Self-cleaning glass coated with Fe^3＋ -TiO2 thin film

The self-cleaning glass coated with Fe^3 -TiO2 photocatalytic thin film was prepared by sol-gel process from the system Ti(OC4H9),-NH(C2H4OH)2-C2H5OH-H2O containing FeCl3. The microstructure and properties of the film were studied using differential thermal analysis-thermogravimetry(DTA-TG), X-ray diffration (XRD) and scanning electron microscope(SEM). The transmittance of the self-cleaning glass was measured by using UV-Vis spectrometer. The effects of content of Fe^3 and the thickness of Fe^3 -TiO2 thin film on the photocatalytic ac-tivity were examined. The results show that the photocatalytic thin films are mainly composed of Fe3O4 and TiO2 particles within 10-100 nm. The appropriate amount of Fe^3 is effective for improving the photocatalytic activities of TiO2. The best photocatalytic activity is obtained when the molar ratio of Fe^3 to TiO2 is 0. 005 and the glass is coated with 9 layers.     

Mechanism and behaviors of Cr3+-doped TiO2

TiO2 powder and TiO2 thin film on the surface of glazed ceramic tile were prepared by sol-gel method.The influences of different doping Cr3 concentration on the photocatalytic activity of TiO2 were discussed, UV-visible and X-ray diffraction analysis were used to test the performance of TiO2 powder and film. The results indicate that photocatalytic activity of doping Cr3 -TiO2 thin film is higher than that of powder, and the interaction between Cr3 -doped and substrate can greatly enhance the photocatalytic activity. The results of X-ray diffraction and photoabsorption show that the Cr3 -doped energy level in TiO2 is 0. 62 eV high from the top of valence band, which belongs to the type of deep energy level doping. On the basis of the semiconductor energy level theory and Cr3 dopant energy level, the semiconductor energy level model of Cr3 in TiO2 powder and thin film were established, and the doping mechanisms of Cr3 -doped in TiO2 powder and thin film were analyzed.     

Cu~(2+)/Ce~(4+)-TiO_2可见光催化降解活性艳红X-3B

采用溶胶凝胶法合成了掺杂Cu~(2+)和Ce~(4+)的Ti O2可见光催化剂,用活性艳红X-3B降解脱色为模型反应,结合紫外-可见光谱法、XRD和SEM等表征手段,考察了制备条件与光催化活性的关系.实验结果表明:适量掺杂稀土元素Ce~(4+)较单独掺杂Cu~(2+)能更加有效地提高催化剂在可见光下的催化活性,掺杂后使催化剂的吸收带边位置发生红移,晶型结构为锐钛矿和金红石的混合晶型.掺杂Ce~(4+)量为1.5%时,0.4 g催化剂对30 m L浓度为5 mg/L的活性艳红X-3B模拟印染废水降解率达到61.1%.     

Preparation and Properties of Ag—TiO2 Thin Films on Glass SUbstrates

Ag-TiO2 thin films were prepared on glasses.The morphology and structure of Ag-TiO2 films were investigated by XRD.SEM and FT-IR.The photocatalytic and hydrophilic properties of Ag-TiO2 thin films were also evaluated by examining photocatalytic degradation dichlorophos under sunlight illumination and the change of contact angle respectively.The research results show that the Ag-TiO2 thin film is mainly composed of 20-100nm Ag and TiO2 particles,The Ag-TiO2 thin films possess a super-hydrophilic ability and higher photocatalytic activity than that of pure TiO2 thin film.     

沸石负载Mn,N共掺杂TiO2及光催化性能

为提高传统TiO₂光催化剂的可见光催化活性,本文采用溶胶-凝胶法合成了Mn,N共掺杂TiO₂光催化剂,改善了传统TiO₂光生载流子易复合的问题;进一步采用沸石作为载体对改性后的TiO₂样品进行负载,解决了传统光催化剂存在的难分离回收问题,以达到光催化剂可重复使用的目的.借助X-射线衍射仪、扫描电子显微镜、紫外分光光度计、傅立叶变换红外光谱仪等测试手段对Mn,N共掺杂TiO₂光催化剂的结构、元素组成、微观形貌和光催化降解性能进行系统分析与研究.研究结果表明,沸石负载Mn,N共掺杂TiO₂的样品较未改性的TiO₂样品具有更高的光催化降解活性,在可见光照射下,在最优掺杂条件下获得的TiO₂光催化剂在60 min内对孔雀石绿的降解率可达到97%,这主要归因于锰离子掺杂能够对TiO₂光生载流子的复合产生抑制作用,促进光生电荷分离,与此同时氮元素掺杂可有效拓宽TiO₂半导体光催化剂光响应范围.此外,经过5次循环使用后,对孔雀石绿的降解率没有较大程度的减弱,依然能够维持在88%以上,表明沸石负载Mn,N共掺杂TiO₂的样品具有较好的光催化循环稳定性.     

TiO2/ML-Ti3C2复合纳米材料的制备及其光催化性能

通过水热技术在二维(2D)多层材料Ti_3C_2 (multi-layer Ti_3C_2, ML-Ti_3C_2)的表面及层间原位晶化和生长锐钛矿相TiO_2纳米球,制备出TiO_2/ML-Ti_3C_2复合纳米材料。采用XRD、SEM、氮吸附等表征技术对TiO_2/ML-Ti_3C_2纳米复合材料进行分析表征,并以亚甲基蓝(MB)为模拟污染物,对纯TiO_2和TiO_2/ML-Ti_3C_2复合纳米材料的光催化性能进行了评价。实验结果表明,两种材料的耦合抑制了Ti O_2中光生电子-空穴对的湮灭,延长了复合光催化剂中载流子寿命,拓宽了复合材料的光谱响应范围。在紫外光照射下,以TiO_2/ML-Ti_3C_2复合纳米材料为光催化剂,200 mg/L的MB溶液在20 min内几乎完全脱色,降解率为98.98%。TiO_2/ML-Ti_3C_2纳米复合材料的光催化性能优于纯TiO_2和Ti_3C_2, Ti_3C_2优异的电子传输能力和超强的吸附性能优化了TiO_2的光催化性能。本研究为使用光催化技术处理废水提供了一种新的思路,具有一定的实际应用前景。     

Ferroelectric properties of Bi3.4Ho0.6Ti3O12 thin films prepared by sol-gel method

We have prepared the Ho-substituted bismuth titanate (Bi_3.4Ho_0.6Ti₃O₁₂, BHT) thin films on Pt/Ti/SiO₂/Si substrates using sol-gel method. The crystal structure and morphology of the films were characterized using X-ray diffraction and atomic force microscopy. The BHT film shows a single phase of Bi-layered Aurivillius structure and dense microstructure. The 2Pr and 2Ec of the 600-nm-thick BHT film were 38.4 μC/cm² and 376.1 kV/cm, respectively at applied electric field 500 kV/cm. The dielectric constant and dielectric loss are about 310 and 0.015 at a frequency of 1 MHz, respectively. The Pr value decreased to 93% of its pre-fatigue values after 4.46×10⁹ switching cycles at 1 MHz frenquency, and the BHT film shows good insulating behavior according to the test of leakage current. Supported by the Hubei Province Natural Science Foundation (Grant No. 2007ABA309)     

Luminescent properties of BaO-La2O3-B2O3 glasses with dopant

The luminescent properties of glasses synthesized in air atmosphere by conventional high temperature process were stud{ed. The emissions spectra of Eu^2 and Eu^3 were observed in BaO-La2O3-B2O3-Eu2O3 glasses.The results show that the broad emission peaks at 430 nm correspond to 5d→4f emission transition of Eu^2 , the sharp emission peaks at 592, 616, 650 and 250 nm correspond to 5^D0→1Fj(j=1--4) emission transition of Eu^3 ,respectively, which indicates that the BaO-La2O3a-B2O3-Eu2O3 glass can convert ultraviolet and green omponents of sunlight into blue and red light so as to increase the intensity of blue and red light, respectively. The luminescent in--tensity of Eu^2 increases with increasing the molar ratio of Tb^3 in BaO-La2O3-B2O3-Eu2O3a-Tb4O3 glasses, whereas the luminescent intensity of Eua^3 decreases. So the luminescent intensity of Eu(Ⅲ,Ⅱ) is influenced by Tb^3 .These phenomena can be explained by electron transfer mechanism; Eu^3 (4f6) Tb^3 (4f^8)→Eu^2 (4f′) Tb^4 (4f′). Taking advantage of the luminescent properties of BaO-La2O3-B2O3-Eu2O3 glasses, light-conversion glass for agriculture can be produced.     

Preparation and Characterization of Fe^3＋ -doped Nanometer TiO2 Photocatalysts

Fe^3＋ -doped nanometer TiO2 photocatalysts were prepared by sol-gel technique. TiO2 powders with different Fe^3＋ / Ti^4 ＋ molar ratios ranging from 0. 05% to 25% were synthesized by calcinating the gels in the temperature range of 200-600 ℃ . The effects of the content of iron ions and calcination temperature on the physical properties of the powders and their photocatalytic activities were examined by the photodecorapositon of methyl orange in sunlight. The results show that Fe dopant can decrease the temperature of nanatase-ratile transformation. The ideal photocatalytic property was achieved when the sample with an Fe^3＋ / Ti^4＋ ratio of 20 at% was calcined at about 300 ℃ for an hour, which is superior to that of commercial Degussa P-25. The optimum microstructure of the Fe-doped TiO2 for a high photocatalytic activity in sunlight is consisted of nanatase and ratile.     

Light energy conversion device for photocatalyst 2.0%WO3-TiO2 with oxygen vacancies for water splitting

Using carbon felt, polytetrafluoroethylene latex and powder catalyst to assembly a light energy conversion device, the photocatalytic activity of catalyst 2.0%WO₃-TiO₂ (2%WO₃ compounding TiO₂) with oxygen vacancies was studied through the water splitting for O₂ evolution, using a high pressure mercury lamp as the light source and Fe³⁺ as the electron acceptor in two different devices: an ordinary photolysis device with catalyst powder suspending through a magnetic stirrer and a self-assembly light energy conversion device. The results show that after 12 h irradiation, the photocatalytic activity of 2.0%WO₃-TiO₂ with oxygen vacancies in the self-assembly light energy conversion device is higher than that of the ordinary photolysis device, and the amount of oxygen evolution is about 12 and 9 mmol/L respectively in these two devices. After 12 h, the rates of O₂ evolution are slow in each device and the photocatalyst almost loses the photoactivity in the ordinary photolysis device. So, compared with the ordinary photocatalytic device, the rate of oxygen evolution and the life time of the catalyst are improved in the self-assembly light energy conversion device.     

Photocatalytic performance of TiO<Subscript>2</Subscript> thin films connected with Cu micro-grid

Aiming at reducing the recombination of photo-induced carriers in semiconductor photocatalytic process, we prepared TiO₂ thin film with its surface modified by a connected Cu micro-grid via a microsphere lithography strategy, which showed higher photocatalytic activity than the pure TiO₂ film. The improvement of photocatalytic activity of Cu micro-grid to the TiO₂ film is due to the charge carrier separation and electron transfer by the conducting metal grid. The photocatalytic activity was improved as metal loading increased, which obtained the best performance at a certain loading amount, and then decreased at higher loading amount. This phenomenon was attributed to the metal’s bulk effect which could be explained by the relationship between the energetic positions and the metal cluster size. Supported by the National Natural Science Foundation of China (Grant Nos. 50672003, 50872005) and the National Basic Research Program of China (“973” Project) (Grant No. 2007CB613302) and the Fok Ying Tong Education Foundation (Grant No. 111050)     

Influence of oxides on high velocity arc sprayed Fe-Al／Cr3C2 composite coatings

Fe-Al/Cr3C2 coatings were sprayed on low steel by high velocity arc spraying(HVAS) technology. The influences of oxides on erosion, corrosion and wear behavior for high velocity arc sprayed Fe-Al/Cr3C2 coatings were studied. The results show that HVAS-sprayed Fe-Al/Cr3C2 coatings have good erosion, heat corrosion and wear resistance. The erosion resistance improves with the increase of the temperature. On one hand, the ferrous oxides are incompact, so they peel off the surface of the coatings easily during the high temperature erosion. On the other hand, compact Al2O3 films on the surface can protect the coatings.     

Study on the isothermal oxidation behavior in air of Ti3AlC2 sintered by hot pressing

The isothermal oxidation behavior at 900–1300°C for 20 h in air of bulk Ti₃AlC₂ with 2.8 wt% TiC sintered by means of hot pressing was investigated in the work. The isothermal oxidation behavior generally followed a parabolic rate law. The parabolic rate constants increased from 1.39×10⁻¹⁰ kg²·m⁻⁴·s⁻¹ at 900°C to 5.56×10⁻⁹ kg²·m⁻⁴·s⁻¹ at 1300°C. The calculated activation energy was 136.45 kJ/mol. It was demonstrated that Ti₃AlC₂ had excellent oxidation resistance due to the continuous, dense and adhesive protect scales consisted of a mass of α-Al₂O₃ and a little of TiO₂ and/or Al₂TiO₅. In principle, the oxide scale was grown by the inward diffusion of O²⁻ and the outward diffusion of Ti⁴⁺ and Al³⁺. The rapid outward diffusion of cations usually resulted in the formation of cracks, gaps, and holes.     

Local segregation in Cu-In precursors and its effects on microstructures of selenized CuInSe2 thin films

Local segregation in Cu-In precursors and its effects on the element distribution and microstructures of selenized CuInSe₂ thin films were investigated. Cu-In precursors with an ideal total mole ratio of Cu to In of 0.92 were prepared by middle frequency alternating current magnetron sputtering with Cu-In alloy target, then CuInSe₂ absorbers for solar cells were formed by selenization process in selenium atmosphere. Scanning electron microscope and energy dispersive X-ray spectroscope were used respectively to observe the surface morphologies and determine the compositions of both Cu-In precursors and CuInSe₂ thin films. Their microstructures were characterized by X-ray diffractometry and Raman spectroscope. The results show that Cu-In precursors are mainly composed of Cu₁₁In₉ phase with In-rich solid solution. Stoichiometric CuInSe₂ thin films with a homogeneous element distribution and single chalcopyrite phase can be synthesized from a segregated Cu-In precursor film with an ideal total mole ratio of Cu to In of 0.92. CuInSe₂ thin film shows P-type conductivity and its resistivity reaches 1.2×10³ Θ·cm. Foundation item: Project(2004AA513023) supported by the National High Technology Research and Development Program of China     

Preparation, characterization and photocatalytic behavior of WO3-TiO2/Nb2O5 catalysts

TiO2/Nb2O5 photocatalyst loaded with WO3 (WO3-TiO2/Nb2O5) was prepared by a modified hydrolysis process, and characterized by X-ray diffractometry, transmission electron microscopy, Raman spectra and UV-Vis diffuse refraction spectroscopy. The photocatalytic activity of WO3-TiO2/Nb2O5 was investigated by employing splitting of water for O2 evolution. The results indicate that WO3 loading can pronouncedly improve the photocatalytic activity of TiO2/Nb2O5 by using Fe3 as an electron acceptor under UV irradiation. The optimum molar fraction of the loaded WO3 is 2%, and the largest speed of O2 evolution for 2% WO3-TiO2/Nb2O5 catalyst is 151.8 μmol/(L·h).     

Preparation and sintering of nano Fe coated Si3N4 composite powders

Fe/Si₃N₄ composite powder was synthesized by the heterogeneous precipitation-thermal reduction process, and then pressed into flakes under a pressure of 10 MPa. Flakes were sintered by pressureless and hot-pressing at 1 600 °C under 0.1 MPa N₂. The chemical composition, phases and microstructure of composite powder and sintered flakes were investigated by energy dispersive spectroscopy (EDS), X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results show that the structure of composite powders is Si₃N₄ coated by nano Fe. The crystal phases of sintered flakes by pressureless are Fe(Si) compound, SiC and Si₃N₄. The crystal phases of the sintered samples by hot-pressing are Fe, Fe(Si) compound and Si₃N₄. It is found that crystal phases flakes obtained by pressureless and hot-pressing are very different. Foundation item: Project(50804016) supported by the National Natural Science Foundation of China     

氧空穴对二氧化钛/磷酸银光催化活性的影响机制

采用磷酸银与具有可见光吸收能力的TiO_2基光催化剂相复合的方法,对带有氧空穴的二氧化钛(TiO_2-OV)的复合磷酸银光催化材料的性能进行了研究.采用光处理法成功制备出了具有可见光吸收能力的氧空穴二氧化钛材料,利用化学吸附法成功制备出了磷酸银/氧空穴二氧化钛复合光催化剂.透射电镜结果显示,磷酸银纳米颗粒均匀分散于氧空穴二氧化钛表面,形成结构完美的复合光催化剂;光催化降解罗丹明B实验结果表明,所制备的磷酸银/氧空穴二氧化钛复合光催化剂的光催化活性明显优于磷酸银光催化材料.     

Review:Nanostructured TiO2 for Enhanced Photocatalytic Property by Glancing Angle Deposition Method

物理气相沉积GLAD法在二氧化钛光催化剂的应用

双爽¹,谢拯^1,2,张政军³

（1.清华大学 新型陶瓷与精细工艺国家重点实验室（材料科学与工程学院）,北京 100084;2. 西安高新技术研究所, 西安 710025;3. 清华大学 先进材料教育部重点实验室（材料科学与工程学院）,北京 100084）

创新点说明：

1）通过气相沉积的物理方法,制备垂直或倾斜生长的纳米阵列作为光催化剂,提高催化剂回收效率,减少二次污染;

2）运用掺杂、修饰以及复合其他材料的方法,拓展二氧化钛在可见光范围的利用;

3）通过表征手段分析,分析内在光催化效率提高机理。

研究目的：

通过多种方法,提高气相沉积GLAD法制备的二氧化钛在可见光范围的利用率,分析催化反应提高机理。

研究方法：

磁控溅射、电子束蒸镀、原子层沉积

结果：

1）通过气相物理沉积GLAD方法,制备了垂直或倾斜生长的纳米阵列作为光催化剂,提高回收效率,减少二次污染;

2）利用掺杂、修饰以及复合其他材料的方法,提高二氧化钛在可见光范围的利用率;

3）通过表征手段分析,分析内在光催化效率提高机理。

结论：

1）实现了在特定基底生长纳米阵列光催化剂的制备,提高回收效率减少二次污染;

2）使用化学方法复合窄带隙硫氧化物、贵金属及石墨烯提高催化剂在可见光范围的利用率,并分析其内在增强机理。

关键词：二氧化钛纳米阵列,倾斜生长阴影效应,带隙匹配

     

Energy transfer mechanism of GdPO4: RE3+ (RE = Tb, Tm) under VUV-UV excitation

Polycrystal of GdPO₄:RE³⁺ (RE=Tb, Tm) phosphors were prepared by solid-state method. Vacuum ultraviolet excitation and emission spectrum and the energy transfer mechanism between the host and dopants of Tb³⁺ and Tm³⁺ were investigated respectively. The emission of Gd³⁺ at 313 nm was enhanced by the strong absorption of CTS of Tm³⁺ at 180 nm in GdPO₄: Tm. It has also been concluded that the excitation of Gd³⁺ is transferred to Tb³⁺ and then emission peaks of ⁵D_J→⁷F_J of Tb³⁺ were observed.     

二氧化钛光催化剂掺杂改性的研究进展

半导体材料TiO2作为光催化剂得到了广泛的研究和应用.介绍了TiO2光催化反应机理以及光催化剂掺杂改性的研究进展,包括金属离子、非金属以及金属/非金属共掺杂,并且指出了TiO2光催化剂改性的研究热点和研究方向.