N掺杂TiO2纳米粉体的表面特性及可见光活性

旨在探究N掺杂纳米TiO2具有可见光活性的本质,采用XPS、ESR、XRD、SEM、DRS、SPS和PL分析技术对sol-gel法制备的未掺杂和N掺杂TiO2纳米粉体进行了对比研究,并以亚甲基蓝(MB)溶液在可见光下的光催化脱色评价其可见光活性。结果表明,N掺杂TiO2纳米粉体具有良好的可见光活性,未掺杂样品几乎没有可见光活性。N取代TiO2晶格中O形成了N─Ti─O和O─N─Ti键合结构产生杂质能级,N掺杂导致TiO2表面形成了大量束缚单电子的氧空位产生缺陷能级,二者协同作用致使带隙窄化,光吸收带边红移,产生可见光活性。N掺杂导致TiO2晶格中p-n结的形成及表面氧空位和表面羟基的增加均能促进光生e-/h+分离,有效抑制光生e-/h+复合,提高量子效率,进而提高其光活性。     

Eu3+和Sm3+共掺杂TiO2光催化剂的协同效应

采用溶胶-凝胶法制备了纯TiO2和Eu3+/Sm3+共掺杂TiO2复合粉体,采用XRD,DRS和SEM等技术进行表征,以亚甲基蓝(methylene blue,MB)的光催化降解为目标反应,评价了其光催化活性,探讨了Eu3+/Sm3+共掺杂对TiO2粉体光催化的影响机制.结果表明,Eu3+/Sm3+共掺杂可以显著提高TiO2粉体光催化活性,Eu3+/Sm3+共掺杂在TiO2粉体中产生协同作用,可以抑制TiO2由锐钛矿相向金红石相转变,使TiO2的粒径减小.Eu3+/Sm3+共掺杂增大了TiO2粉体的晶格畸变,使TiO2粉体吸收带边蓝移.当Eu3+/Sm3+的掺杂量分别为0.05%和0.1%,TiO2光催化活性最高,光催化降解率达到84.8%.     

N掺杂介孔TiO_2纳米粉体的制备

以聚乙二醇400为表面活性剂、二乙醇胺为抑制剂,采用蒸发诱导自组装法(EISA)制备了介孔TiO2纳米粉体,并利用尿素为掺杂剂通过固相反应制备出高活性N掺杂介孔TiO2纳米粉体.利用XRD、FE-SEM、TG-DSC等方法对粉体的物相和形貌进行分析表征.结果表明,合成的粉体尺寸分布均匀、纯度高、具有均匀分布的介孔网状结构;N掺杂使介孔TiO2纳米粉体的UV-Vis光吸收曲线产生红移.     

流化床化学气相沉积法制备CNT/Fe-Ni/TiO2及其光催化性能研究

以Fe-Ni/TiO2为催化剂,采用流化床化学气相沉积法(FBCVD)在TiO2表面原位生长碳纳米管(CNT),得到CNT/Fe-Ni/TiO2复合光催化剂.通过SEM、XRD、UV-Vis等方法表征其结构和性能,以亚甲基蓝溶液降解为模型考察其光催化性能.结果表明:Fe-Ni/TiO2催化剂在FBCVD过程中,镍主要起到了CNT生长催化活性位的作用;在生长CNT后的复合光催化剂中,比例较低的Fe3+主要作为电子俘获剂,抑制TiO2光生电子空穴的复合;Ni和CNT共同起到将电子迅速地从TiO2中导出,从而降低光生电子空穴复合几率的作用.三者的协同作用显著改善了TiO2的光催化性能.其中Fe和Ni掺杂量分别为0.25mol%和4.75mol%样品的光催化活性较高,生长CNT后得到的复合光催化剂对亚甲基蓝的降解效率较纯TiO2提高约70%.     

Sb对直流反应磁控溅射制备TiO2薄膜的影响

用直流磁控溅射方法在Si(100)面及载玻片上制备了Sb掺杂TiO2薄膜.利用XRD光谱研究了Sb对其薄膜结晶情况的影响,用AFM观察其表面形貌,利用分光光度计测量了TiO2薄膜的光学特性及其对亚甲基蓝的分解活性,通过测量和计算表面对水的接触角来衡量光致亲水性.研究结果表明纯TiO2薄膜为锐钛矿型,适量Sb的掺杂能使TiO2薄膜的结晶有显著改善,并出现Ti2O3和金红石相TiO2,薄膜的光催化活性和光致亲水性明显改善.随着掺杂量的增加,TiO2薄膜的吸收边逐渐红移.但Sb掺杂过量时,破坏了二氧化钛原有的晶格结构,光催化活性和光致亲水性也相应降低.     

氧化钛基光催化材料的离子掺杂和酸化改性

本文基于光催化反应的机理分析,采用了金属离子掺杂和表面酸化相结合的改性方法对TiO2颗粒做了优化处理.对改性后的样品利用XRD、FTIR和PL等测试技术对样品进行了表征并以亚甲基兰为模拟污染物进行了光催化降解实验.结果表明包覆在粉体表面的新相以金红石为主;Fe离子掺杂降低了光生电子和空穴的复合几率;表面酸化增加了TiO2表面以双齿桥方式配位的羟基,此种羟基对TiO2光催化活性有重要影响;铁离子掺杂和表面酸化协同的改性方法可以明显提高TiO2粉体的光催化活性.     

Sm3+和Gd3+共掺杂TiO2粉体的制备和性能表征

采用溶胶-凝胶法制备了纯TiO2,1%Sm3+或2%Gd3+单掺杂和1%Sm3+/2%Gd3+共掺杂TiO2复合粉体,采用XRD和SEM/EDAX等技术进行表征。以对亚甲基蓝的光催化降解为目标反应,评价了TiO2复合粉体的光催化活性,探讨了Sm3+/Gd3+共掺杂、亚甲基蓝初始浓度和粉体投加量对TiO2粉体光催化活性的影响机制。结果表明,Sm3+/Gd3+共掺杂可以显著提高TiO2粉体的光催化活性;Sm3+/Gd3+共掺杂在TiO2粉体中产生协同作用,抑制了TiO2由锐钛矿相向金红石相转变,使TiO2粒径尺寸减小,增大了TiO2的晶格畸变。当亚甲基蓝初始浓度为4mg/L和粉体投加量为2g/L时,TiO2复合粉体的光催化活性最高,对亚甲基蓝光催化降解率达99.71%;降解亚甲基蓝反应符合Langmuir-Hinshelwood动力学方程。     

Bi掺杂纳米TiO2光催化甘油水溶液制氢性能研究

采用溶胶–凝胶法制备了TiO2和Bi掺杂的TiO2纳米颗粒,用N2吸附-脱附、SEM、XRD、FT-Raman、UV-VisDRS对光催化材料的孔结构、表面构造、能带结构、吸光特性进行了表征,并考查了其光催化甘油水溶液制氢反应的活性.结果表明:Bi掺杂后的TiO2为介孔结构的锐钛矿晶型纳米颗粒,其分散度明显增加,晶粒变小,比表面积增大;Bi掺杂使得TiO2禁带内形成杂质能级,降低了禁带能量,增加了光生电子和空穴的分离效率,有利于将TiO2的吸光带边界扩展至可见光区;Bi掺杂的TiO2样品表现出了远高于纯TiO2的光催化甘油水溶液制氢性能,2mol%Bi掺杂的样品在紫外光和模拟太阳光辐射下表现出了最高产氢活性,其速率分别为3534.8μmol/(h.gcat)和455.7μmol/(h.gcat).     

纳米La-TiO2光催化降解甲基橙废水的研究

采用溶胶-凝胶法制备了纯TiO2和La掺杂TiO2复合纳米粉体,通过XRD,UV-Vis等测试手段分析了在紫外光照射下,以降解甲基橙为探针反应研究其可见光催化性能。结果显示样品均为锐钛矿相纳米TiO2,稀土元素镧掺杂后纳米TiO2特征衍射峰宽化,强度降低;掺入的La主要以La2O3的形式存在,同时有一部分形成Ti-O-La键;La掺杂可减小TiO2晶粒尺寸及增大催化剂比表面积;与未掺杂的二氧化钛相比较,适当含量的镧掺杂可有效促进TiO2表面光生载流子的分离,从而显著提高其光催化活性。当La/Ti的摩尔比为0.010时,可见光催化性能最好。     

S／TiO2纳米氧敏材料的结构与吸脱附特性

以TiCl3为钛源,采用溶胶一凝胶法,在500℃(1h)烧结获得非金属离子(硫)掺杂TiO2的纳米粉体,利用XRD,FT-IR,UV-vis,ESEM,Zeta电位,XRF,TPD等表征S/TiO2结构特性.结果表明,硫掺杂有利于其向金红石相转变,低掺杂浓度(2at%)时,硫主要以S4 形式存在,当掺杂量为25at%时,部分掺杂硫以S2-形式替代O2-,由于两者间的电负性差异,导致表面上Ti3 、Ti4 周围的电子云密度增加,从而提高样品对氧气的吸附活性,使其表面的富余电子向吸附氧转移,提高了氧敏特性.S/TiO2敏感体表面的吸附氧以氧分子形式脱附(≤550℃),而在高温(≥600℃)下主要以SO2形式脱附.     

VLE data for CO2-CF2Cl2, N2-CO2, N2-CF2Cl2 and N2-CO2-CF2Cl

Knowledge about vapour-liquid (VLE) is required as a basis of reliable calculations for separation processes. Correlations available for the prediction of T, p, x, y data are less accurate for mixtures at high pressures and mixtures containing supercritical components. The results of VLE experiments are reported and compared with data calculated with equations of state.     

Preparation of ZrO2-CeO2 and HfO2-CeO2 nanopowders

We prepared weakly agglomerated powders of ZrO₂-CeO₂ and HfO₂-CeO₂ solid solutions 5–8 nm in particle size, consisting of monoclinic and tetragonal phases. After heat treatment at 1200°C, the crystallite size was 30 and 14 nm, respectively. We also examined the effect of precipitate freeze drying on the crystallization of hafnia-based solid solutions containing up to 20 mol % CeO₂.     

Thermal diffusion in binary mixtures H2-CCl2F2 and H2-CHClF2

Thermal diffusion coefficients were measured in two gaseous mixtures, in which one component was close to the critical temperature, in the pressure range (19.6–127.4)·10⁴ N/m² and at a freon concentration of 0.25–0.8.     

Comparison of the Electronic Structures of La2CuO4, Sr2CuO2Cl2, and Sr2CuO2F2

First-principles cluster calculations are reported of the local electronic structure of the three compounds: La₂CuO₄, Sr₂CuO₂Cl₂, and Sr₂CuO₂F₂. The copper ${\text{3d}}_{x^2 - y^2 } $ and the planar oxygen 2p _σ atomic orbitals exhibit a similar degree of covalency. The out-of-plane orbitals, however, are quite different with the ${\text{3}}d_{3z^2 - r^2 } $ atomic orbital lowered significantly in energy for chlorine and fluorine apical positions.     

Radial GRIN glasses in Li2O-Na2O-Al2O3-TiO2-SiO2 systems

A series of GRIN glass rods have been developed in Li2O-Na2O-Al2O3-TiO2-SiO2 systems. Negative radial refractive index profiles were generated by exchanging Na+ for Li+ ions in these glass rods. It has been observed that TiO2 plays a vital role in increase in the profile depth and maximum change in the refractive index because of its ambivalent nature. Change in the refractive index can be further increased by increasing the concentration of exchanging cation in the base glass.     

Elastic and Electronic Properties of Superconducting CaPd 2 As 2 and SrPd 2 As 2 vs. Non-superconducting BaPd 2 As 2

The first-principles calculations were performed to predict the elastic and electronic properties of the superconducting ThCr₂Si₂-type phases CaPd₂As₂ and SrPd₂As₂ in comparison with the non-superconducting CeMg₂Si₂-type phase BaPd₂As₂. Besides, the same properties were compared for CeMg₂Si₂- and ThCr₂Si₂-type polymorphs of BaPd₂As₂. We found that all these phases are mechanically stable and belong to soft materials with low hardness. The near-Fermi region is formed by the valence states of the blocks [Pd₂As₂] with decisive contributions of Pd 4d states. The values of N(E _F) increase in the sequence: CaPd₂As₂ < SrPd₂As₂ < BaPd₂As₂, i.e. in the reverse sequence relative to the transition temperatures T _C. Thus, the change in T _C cannot be explained by the electronic factor, i.e. by the simple correlation T _C～N(E _F). Most likely the decrease in T _C in the sequence CaPd₂As₂ → SrPd₂As₂ and the absence of a superconducting transition in BaPd₂As₂ are related to the structural factors and the peculiarities of the electron–phonon coupling mechanism.     

Si_2N_2O-Al_2O_3-La_2O_3和Si_2N_2O-Al_2O_3-CaO系统的亚固相关系

本文给出了 Si_2N_2O-Al_2O_3-La_2O_3和 Si_2N_2O-Al_2O_3-CaO 系统的亚固相图。实验结果表明:在 Si_2N_2O-Al_2O_3-CaO 系统中有一个未知结构的新化合物 CaO·Si_2N_2O,在3CaO·Si_2N_2O 和3CaO·Al_2O_3两化合物之间形成连续立方固溶体。而 Si_2N_2O-Al_2O_3-La_2O_3系统中则没有发现新化合物。在两个系统的富 Si_2N_2O区,过量的 Si_2N_2O 与 La_2O_3和 CaO 分别反应形成 Si_3N_4与 La_(10)[SiO_4]_(?)N_2(H-相)(和 CaSiO_3。所研究的这两个三元系统中,分别形成了如下几个四元相容性区。在 Si_2N_2O-Al_2O_3-La_2O_3系统内有:H-Si_3N_4-La_2O_3·Si_2N_2O-La_2O_3·Al_2O_3;H-Si_3N_4-La_2O_3·Al_2O_3-La_2O_3·11 Al_2O_3;H-Si_3N_4-La_2O_3·11 Al_2O_3-Al_2O_3;H-Si_3N_4-Al_2O_3-O′s.s;H-Si_3N_4-O′s.s-Si_2N_2O在 Si_2N_2O-Al_2O_3-CaO 系统内有:Si_3N_4-CaSiO_3-CaO·Si_2N_2O-3CaO·Al_2O_3;Si_3N_3-CaSiO_3-3CaO·Al_2O_3-2CaO·Al_2O_3·SiO_(?);Si_(?)N_(?)-CaSiO_3-2CaO·Al_2O_3·SiO_2-Al_2O_3;Si_3N_4-CaSiO_3-Al_2O_(?)-O′s.s;Si_3N_4-CaSiO_3-O′s.s-Si_(?)N_(?)O