气相法制备的纳米二氧化钛的脱酸方法

本发明公开了一种用于气相法制备纳米二氧化钛（TiO2）的脱酸方法。所述方法采用高温的热空气与水蒸气的混合气体为流化气体，在流化床反应器中对纳米TiO2进行脱酸，使脱酸后的纳米TiO2的pH在3．5—4．5，水质量分数小于2％。本发明通过混合水蒸气的引入，降低了脱酸温度，抑制了二氧化钛晶型由锐钛矿型向金红石型的转变，保持了其催化活性。     

混晶结构纳米TiO2粉体的制备与性能表征

以钛酸丁酯为前驱体,采用溶胶-凝胶法制备了具有混晶结构的二氧化钛纳米粉体材料.研究了煅烧温度、pH值对二氧化钛晶型的影响,并用X射线衍射(XRD)、场发射扫描电镜(SEM)、分光光度计等对其进行测试表征.光催化降解性能测试表明:同一pH值下,随着温度的升高,金红石型TiO2的含量增加,锐钛矿型TiO2的含量减少.随着溶胶pH值的减小,TiO2由锐钛矿相向金红石相的转变温度也随之降低.光催化降解亚甲基兰实验表明,锐钛矿含量为76.12%、金红石含量为23.88%时1h内光降解率达98%.     

稀土掺杂对TiO2-SiO2薄膜晶相转变及性能的影响

采用溶胶-凝胶法在釉面砖上制备了均匀的稀土离子La3+掺杂和ce4+掺杂的TiO2-SiO2,光催化薄膜.应用X射线衍射(XRD)和紫外可见分光光度计研究了La3+掺杂和ce4+掺杂对TiO2-SiO2,薄膜晶相转变、光催化性能及亲水性能的影响,用紫外光照射亚甲基蓝的光催化降解实验比较了不同薄膜的光催化性能.结果表明:La3+掺杂后,抑制了TiO2-SiO2薄膜中的TiO2,从锐钛矿向金红石相的晶型转变,显著提高了TiO2-SiO2,薄膜的光催化性能,也提高了其亲水性能;ce4+掺杂后,则促进了TiO2-SiO2,薄膜中TiO2从锐钛矿向金红石相的晶型转变,同时降低了薄膜的光催化性能.     

银掺杂对二氧化钛晶型转变的影响

采用溶胶-凝胶法制备了银掺杂的TiO2粉末,用XRD分析了掺银TiO2胶体经不同温度热处理后的晶型转变。结果表明:与未掺银的TiO2粉末相比,掺银TiO2从锐钛矿相向金红石相转变的起始温度较高,而且锐钛矿-金红石相变的温区范围变窄,晶型转变过程较快。     

沉淀法制备条件对氧化钛相变的影响

采用沉淀方法制备了纳米TiO2,探讨了制备过程中前驱体及溶剂对二氧化钛从锐钛矿到金红石相变的影响。结果表明:采用钛酸四丁酯(Ti(OBu)4)、异丙醇钛(TTIP)及钛酸四乙酯(Ti(OEt)4)为前驱体时,TiO2相变温度顺序为Ti(OBu)4>TTIP>Ti(OEt)4;不同溶剂制备的TiO2相变的温度不同,从锐钛矿转化为金红石晶相的温度由乙二醇<甲醇<乙醇方向增加。     

影响TiO2从锐钛型转变为金红石型的相变因素的研究

考察了V2O5、MoO3、醋酸及钾盐对TiO2由锐钛型向金红石型转变的影响，在相同条件下，V2O5对转化的促进作用优于MoO3，并且转化率随V2O5用量的增加而增大，适当使用醋酸和钾盐，也可促进TiO2由锐钛型到金红石型的相变过程。     

纳米二氧化钛改性氟碳涂料

湖南大学余刚、胡波年和杨景花等人日前研究成功一种纳米二氧化钛改性氟碳涂料及其制备工艺，该涂料是将锐钛矿型纳米TiO2和金红石型纳米TiO2混合物添加到现有氟碳涂料中，添加比例为：锐钛矿型纳米TiO2和金红石型纳米TiO2混合物在氟碳涂料的重量比为1～4：100；而上述锐钛矿型纳米TiO2和金红石型纳米TiO2混合物中，锐钛矿型纳米TiO2和金红石型纳米TiO2二者重量配比为4：1。本发明还包括所述改性氟碳涂料的制备工艺及用于涂敷铝合金板材的前处理工艺。使用这种氟碳涂料涂装后的铝合金型材和板材具有良好的自清洁性能，耐沾污和耐洗刷性能，良好的耐候性、耐化学腐蚀性，防水防潮，质量轻、防震、隔声、隔热、色泽均匀、不开裂、不变形、不剥落、不褪色等特点。     

TiO2负载玄武岩纤维毡复合材料的制备及其光催化性能

采用浸渍法将热蚀处理后的玄武岩纤维毡浸渍在Ti溶胶中负载成膜,在300 ～ 650℃烧结制备出TiO2负载玄武岩纤维毡光催化复合材料.利用XRD和SEM对TiO2和纤维毡进行了表征,并通过甲基红配制的模拟印染废水的降解考察了浸渍次数和烧结温度对光催化性能的影响.实验表明:随着玄武岩纤维毡在Ti溶胶中浸渍次数的增加,TiO2负载率增加,甲基红降解率具有先急剧增加后缓慢减小的趋势,TiO2负载率为4.83％时降解率达到极值98.58％.随着烧结温度升高,TiO2晶型由无定形态→锐钛矿→锐钛矿+金红石混晶转变,当锐钛矿与金红石混晶比例为9∶1 ～4.5∶1时,光催化性能较好,随着金红石相增加,甲基红降解率大幅降低.     

热处理温度对纳米TiO2薄膜光催化性能的影响（英文）

以TiCl4为原料,氨水为沉淀剂,采用水解沉淀法在硅藻土基多孔陶瓷上负载了TiO2薄膜。通过热重–差示扫描量热分析、X射线衍射对经不同温度热处理的样品进行了表征,探讨了热处理温度对TiO2晶相、晶粒尺寸等因素的影响。以甲醛为目标降解物,考察了热处理温度对TiO2光催化性能的影响。结果表明:随着热处理温度的升高,薄膜由锐钛矿型转变为金红石型,TiO2晶粒尺寸由6.5 nm(350℃)增加到52.8 nm(1 000℃);经750℃热处理的薄膜组成中出现金红石相,温度升至1 000℃,锐钛矿型TiO2完全消失;经550℃热处理的TiO2光催化效果最好,在1 m3环境仓内,8 W紫外灯下光照240 min,初始浓度0.526 mg/m3的甲醛去除率达到95.2%。     

TiO2对烧成镁钙砖烧结性能的影响

研究了两种晶型的TiO2(锐钛矿型和金红石型)作为添加剂对烧成镁钙砖烧结性的影响.结果表明,两种晶型的TiO2都能显著促进镁钙砖的烧结,其中以锐钛矿晶型为添加剂的效果好于金红石型的.XRD分析结果表明,TiO2与CaO反应生成了CaTiO3,这是加入TiO2使镁钙砖烧结性变好的主要原因.     

Fabrication and characterization of Ag–TiO2 multiphase nanocomposite thin films with enhanced photocatalytic activity

Ag–TiO₂ multiphase nanocomposite thin films were prepared on quartz substrates by the liquid phase deposition (LPD) method from a mixed aqueous solution of ammonium hexafluouotitanate, silver nitrate and boric acid under ambient temperature and atmosphere followed by calcination at 500 °C for 1 h. The grain growth of anatase was depressed upon Ag⁺ doping. However, silver ions not only promoted (or catalyzed) the formation of brookite phase but also reduced the phase transformation temperature of anatase to rutile. With increasing AgNO₃ concentration, the transmittance and band gap of the composite thin films decreased; however, the intensity of surface plasmon absorption (SPA) peaks increased and their peak position shifted to a longer wavelength range. When AgNO₃ concentration was higher than 0.03 M, the prepared samples consisted of anatase, brookite, rutile and metal silver nanocrystal particles, and their grain size ranges were 5–30 nm. The photocatalytic activity of the Ag–TiO₂ multiphase nanocrystal composite thin films prepared by this method exceeded that of pure TiO₂ thin films by a factor of more than 6.3 when AgNO₃ concentration was kept in the range of 0.03–0.05. This was attributed to the fact that there were many hetero-junctions, such as anatase/rutile, anatase/brookite, Ag/anatase, Ag/rutile and so on, existed in the Ag–TiO₂ multiphase nanocomposite films.     

Effect of sulfate ions for sol–gel synthesis of titania photocatalyst

We have found that the use of sulfuric acid in the peptization process of sol–gel method produced SO₄²⁻-incorporated TiO₂ which is mechanically strong by firing at low temperature such as 200°C. The synthesized TiO₂ has larger specific surface area and retards the phase transition from anatase to rutile compared with that prepared from the peptization with nitric acid. The S-content of the TiO₂ fired at 200°C was 1.52 wt.%; the value has a maximum of 2.74 wt.% at 400°C. The XPS measurements indicate that S exists mainly as SO₄²⁻. The TiO₂ fired at 400°C showed the highest photocatalytic activity for ethylene degradation. Especially, we would like to emphasize the TiO₂ sintered at 200°C because they are extremely hard in spite of such a low sintering temperature. This photocatalyst may provide a great opportunity for extensive applications as self-supporting membranes.     

Facile synthesis and enhanced visible-light photocatalytic activity of Ti3+-doped TiO2 sheets with tunable phase composition? ?

Ti³⁺-doped TiO₂ nanosheets with tunable phase composition (doped TiO₂ (A/R)) were synthesized via a hydrothermal method with high surface area anatase TiO₂ nanosheets TiO₂ (A) as a substrate, structure directing agent, and inhibitor; the activity was evaluated using a probe reaction-photocatalytic CO₂ conversion to methane under visible light irradiation with H₂ as an electron donor and hydrogen source. High-resolution transmission electron microscope (HRTEM), field emission scanning electron microscope, UV-Vis diffuse reflectance spectra, and X-ray diffraction (XRD) etc., were used to characterize the photocatalysts. XRD and HRTEM measurements confirmed the existence of anatase-rutile phase junction, while Ti³⁺ and single-electron-trapped oxygen vacancy in the doped TiO₂ (A/R) photocatalyst were revealed byelectron paramagnetic resonance (EPR) measurements. Effects of hydrothermal synthesis temperature and the amount of added anatase TiO₂ on the photocatalytic activity were elucidated. Significantly enhanced photocatalytic activity of doped TiO₂ (A/R) was observed; under the optimized synthesis conditions, CH₄ generation rate of doped TiO₂ (A/R) was 2.3 times that of Ti³⁺-doped rutile TiO₂.     

不同晶型TiO2消光PET的流变性能研究

分别以金红石型二氧化钛(TiO₂)粉体和锐钛矿型TiO₂粉体为消光剂,通过原位聚合制备不同TiO₂粉体含量的消光聚对苯二甲酸乙二醇酯(PET),研究了不同晶型TiO₂消光PET的流变性能。结果表明:在剪切速率()为4000~7000 s^-1,金红石型TiO₂和锐钛型TiO₂消光PET熔体的表观黏度(η_a)随的变化幅度均较小,均具有良好的纺丝稳定性;相同温度下,金红石型TiO₂消光PET的非牛顿指数(n)小于锐钛型TiO₂消光PET,但随着温度升高,金红石型TiO₂消光PET的n上升幅度大,其η_a对变化更为敏感;在常规纺丝条件下,金红石型TiO₂消光PET的黏流活化能(E_η)明显小于锐钛型TiO₂消光PET,TiO₂含量较低时金红石型TiO₂消光PET的η_a对温度变化的敏感程度较小;相同温度下,金红石型TiO₂消光PET熔体的结构黏度指数(η)高于锐钛型TiO₂消光PET;在纺丝温度有波动的情况下,金红石型TiO₂消光PET可纺性好,但其纺丝工艺窗口较窄,应采用更高的纺丝温度以获得良好的纺丝效果。     

硅藻土负载La~(3+)/TiO_2光催化剂的制备及其光催化性能

以钛酸四丁酯为前驱体,硅藻土为载体,采用溶胶-凝胶法制备TiO_2/硅藻土负载型光催化剂。以硝酸镧为镧源,采用等体积浸渍-焙烧法制备La~(3+)/TiO_2硅藻土光催化剂。通过XRD和SEM对制备的催化剂进行表征,以亚甲基蓝溶液模拟有机废水,考察n(Ti)∶n(Si)及La3+掺杂量对催化剂光催化性能的影响,结果表明,硅藻土可提高TiO_2分散性,降低TiO_2晶粒尺寸,并抑制其由锐钛矿相向金红石相的转变。在n(Ti)∶n(Si)=1∶1、焙烧温度550℃和La3+掺杂质量分数1%条件下,La~(3+)/TiO_2硅藻土光催化剂的光催化活性较好,紫外光连续照射180 min,亚甲基蓝降解率可达99.9%。     

Local structure and photocatalytic activity of B2O3–SiO2/TiO2 ternary mixed oxides prepared by sol–gel method

The local structure and the photoactivity of B₂O₃–SiO₂/TiO₂ ternary mixed oxides (SiO₂ content was fixed as 30 at.% with respect to TiO₂) was investigated by using XRD, FT-IR, BET, UV-vis spectra, and electron paramagnetic resonance (EPR) measurement. In FT-IR analysis, boron was incorporated into the framework of titania matrix with replacing Ti---O---Si with Si---O---B or Ti---O---B bonds. Also, paramagnetic species such as O⁻ and Ti³⁺ defects were formed by the boron incorporation. In SiO₂/TiO₂ mixed oxides, a blue shift in the light absorption band was observed due to the quantization of band structure. All B₂O₃–SiO₂/TiO₂ samples had pure anatase phase and no rutile phase was formed even though the calcination temperature was over 900 °C. Incorporating boron oxides of more than 10% enlarges the grain size of anatase phase and causes a red shift of the light absorption spectrum. The surface area was monotonically decreased with increasing the content of boron content. As a result, the photoactivity of B₂O₃–SiO₂/TiO₂ ternary mixed oxides was greatly influenced by the content of boron oxide. The highest photoactivity (g moles/min l) was obtained when the boron content was 5% and seven times higher than that of silica/titania binary mixed oxide. In addition, the specific photoactivity (g moles/m² l) was maximum still at 5%. It was concluded that the large reduction of surface area, the change of band structure, and more formation of bulk Ti³⁺ sites are responsible for the deterioration in the photoactivity of B₂O₃–SiO₂/TiO₂ ternary mixed oxides when the content of boron is over 10%, although their crystallinity was enhanced by increasing the calcination temperature with keeping anatase phase.     

Catalytic oxidation of low concentration formaldehyde over Pt/TiO2 catalyst

Formaldehyde(HCHO) is an important indoor pollutant.Catalytic oxidize low concentration HCHO is an effective way to eliminate indoor pollution.In this study,a series of Pt/TiO_2 catalysts are prepared by impregnation and reduced by NaBH_4.The effects of loading amount of Pt and cry stal type of TiO_2 on the physical and chemical properties and the catalytic performance in HCHO oxidation reaction are investigated.The results show that the quantity of active site and the oxygen vacancy of catalysts increa sed with increasing Pt content,which is beneficial to promote the further performance of catalysts.Nevertheless,with the further rises of Pt content,the specific surface area further decreases,and the proportion of Pt~(2+) species on the catalyst surface which is significant to catalytic properties also decreases,causing catalytic performance decreases.Compared with the catalyst supporting on rutile,the Pt/α-TiO_2 catalyst supporting on anatase has larger specific surface area,more Pt~(2+) phase and easier to form oxygen vacancy in the support,which cause better catalytic performance.The catalyst with Pt content of0.1 wt% and supported by anatase TiO_2 has the best catalytic performance.The HCHO conversion efficiency reaches 98% and 100% at 50℃ and 100 ℃, and the stabilization time is longer than 140 h.     

活性炭纤维负载Pr3+:Y2SiO5/TiO2复合材料的制备与性能

为了提高纳米TiO₂对太阳光的利用率和实现光催化剂的回收再利用,采用溶胶-凝胶法将上转换荧光材料与纳米TiO₂复合,通过负载于活性炭纤维（ACF）表面制备了Pr³⁺：Y₂SiO₅/TiO₂/ACF复合材料。运用XRD、FT-IR、SEM、FS、UV-vis DRS等对材料的结构及性能进行了综合表征,并以亚甲基蓝为模拟污染物评价复合材料的可见光催化活性,考察了材料制备过程中煅烧温度、负载次数等制备条件对复合材料可见光下催化性能的影响。结果表明,在浸渍2次、800℃煅烧的制备条件下,复合材料中TiO₂为锐钛矿相（占34.1%）与金红石相（占65.9%）的混合相,亚甲基蓝（15 mg·L^-1）12 h内去除率高达93.8%,反应符合拟一级动力学,反应速率常数为0.2471 h^-1,回收再生利用4次后去除率仍保持在75%以上。     

Origin of Microwave Dielectric Loss in ZnNb2O6-TiO2

(1− x )ZnNb₂O₆· x TiO₂ ceramics were prepared using both anatase and rutile forms of TiO₂. At a composition of x = 0.58, a mixture region of ixiolite (ZnTiNb₂O₈) and rutile was observed and the temperature coefficient of resonant frequency (τ_f) was ∼0 ppm/°C. We found that although ɛ_r and τ_f were comparable, the quality factor ( Q × f , Q ≈ 1/ tan δ, f = resonant frequency) of 0.42ZnNb₂O₆·0.58TiO₂ prepared from anatase and rutile was 6000 and 29 000, respectively. The origin of the difference in Q × f of both samples was investigated by measuring electrical conductivity and by analysis of the anatase–rutile phase transition. The anatase-derived sample had higher conductivity, which was related to the reduction of Ti⁴⁺. It is suggested that the increase of dielectric loss originates from an increase in Ti³⁺ and oxygen vacancies due to an anatase–rutile phase transition.     

Interfacial potassium induced enhanced Raman spectroscopy for single-crystal TiO2 nanowhisker

Structural control and element doping are two popular strategies to produce semiconductors with surface enhanced Raman spectroscopy(SERS) properties. For TiO_2 based SERS substrates, maintaining a good crystallinity is critical to achieve excellent Raman scattering. At elevated temperatures(N600 °C), the phase transition from anatase to rutile TiO_2 could result in a poor SERS performance. In this work, we report the successful synthesis of TiO_2 nanowhiskers with excellent SERS properties. The enhancement factor, an index of SERS performance, is 4.96 × 10~6 for methylene blue molecule detecting, with a detection sensitivity around 10~(-7) mol·L~(-1).Characterizations, such as XRD, Raman, TEM, UV–vis and Zeta potential measurement, have been performed to decrypt structural and chemical characteristics of the newly synthesized TiO_2 nanowhiskers. The photo absorption onset of MB adsorbed TiO_2 nanowhiskers was similar to that of bare TiO_2 nanowhiskers. In addition, no new band was observed from the UV–vis of MB modified TiO_2 nanowhiskers. Both results suggest that the high enhancement factor cannot be explained by the charge-transfer mechanism. With the support of ab initio density functional theory calculations, we reveal that interfacial potassium is critical to maintain thermal stability of the anatase phase up to 900 °C. In addition, the deposition of potassium results in a negatively charged TiO_2 nanowhisker surface, which favors specific adsorption of methylene blue molecules and significantly improves SERS performance via the electrostatic adsorption effect.