TEM等分析了不同热处理温度对纳米TiO2的晶型结构、晶粒粒径及微观形貌的影响.以甲基橙溶液为目标降解物,探讨了热处理温度对纳米TiO2光催化活性影响.利用Eastman的粒子生长理论对晶粒生长的动力学过程进行初步分析.研究表明:随着热处理温度升高,TiO2粒径逐渐从11.2 nm增大到78.6 nm;热处理温度为450～ 550℃时,纳米TiO2晶粒以锐钛矿为主,温度升至650℃时,出现了锐钛矿和金红石的混合相(质量比A∶R =9∶1),此时晶粒对甲基橙的降解率达到97.75;.而煅烧温度高于850℃后,TiO2几乎完全为金红石相,光催化活性显著下降.50;锐钛矿型TiO2转变金红石型TiO2的温度约为730℃,锐钛矿和金红石相晶粒表观活化能分别18.15 kJ/mol和42.56 kJ/mol;晶粒生长最快温度分别为546℃和1280℃.     

密度泛函理论研究MgH2的电子和光学性质

基于密度泛函理论,采用平面波赝势和BFGS法计算研究了金红石相MgH2电子结构性质和线性光学性质.基态下,金红石相MgH2晶体具有良好的弹性力学稳定性,基本结构参数与实验值及其其他理论值符合得较好.Mulliken电荷分布和集居数分析发现:金红石相MgH2晶体中电荷主要从Mg原子向H原子转移,电荷总数主要来源于Mg2p态电子和H1s态电子,金红石相MgH2属于共价键和离子键混合型化合物.结合电子性质和频率相关介电函数ε(ω)计算研究了金红石相MgH2的介电函数、线性吸收系数、复折射率及消光系数、反射率和能量损失谱,结果表明:金红石相MgH2的主要吸收区间位于紫外光区;24.88~42.35 eV能量区间金红石相MgH2具有很强的透过性;高频情况下,金红石相MgH2具有极高的反射率.     

不同价态稀土元素Eu掺杂锐钛矿相TiO2的电子结构及光学性质

基于密度泛函理论(DFT)的第一性原理的平面波超软赝势法对锐钛矿TiO2晶体和Eu3+,Eu2分别掺杂的锐钛矿TiO2晶体的晶格参数、能带结构、态密度、差分电荷密度以及吸收光谱进行了计算.结果表明:不同价态Eu掺杂后锐钛矿TiO2晶胞膨胀,晶格都发生畸变;同时引入了杂质能级,减小了锐钛矿相TiO2的禁带宽度,TiO2的光吸收带边发生明显红移,在紫外区和可见光区的吸收系数增大.     

Phase transformation and crystal growth behaviors of La3+/Ce3+-doped TiO2–20 wt% SnO2 gels

The transformation behaviors of La³⁺/Ce³⁺-doped TiO₂–SnO₂ gels were studied by using differential thermal analysis and X-ray diffraction methods so as to improve the phase transformation and decrease the granularity of crystals. Experimental results show that, anatase, rutile and SnO₂ nanocrystals can exist in the sintering products by varying La³⁺/Ce³⁺ contents and sintering temperatures. 0.8–1.1 wt% of La₂O₃ or CeO₂ doping greatly depresses the growth of anatase and rutile crystals, obtaining nanosized crystals when sintered up to 600 °C for 2 h. With La³⁺/Ce³⁺-doping and increasing their contents, the transformations of gel to anatase and anatase to rutile, as well as the growth of anatase and rutile crystals can be depressed, while the transformation temperature of anatase to rutile receives much less affect. Moreover, the La³⁺-doping has stronger effects on them than Ce³⁺ doping, but has a weaker inhibiting effect on precipitation and growth of SnO₂ crystals.     

The phase transformation behaviors of Sn2+-doped Titania gels

The transformation behaviors of Sn²⁺-doped titania gels, such as transformation temperature, conversion rate and the crystal granularity, were studied by using thermo-gravimetric/differential thermal analysis and X-ray diffraction methods. Experimental results show that, anatase, rutile and SnO₂ phases can exist in the sintering products by varying Sn²⁺ content and sintering temperature. Sn²⁺-doping greatly depresses the growth of anatase and rutile crystals and so obtaining nanosized crystals The transformation temperatures of gel to anatase and anatase to rutile first decrease and then increase with an increase of Sn²⁺ content, while both of the transformation rates are associated with Sn²⁺ content, change in its valence and the sintering temperature. It is suggested that by adjusting Ti⁴⁺/Sn⁴⁺ ratio and sintering temperature, the crystal granularity and the ratio of anatase to rutile can be tailored to optimize properties of TiO₂–SnO₂ humidity sensing ceramics.     

水热法制备银修饰混晶二氧化钛及其光催化性能研究

采用水热法制备了锐钛矿、金红石、板钛矿三相混晶TiO₂,对其进行了Ag修饰改性。利用XRD、SEM、TEM、PL、DRS等测试技术研究了样品的晶体结构、形貌以及光学性质。结果表明,制备的TiO₂为锐钛矿/金红石/板钛矿三相混晶结构,Ag修饰后金红石含量增加,锐钛矿、板钛矿含量减小。Ag以单质Ag以及AgCl的形式存在,Ag@TiO₂异质结构更加有利于光生电荷的转移,提高了光催化活性。光照90 min后,银修饰TiO₂对盐酸四环素(TC)的降解率由纯TiO₂的78.5%提高到91.6%。     

不同晶型TiO2的制备与光催化性能研究

采用溶胶凝胶法,利用不同温度热处理制备了不同晶体结构的TiO2纳米晶.利用XRD、SEM、EDS、XPS等分析方法对样品的晶体结构、形貌、化学元素组成以及价态进行了表征.结果表明400 ℃、500 ℃热处理TiO2为锐钛矿晶型,600 ℃ 热处理为锐钛矿金红石混合晶型,700 ℃热处理为金红石晶型,单颗粒子呈现类似球形形貌.以罗丹明B为目标污染物,测试了样品的光催化性能,结果表明400 ℃热处理TiO2具有最高的光催化活性,3 h后对罗丹明B的降解率达到94.6;,其反应速率常数达到0.969 h-1.     

TiO2 thin films as sensing gas materials

TiO₂ thin films were prepared by DC reactive magnetron sputtering on heated Si, quartz and glass substrates using O₂ and water vapor as reactive gases. The percentage of anatase and rutile as well as the grain size strongly depend on the deposition conditions, as revealed by X-ray diffraction patterns. The films deposited on Si substrates are pure rutile, while a mixed anatase/rutile structure occurs in the films deposited on glass and quartz substrates. Smaller grain rutile and anatase films were prepared in a water vapor atmosphere, in contrast to the films grown in oxygen. The former choice considerably increases the sensing properties of titanium dioxide films. The gas sensitivity was investigated for some reducing gases (methane, acetone, ethanol and liquefied petroleum gas) and the optimum operating temperatures were found.     

La,Pr,Nd掺杂对纳米TiO2光催化性能的影响

采用水解共沉淀法制备了稀土元素(La, Pr, Nd)掺杂量为0.5wt;～1.5wt;的TiO2光催化剂样本,并对其进行了XRD、TG-DTA、TEM、BET和UV-Vis表征.结果表明,所制备的TiO2光催化剂是以锐钛矿晶型为主的纳米颗粒,掺杂抑制了TiO2晶型由锐钛矿向金红石的转变,同时减小了晶粒尺寸、增大了比表面积、提高了吸光度,且使TiO2半导体的吸光范围发生了红移.将制得的TiO2光催化剂应用于溶液中草酸的降解反应,用K2MnO4滴定法分析降解效率,发现经掺杂改性后的TiO2样本光催化效率均有提高.其中,以掺杂量为1.0wt;的La掺杂样本具有最高的降解效率,与纯TiO2样本相比对草酸的降解率提高了近45;.     

射频磁控溅射制备纳米TiO2薄膜的表征和亲水性能

采用射频磁控溅射TiO2陶瓷靶的方法在硅和石英衬底上制备纳米TiO2薄膜,并经950℃退火1h.通过X射线衍射(XRD)、原子力显微镜(AFM)、紫外可见光谱(UV-Vis)和接触角仪对薄膜相结构、表面形貌、光学性能和亲水性能进行表征.结果表明,与950℃退火1h相比,未退火薄膜是无定形结构并呈现较高的光致亲水性能.退火薄膜是锐钛矿和金红石混合相,其中锐钛矿相质量分数是11.34％.未退火和950℃退火1h的薄膜样品的能隙分别是3.03 eV和3.11 eV.未退火薄膜具有较高的光致亲水性能主要归因于其较低的光学能隙.退火薄膜的热致亲水性能与其相结构、表面清洁度和粗糙度有关.     

Effect of the substrate temperature on the crystallization of TiO2 films prepared by DC reactive magnetron sputtering

Titanium oxide (TiO₂) films were deposited on silicon substrates at the temperature in the range 50–600 °C by DC reactive magnetron sputtering. It was found that the anatase and rutile phases co-existed in the TiO₂ films deposited at 450–500 °C, while only the anatase phase existed in those deposited at other temperatures. The mechanism of such a crystallization behavior of TiO₂ films is preliminarily explained.     

Influence of La/Ce-doping on phase transformation and crystal growth in TiO2-15 wt% ZnO gels

Titania based ceramic is a good candidate for environmental sensing materials. Ion doping is an effective method to improve the properties by modifying their microstructure and phase composition. By using differential thermal analysis and X-ray diffraction methods, the transformation behaviors of La³⁺/Ce³⁺-doped TiO₂-15  wt% ZnO gels were studied so as to modify the phase transformation and decrease the granularity of crystals. Experimental results show that, anatase, rutile and ZnTiO₃ nanocrystals can be tailored by varying La³⁺/Ce³⁺ contents and sintering temperatures. La³⁺/Ce³⁺ doping decreases the transformation temperature of gel to anatase and the forming temperature of ZnTiO₃ phase, enhances the transformation temperature of anatase to rutile and results in appearance of Zn₂Ti₃O₈ interphase. With the increases of La³⁺/Ce³⁺ contents, the transformation rates of ZnTiO₃, gel to anatase and anatase to rutile, as well as the granularity of the crystals are reduced. Ultimately, the action mechanism of La³⁺/Ce³⁺ doping was discussed.