Microwave dielectric properties of BaO–TiO2–TeO2 ternary system

Besides the applications as optical functional materials, tellurium oxides also have attracted interest as microwave dielectric materials. Most TeO₂-based binary and ternary system have large negative temperature coefficient of resonant frequency (τ_f), which is not compatible for the low-temperature cofired ceramic. To compensate τ_f close to zero, two single-phase predecessors of BaTe₄O₉ and TiTe₃O₈ are synthesized in air at 530–560 and 620–680 °C, respectively. The two predecessors show exceptional dielectric properties and their τ_f are opposite. The BaO–TiO₂–TeO₂ ternary system compounds are investigated by adjusting the ratio of BaTe₄O₉ and TiTe₃O₈ and sintered at 520–580 °C to develop the microwave properties and compensate the τ_f. After sintered at 560 °C, the ceramic sample with the composition of 0.47BaTe₄O₉–0.53TiTe₃O₈ exhibits a dielectric permittivity of 28, a Q × f-value of 12,200 GHz, and a τ_f of 4.0 ppm/°C measured at 10 GHz.     

超临界流体干燥法制备TiO2/ Fe2O3 和TiO2/ Fe2O3/ SiO2 复合纳米粒子及光催化性能

以TiCl₄ 、Fe (NO₃ )₃·9H₂O 和Na₂SiO₃19H₂O 为原料, 采用溶胶凝胶法结合超临界流体干燥法(SCFD)制备了纳米级TiO₂/ Fe₂O₃ 和TiO₂/ Fe₂O₃/ SiO₂ 复合光催化剂。以光催化降解苯酚对所得催化剂的催化活性进行了评价。结果表明, 纳米TiO₂/ Fe₂O₃ 复合粒子与单组分TiO₂ 比较, 复合粒子光催化活性高于单组分的TiO₂, 6h 苯酚降解率高达95.9 %。SiO₂ 的加入可以抑制纳米粒子粒径的长大和晶相的转变, 增强TiO₂ 纳米粒子的热稳定性。复合光催化剂中Fe₂O₃ 最佳掺入量为0.06 %, SiO₂ 最佳掺入量为10 %(摩尔分数) 。并用XRD、TEM 和FTIR 等手段进行了表征。TiO₂ 以锐钛矿型形式存在, SiO₂ 以无定性形式存在。比较了不同制备方法制得的TiO₂/ Fe₂O₃ 复合光催化剂, 得出超临界干燥法制备的光催化剂具有粒径小、比表面积大、分散性好、光催化活性高等特点。采用超临界流体干燥可直接得锐钛型纳米复合光催化剂。     

Optical properties and structure of R2O–Ga2O3–SiO2 and RO–Ga2O3–SiO2 glasses

Refractive index and molar refraction of Li₂O–, Na₂O–, CaO–, and BaO–Ga₂O₃–SiO₂ glasses have been used to test the validity of a structural model of silicate glasses containing Ga₂O₃ glasses. Ga₂O₃ enters these types of glass in a similar manner as Al₂O₃. It is assumed that, for (SiO₂/Ga₂O₃) >1 and (Ga₂O₃/R₂O) ≤1, Ga₂O₃ associates primarily with modifier oxides to form GaO₄ units. The rest of modifier oxide forms silicate units with non-bridging oxygen ions. Silicate structural units have the same factors as found for binary alkali- and alkaline earth silicate glasses. Differences between experimental and model values suggest another structure for (Ga₂O₃/SiO₂) ≥1.     

Synthesis of (Zn,Mg)TiO3–TiO2 composite ceramics for multilayer ceramic capacitors

(Zn_0.8Mg_0.2)TiO₃–xTiO₂ composite ceramics has been prepared via the solid-phase synthesis method. TiO₂ was employed to tone temperature coefficient of resonant frequency (τ_f) and stabilize hexagonal (Zn, Mg)TiO₃ phase. 3ZnO–B₂O₃ was effective to promote sintering. The movement of grain boundary was obvious because of the liquid phase sintering. The scanning electron microscope (SEM) photographs and energy dispersive spectrometer (EDS) patterns showed that segregation and precipitation of dissociative (Zn, Mg)TiO₃ grains occurred at grain boundary during sintering. SnO₂ was used as inhibitor to prevent the grain boundary from moving. The dielectric behaviors of specimen strongly depended on structural transition and microstructure. We found that 1.0 wt.% 3ZnO–B₂O₃ doped (Zn, Mg)TiO₃–0.25TiO₂ ceramics with 0.1 wt.% SnO₂ additive displayed excellent dielectric properties (at 1000 °C): ?_r = 27.7, Q × f = 65,490 GHz (at 6.07 GHz) and τ_f = −8.88 ppm °C⁻¹. The above-mentioned material was applied successfully to make multilayer ceramic capacitors (MLCCs), which exhibited an excellent electrical property. The self-resonance frequency (SRF) and equivalent series resistance (ESR) of capacitor decreased with capacitance increasing, and the quality factor (Q) of capacitor reduced as frequency or capacity increased.     

TiO2光催化还原CO2研究进展

简要综述了近年来用于光催化还原CO2的Ti O2材料,包括单一Ti O2光催化材料、金属负载型Ti O2材料、半导体复合Ti O2光催化材料、有机光敏化剂修饰Ti O2光催化材料、Ti O2分子筛光催化材料及其他Ti O2光催化材料,总结了各种Ti O2材料光催化CO2的优势,并介绍了其相应的光催化反应机理。     

Glass formation and third-order optical nonlinear characteristics of bismuthate glasses within Bi2O3–GeO2–TiO2 pseudo-ternary system

Glass-forming region of Bi₂O₃–GeO₂–TiO₂ (BGT) pseudo-ternary system was determined by using melt-quench method. A series of high transparent glass samples were selected and their structural characteristics were investigated by FT-IR and Raman spectra. By employing Z-scan and optical Kerr shutter techniques with femtosecond laser pulses as excitation source, third-order optical nonlinearities (TON) of the BGT glasses as well as the TON response time were investigated at wavelength of 800 nm. The ultrafast nonlinear response and high figure of merit suggest great potentials of BGT glasses in applications of all-optical switching or related optical devices.     

Synthesis and properties of glasses in the K2O–SiO2–Bi2O3–TiO2 system and bismuth titanate (Bi4Ti3O12) nano glass–ceramics thereof

Glasses were prepared by the melt-quench technique in the K₂O–SiO₂–Bi₂O₃–TiO₂ (KSBT) system and crystallized bismuth titanate, BiT (Bi₄Ti₃O₁₂) phase in it by controlled heat-treatment at various temperature and duration. Different physical, thermal, optical, and third-order susceptibility (χ³) of the glasses were evaluated and correlated with their composition. Systematic increase in refractive index (n) and χ³ with increase in BiT content is attributed to the combined effects of high polarization and ionic refraction of bismuth and titanium ions. Microstructural evaluation by FESEM shows the formation of polycrystalline spherical particles of 70–90 nm along with nano-rods of average diameter of 85–90 nm after prolonged heat treatment. A minor increase in dielectric constants (ε_r) has been observed with increase in polarizable components of BiT in the glasses, whereas a sharp increase in ε_r in glass–ceramics is found to be caused by the formation of non-centrosymmetric and ferroelectric BiT nanocrystals in the glass matrix.     

Highly active sulfided CoMo catalysts supported on (ZrO2–TiO2)/Al2O3 ternary oxides

(ZrO₂–TiO₂)/Al₂O₃ ternary oxide at 20 mol% Al₂O₃ (80% ZrO₂–TiO₂, in turn at 40–60 mol ratio) prepared by controlled co-precipitation (by urea thermal decomposition) of zirconium (ZrOCl₂·8H₂O) and titanium (TiCl₄) chlorides over a ground alumina substrate constitutes a promising material to be used as carrier of sulfided hydrodesulfurization (HDS) catalysts. After calcining (at 500 °C), the ternary oxide presented textural properties (S_g = 387 m² g⁻¹, V_p = 0.74 ml g⁻¹, mean pore diameter = 7.6 nm) suitable to its utilization as carrier of catalysts applied in the oil-derived middle distillates HDS. As determined by temperature programmed-reduction and Raman and UV–vis spectroscopies ZrO₂–TiO₂ deposition over alumina substrate resulted in decreased proportion of Mo⁶⁺ species in tetrahedral coordination on the oxidic impregnated material. As those species constitute hardly reducible precursors, their diminished concentration could be reflected in enhanced amount of Mo species susceptible of activation by sulfiding (H₂S/H₂ at 400 °C) over our ternary carrier. Limiting the concentration of zirconia-titania (at 40–60 mol ratio) to 20 mol% in the mixed oxides support allowed the preparation of highly active promoted (by cobalt, at Co/(Co + Mo) = 0.3) MoS₂ phase (at 2.8 atoms/nm²), that formulation showing excellent properties in hydrodesulfurization (HDS) of both dibenzothiophene and highly-refractory 4,6-dimethyl-dibenzothiophene. Due to alike yields to various HDS products over CoMo/(ZrO₂–TiO₂)/Al₂O₃ and the corresponding Al₂O₃-supported formulation, presence of similar actives sites over those catalysts was strongly suggested. It seemed that enhanced concentration of octahedral Mo⁶⁺ over the oxidic impregnated precursor with (ZrO₂–TiO₂)/Al₂O₃ ternary carrier resulted, after sulfiding, in increased amount of MoS₂ phase that could be efficiently promoted by cobalt.     

A heterostructured SnO2–TiO2 thin film prepared by Langmuir–Blodgett technique

SnO₂–TiO₂ heterostructure films were prepared through Langmuir–Blodgett (LB) route. LB films of octadecyl amine (ODA)–titanyl oxalate multilayer deposited on Si (100) and decomposed at 600 °C showed rutile and anatase phases of ultrathin TiO₂ film. Subsequently, multilayer LB film of ODA–stannate deposited on the pre deposited TiO₂ film after decomposition at 600 °C resulted in thin SnO₂ films on the TiO₂ thin film. The phase analysis of the SnO₂–TiO₂ film showed cassiterite phase of SnO₂ as well as the rutile/anatase mixture of TiO₂ indicating a SnO₂–TiO₂ heterostructured film. Surface morphology of the pure TiO₂ film and SnO₂–TiO₂ film were analyzed by using AFM. Electrical characterization by AC impedance analysis suggested SnO₂–TiO₂ heterostructure formation. DC current voltage measurement showed increase in photocurrent indicating visible light absorption and efficient charge separation under the sunlight type radiation.     

Al2O3/TiO2复配改性环氧树脂的绝缘特性

为了满足高压直流输电体系对绝缘子性能的特殊要求,使用三氧化二铝(Al₂O₃)和二氧化钛(TiO₂)复配掺杂的方法改性环氧树脂基底,对复合物表面结构以及绝缘特性进行了分析。绝缘性能测试结果表明,相比于Al₂O₃或者TiO₂单独掺杂,共掺杂可以更显著降低复合物表面电阻率并且增加电气强度。将2种纳米材料的质量调到合适比例时,纳米粉体/树脂基底界面上会形成一定的导电通道,载流子可以沿着通道被传导出去,从而改善表面电阻率。而适当量Al₂O₃的引入可以进一步改善材料的电气强度。优化后复合物的表面电阻率为8.62×10¹³Ω,电气强度可达到29.01 kV/mm,共掺杂的协同效应对于树脂绝缘性能的提升十分有意义。     

WO3添加方式对V2O5/TiO2催化剂性能影响

以TiO2为载体,采用挤压成型法制备了钒系蜂窝整体式SCR脱硝催化剂,通过N2吸附-脱附(BET)、X射线衍射(XRD)、扫描电镜(SEM)、FT-Ra-man光谱等表征手段和催化活性测试对混合练泥工序中助催化剂WO3不同引入方式制备的催化剂进行了对比研究。实验结果表明,由钛钨粉制备的催化剂具有较大的比表面积及孔容积;而由偏钨酸铵制备的催化剂具有较均匀的微观结构形貌,活性物种分散性好,拥有更多的VO6八面体结构,且出现了WOx四面体结构,表现出良好的NH3-SCR活性和较宽的活性温度窗口,在空速为10000h-1,氨氮比为1.0时,活性温度范围内NO脱除率达到了93%。     

纳米CaCO3/TiO2复合粒子制备超疏水膜

采用溶胶-凝胶法,用γ-(2,3-环氧丙氧基)丙基三甲基氧硅烷和油酸修饰纳米CaCO3/TiO2复合粒子,制备具有类似荷叶表面形貌的超疏水涂层。结合扫描电镜、红外光谱、热重和示差扫描量热仪对复合粒子进行表征。结果表明,纳米TiO2粒子物理复合在纳米CaCO3表面,复合粒子经修饰后引入了疏水性的甲基,形成纳米复合双重粗糙结构,使所制备的涂层表现出优良的超疏水性能,其中接触角为162.1°,滚动角7°。     

四元SCR催化剂V2O5-WO3-MoO3/TiO2脱硝性能

以锐钛型TiO2为载体,V2O5为主要活性成分,同时负载WO3和MoO3作为活性助剂,制备了四元催化剂V2O5-WO3-MoO3/TiO2,并对该催化剂的脱硝活性、催化选择性及微观表征进行了研究。结果表明,该四元催化剂脱硝性能优于相同负载量下单一负载W或Mo的三元催化剂,W可以提高催化剂高温(>400℃)活性,同时抑制Mo在高温区间导致的副反应发生,Mo可以提高低温(<300℃)活性,弥补W在低温区间的活性不足。该四元催化剂最大活性99%,温度窗口(脱硝活性>80%)为280～420℃,在180～380℃范围内SO2氧化率为零,在0～1000℃范围内存在3个失重峰,100～130℃结晶水蒸发,230～270℃有机添加剂分解,500～530℃无机盐分解,微观镜像表明该催化剂颗粒均匀致密,粒径大小一致,没有出现团聚现象,具有完整的微孔结构。     

TiO2掺杂WO3粉体的制备及其性能研究

以Na2WO4和HCl为原料通过液相沉淀法制备了WO3粉体,再用钛酸四丁酯和制备的WO3粉体通过钛酸胶体浸渍法制备了TiO2掺杂的WO3粉体,并利用傅里叶红外光谱仪和紫外-可见分光光度计对产品的性能进行了表征。结果表明,当煅烧温度为550℃、TiO2掺杂量为5%、催化剂最佳用量为0.04g时,TiO2掺杂的WO3粉体的催化降解性能最好,对甲基紫的降解率可达88.56%。     

TiB2基RuO2+TiO2涂层的电催化性能

用磁控溅射法在钛基体表面溅射TiB2中间层,以此为基体用热分解法制备了(Ru,Ti)氧化物涂层钛电极,用SEM、XRD、电化学工作站等手段对样品的性能和结构进行了表征。结果表明,含TiB2中间层的钛阳极表面涂层具有非连续状裂纹结构,钛基体和氧化物涂层的界面呈现紧密结合的状态,其电催化析氯性能优于传统钛阳极。选用TiB2中间层作为催化电极的载体,可改善基体和氧化物涂层的结合,延缓涂层的脱落,可避免基体和涂层间生成TiO2电阻膜,延缓涂层的失效;加入TiB2中间层可降低内阻,改善电子的传输能力,降低析氯电位,提高电极的催化活性和节能降耗。     

Bi2S3量子点敏化TiO2电极用于太阳能电池研究

研究了一种新型的量子点敏化太阳能电池,通过化学浴沉积法(CBD)将光敏化剂Bi2S3量子点沉淀在TiO2纳米多孔薄膜上。在太阳能模拟器照射下(AM 1.5,100mW*cm-2),研究不同CBD周期下制备的太阳能电池的光电特性。光电流的强度随着CBD周期的增加先增加而后降低,CBD循环5次后,光电流密度为0.84mA cm-2,开路电压为330mV,光电转化效率最高达0.065%。进一步研究表面,在开路环境下,CBD循环次数的增加增强了载流子的复合率并且降低了电子寿命。     

Fe-Mn/TiO2低温NH3-SCR脱硝催化剂的SO2中毒机理

Fe-Mn/TiO₂低温脱硝催化剂具有较高的低温活性和热稳定性,但抗SO₂能力差,不能满足工业应用要求。目前对于SO₂中毒位点以及中毒机理仍不明确。通过浸渍法制备了Fe-Mn/Ti、Fe/Ti、Mn/Ti,并在SO₂或NH₃-SCR气氛下对催化剂进行预硫化,通过TPD、H2-TPR、XRD、FTIR、XPS等表征手段对预硫化前后的样品进行表征,发现Ti、Fe/Ti、Mn/Ti和Fe-Mn/Ti催化剂预硫化后,Ti均发生硫酸化。在NH₃-SCR气氛比在SO₂气氛下催化剂中毒更严重,Fe加入后与Mn形成复合氧化物,改变Mn的存在状态,抑制Mn的硫酸化,但并没能阻止Ti的硫酸化。因此催化剂的抗毒性不仅要防止活性组分中毒,也需要防止载体中毒。     

γ-Bi2O3/TiO2复合纤维的制备及光催化性能

采用静电纺丝技术与溶剂热法相结合制备了γ-Bi2O3/TiO2复合纤维光催化材料.利用X射线衍射(XRD)、扫描电镜(SEM)、电子能谱(EDS)、透射电镜(TEM)、高分辨透射电镜(HRTEM)和紫外–可见吸收光谱(UV-Vis)等分析测试手段对材料进行了表征,并以罗丹明B(RB)的脱色降解为模式反应,考察了材料的可见光催化性能.结果表明:γ-Bi2O3纳米片均匀地生长在TiO2纤维上,形成了具有异质结构的γ-Bi2O3/TiO2复合纤维光催化材料,其光谱响应范围拓宽至可见光区,有利于TiO2光生电子和空穴的分离,增强了体系的量子效率.与纯TiO2纤维相比可见光催化活性明显提高,对RB的脱色率达87.8%.     

Bi2O2CO3/TiO2复合粉体的制备及其光催化性能研究

采用水热法制备了Bi2O2CO3,并将其与TiO2进行了复合。XRD数据表明此复合光催化剂中Bi2O2CO3结晶性良好,紫外-可见漫反射光谱说明Bi2O2CO3的加入使其吸收带边有一定的红移。研究了紫外-可见光照射下Bi2O2CO3/TiO2复合光催化剂对亚甲基蓝溶液的降解性能,结果表明当Bi2O2CO3与TiO2的质量比为0.032时,得到性能最优的复合光催化剂,其光催化活性优于TiO2。