Composition, surface structure, and thermal behavior of ZrO2 + TiO2/Ti and ZrO2 + CeOx + TiO2 composites formed by plasma-electrolytic oxidation

Specific surface structures of ZrO₂ + TiO₂ (I) and ZrO₂ +CeO_x + TiO₂ (II) coatings on titanium before and after annealing at 850°C for 24 h in air are studied. Whiskers are found on the surface of type-I coatings before annealing, and perfectly edged crystals composed of TiO₂ and ZrO₂ oxides are found upon annealing. Pores in both coatings have a multilevel structure. In the case of type-I coatings, orifices of pores are covered with titanium. In type-II coatings, pore orifices contain titanium, zirconium, and oxygen. Oxygen deficiency implies that titanium and zirconium are present in pore orifices in metallic state. In type-II coatings, the surface distribution of cerium is heterogeneous. Mechanical treatment of the annealed coatings causes their exfoliation from the substrate metal. In the case of both coatings, the exfoliating surfaces are composed of TiO₂ blocks containing excess oxygen.     

Properties of TiO2 support and the performance of Au/TiO2 Catalyst for CO oxidation reaction

Gold catalysts were prepared on TiO₂ supports of different phase structures (i.e., anatase, rutile and biphasic), TiO₂ crystal size (i.e., 9–23 nm), surface and textural properties (i.e., hydration and surface area). The CO oxidation on the gold catalysts was carried out in an operando-DRIFTS set-up equipped with DRIFTS reactor cell connected on-line to CO gas analyser and gas chromatograph enabling real time monitoring of surface reaction and simultaneous reaction rate measurements. Gold catalysts supported on pure anatase TiO₂ were more resistant to sintering compared to catalysts supported on rutile and bi-phasic TiO₂. Besides catalyst sintering, deposition of surface carbonates is an important cause of catalyst deactivation. The best gold catalyst was prepared on 13 nm anatase TiO₂. It displays both increased activity and stability for CO oxidation reaction at room temperature. Surface and textural properties of TiO₂ also play a role on the performance of the Au/TiO₂ catalyst.     

Photocatalytic methanol reforming on Au/TiO2 for hydrogen production

Methanol can be reformed with water, at ambient temperature, using photocatalysis, and this reaction represents a possible low energy, more sustainable pathway to hydrogen production than (for instance) steam reforming. The requirements for the catalysts are rather strict since titania itself is almost inactive for anaerobic photocatalysis, whereas the addition of a very limited range of metals to the surface renders it active. Surprisingly, this includes gold, which shows one of the highest reactivities for hydrogen production. The mechanism is proposed to involve the methoxy and formate intermediates, the latter being implicated in the route to CO₂ and hydrogen production. One oxygen atom is supplied from the titania support, which is replaced in the catalytic cycle by oxygen from water. The threshold for the excitation is that for bandgap excitation into the titania conduction band, which stores the energy for reactivation, and this is mediated by electrophilic oxygen.     

CO oxidation: Deactivation of Au/TiO2 catalysts during storage

In a study of the phenomenon of catalyst deactivation during storage, Au/TiO₂ catalyst was stored under various conditions, viz. vacuum, nitrogen, air, refrigeration, dark, and light, and tested for CO oxidation activity at regular intervals. The data shows that the catalyst deactivates under all the storage conditions over 12 months and that storage in vacuum significantly enhances the rate and extent of deactivation. Storage in light accelerates the deactivation. The catalyst appears to deactivate through a combination of Au(III) reduction, Au nanoparticle agglomeration, loss of surface hydroxyl groups, loss of surface moisture, and accumulation of surface carbonates and formates. The rate and extent of catalyst deactivation can be limited by storing the catalyst in the dark at sub ambient temperature (refrigerator) and under inert atmosphere.     

Self-organized porous TiO2 and ZrO2 produced by anodization

The present work investigates the electrochemical formation of self-organized high aspect ratio TiO₂ and ZrO₂ nanotube layers. The formation and growth of a self-organized porous layer can be achieved directly by anodization without any templates in fluoride containing electrolytes. The morphology of the porous layers is affected by the electrochemical conditions such as the electrolyte composition, the pH and the exact polarization treatment (such as the potential sweep rate from the open-circuit potential to the anodizing potential). For Ti, nanotube layers are formed with diameters varying from approx. 20 nm to 100 nm and lengths from approx. 0.25 μm to 2.5 μm depending on the electrolytes and pH. On the other hand, for Zr, tubes of 50 nm in diameter and up to approx. 17 μm in length can be grown—a key parameter in this case is the potential sweep rate. The large difference between Ti and Zr in the achievable thickness of nanotube layers indicates a difference in the growth mechanism which may be based on the different chemical dissolution rates of electrochemically formed oxides.     

热喷涂法制备的La3+掺杂纳米TiO2粉末的表征

采用等离子热喷涂法以钛酸四丁酯为主要原料制备出稀土离子掺杂的纳米TiO2光催化剂.通过XRD,XPS,TEM,UV-Vis等检测手段对样品进行表征,同时检测了其光催化性能,并分析了掺杂对TiO2的影响机理.结果表明,所制备的La3 掺杂纳米TiO2是锐钛矿相和金红石相混晶结构,粒径分布在10～50nm之间;La3 掺杂能够促进锐钛矿向金红石的转变,同时抑制TiO2晶粒的长大;La3 掺杂使TiO2紫外-可见吸收光谱发生红移;适量La3 掺杂能显著提高TiO2的光催化活性,最佳掺杂浓度为0.5%(与Ti原子摩尔比),甲基橙降解率在90min内可达到82.4%.比纯TiO2高出13.2%.     

Structure differences between TiO2 and phosphorus implanted TiO2 films caused by thermal treatment

The titanium oxide film has been deposited on Si wafers (110) by unbalance reactive magnetron sputtering and modified by phosphorus ion implantation and succeeding vacuum annealing. The structural, states of surface chemistry and surface morphology of the films have been investigated by X-ray diffraction (XRD), X-ray photoelectric spectroscopy (XPS), atomic force microscope (AFM) and Scanning Electron Microscope (SEM), respectively. The results of XRD show rutile structure of as-deposited film, which is not changed by phosphorus implantation and vacuum annealing. However, a slightly shift of the peaks position to higher degree and the half width increases after ion implanted and vacuum annealing represent that the variety of the structure film caused by these treatments. The surface roughness is inclined to increase with the rising of annealing temperature for both undoped and P doped titanium oxide films. The surface chemistry presents significant difference between undoped and phosphorus doped films after a vacuum annealing, it may be attributed to the different evolvement of the surface defects existing in the film, which may be considered as an important influencing factor in the blood compatibility of the titanium oxide film.     

Preparation of a monolith-supported Au/TiO2 catalyst active for CO oxidation

The development of a method for making an adherent coating of Au/TiO₂ on a cordierite monolith is described. The optimum method entails first forming a wash-coat of TiO₂ by combining a colloidal dispersion of TiO₂ with Degussa P-25 TiO₂ that has been washed, dried and crushed. Subsequent deposition of gold from HAuCl₄ solution at pH 9 resulted in a catalyst that was less active for the oxidation of carbon monoxide than a similar preparation using only P-25, but reproducible values of T₅₀ of about 250 K were obtained.     

保护渣对铝钛系夹杂物溶解的吸收规律

以CaO-SiO₂-Al₂O₃-Na₂O-CaF₂-MgO为基础渣系,采用旋转动力学方法研究了不同碱度、BaO质量分数(0~15%)、B₂O₃质量分数(0~15%)对连铸保护渣吸收Al₂O₃或TiO₂速率的影响以及吸收前后矿相变化。结果表明,保护渣吸收TiO₂的速率要远大于吸收Al₂O₃的速率;添加BaO或B₂O₃后均能提高保护渣吸收Al₂O₃和TiO₂的能力;保护渣主要物相为钙镁黄长石(2CaO·MgO·2SiO₂)、钙铝黄长石(2CaO·Al₂O₃·2SiO₂)、枪晶石(3CaO·2SiO₂·CaF₂)及玻璃相(Na₂O·Al₂O₃·SiO₂);添加BaO后,钙镁黄长石转变为重硅酸钡钙镁(2CaO·MgO·2SiO₂·BaO),并抑制黄长石和枪晶石晶体长大;当添加B₂O₃的质量分数不低于10%,保护渣形成的物相为玻璃相。试验条件下,不同碱度的保护渣和添加B₂O₃的保护渣中TiO₂仍以TiO₂形式存在,而在添加BaO的保护渣中,TiO₂形成钙钛矿。     

液料等离子热喷法制备Fe3+/TiO2纳米粉末

通过对液料等离子热喷前驱物添加掺杂成分实现了液料等离子热喷TiO2纳米粉末的掺杂改性,并利用TEM,XRD及XPS对其进行表征.结果表明,采用液料等离子热喷法可以制备Fe3 掺杂TiO2纳米粉末,所制备粉末形貌基本呈球形或近球形,粒径分布为10～35 nm,掺杂量小于2.0%时粉末为锐钛矿及金红石相混晶,Fd3 掺杂促进锐钛矿向金红石相的转变,掺杂量为10.0%时析出了Fe2Ti3O9相.Fe3 掺杂不会引起TiO2粒径的大范围波动.粉末中含有O,Ti,Fe和C等元素,Fe元素在TiO2中仍为 3价.     

Effect of Nd2O3 addition on the surface phase of TiO2 and photocatalytic activity studied by UV Raman spectroscopy

TiO₂ modified with Nd₂O₃ (Nd-TiO₂) nanoparticles were prepared by a co-precipitation method and utilized as the photocatalysts for the degradation of Rhodamine B (RhB). The influence of Nd₂O₃ on the bulk and surface phase, surface area, particle size, and optical response of TiO₂ was investigated by X-ray diffraction (XRD), UV Raman spectroscopy, transmission electron microscopy (TEM), BET, and UV-visible diffuse reflectance spectra. It is found that the crystalline phase and phase composition in the bulk and surface region of Nd-TiO₂ calcined at high temperatures can be tuned by changing the amount of Nd₂O₃. Based on the results from XPS, EDX, XRD, and UV Raman spectra, it is assumed that Nd³⁺ ions do not enter the TiO₂ lattice, but highly disperse onto the Nd-TiO₂ particle surface in the form of Nd₂O₃ crystallites. These crystallites inhibit the agglomeration, growth in crystal size, and anatase-to-rutile phase transformation of TiO₂. In the photocatalytic degradation of RhB reaction, Nd-TiO₂ nanoparticles with higher surface area and wider optical response are more reactive in case of the same surface anatase phase. When the mixed phases of anatase and rutile exist in the surface region of Nd-TiO₂, the synergetic effect over surface area and optical response is the important parameter which determines optimal photocatalytic activity.     

等离子弧熔覆添加Al2O3+TiO2铁基合金涂层组织和耐磨性

在Q235钢表面用等离子弧熔覆Ni-Cr-B-Si-Fe铁基合金涂层及添加不同含量Al2O3 TiO2铁基合金复合涂层,比较研究了这两种涂层的组织、显微硬度和磨损性能。结果表明,添加Al2O3 TiO2后的铁基复合涂层界面的生长形态发生变化,由初生的细长柱状树枝晶转变为小的枝晶,并且提供了形核的核心,细化了晶粒;其组织主要由晶粒细小的γ-Fe为基,以Cr23C6,Fe3C,Al2O3 TiO2为增强相的复合涂层;熔覆层的显微硬度可达600～655HV0.2。     

TiO2/ SiO2一维光子晶体的制备及其光子带隙特性

以普通载玻片为基体,采用溶胶-凝胶法制备了TiO2/SiO2一维光子晶体,对该结构的截面形貌、各层厚度及结晶形态、反射谱特性进行了分析。结果表明:TiO2和SiO2膜的平均厚度分别为69 nm和83 nm,结晶形态分别为锐钛矿和无定形态;该结构在波长544 nm处的反射率达到了94%,且其FWHM=194 nm(486~680 nm)。运用传输矩阵法对该结构进行仿真计算,得到的计算结果与测试结果趋于一致。最后讨论了入射角对一维光子晶体反射谱的影响。     

Photocatalytic performance of nano-photocatalyst from TiO2 and Fe2O3 by mechanochemical synthesis

Nano-particles of homogeneous solid solution between TiO₂ and Fe₂O₃ (up to 10 mol%) have been prepared by mechanochemical milling of TiO₂ and yellow Fe₂O₃/red Fe₂O₃/precipitated Fe (OH)₃ using a planetary ball mill. Such novel solid solution cannot be prepared by conventional co-precipitation technique. A preliminary investigation of photocatalytic activity of mixed oxide (TiO₂/Fe₂O₃) on photo-oxidation of different organic dyes like Rhodamine B (RB), Methyl orange (MO), Thymol blue (TB) and Bromocresol green (BG) under visible light (300-W Xe lamp; λ > 420 nm) showed that TiO₂ having 5 mol% of Fe₂O₃ (YFT1) is 3-5 times higher photoactive than that of P25 TiO₂. The XRD result did not show the peaks assigned to the Fe components (for example Fe₂O₃, Fe₃O₄, FeO₃, and Fe metal) on the external surface of the anatase structure in the Fe₂O₃/TiO₂ attained through mechanochemical treatment. This meant that Fe components were well incorporated into the TiO₂ anatase structure. The average crystallite size and particle size of YFT1 were found to be 12 nm and 30 ± 5 nm respectively measured from XRD and TEM conforming to nanodimensions. Together with the Fe component, they absorbed wavelength of above 387 nm. The band slightly shifted to the right without tail broadness, which was the UV absorption of Fe oxide in the Fe₂O₃/TiO₂ particle attained through mechanochemical method. This meant that Fe components were well inserted into the framework of the TiO₂ anatase structure. EPR and magnetic susceptibility show that Fe³⁺ is in low spin state corresponding to μ_B = 1.8 BM. The temperature variation of μ_B shows that Fe³⁺ is well separated from each other and does not have any antiferromagnetic or ferromagnetic interaction. The evidence of Fe³⁺ in TiO₂/Fe₂O₃ alloy is also proved by a new method that is redox titration which is again support by the XPS spectrum.     

Fe掺杂TiO2纳米材料的合成及光催化性能

以钛酸丁酯为钛源,Fe(NO3)3·9H2O为铁源,采用溶胶-凝胶法制备Fe/TiO2纳米粉体,利用溶胶结合静电纺丝技术制备Fe/TiO2纳米纤维,从材料改性及形貌改善两个角度共同提高TiO2纳米材料的光催化活性及实用性。借助XRD、SEM、TEM等分析技术,探究了Fe/TiO2纳米材料在可见光区的光催化活性,分析了煅烧温度及掺铁量对Fe/TiO2纳米材料光催化性能的影响。结果显示,铁的掺入及形貌的改善有助于提高TiO2的光催化性能。     

Photocatalytic degradation of MO by complex nanometer particles WO3/TiO2

Complex nanometer particles WO3/TiO2 were prepared using a sol-gel process and characterized using XRD spectra. The photocatalytic activity of TiO2 can be increased by doping W^6＋ with TiO2 because the doped W^6＋ that entered into the crystal lattices of TiO2 led to the formation of defects in the crystal lattices of TiO2 and thereby improved the photocatalytic activity of TiO2.When WO3 doped in TiO2 exceeded 3%, the excess W^6＋ did not enter into the crystal lattices of TiO2 but were uniformly dispersed in TiO2 or they covered the surface of TiO2, which reduced the effective illumination area of TiO2 and thereby lowered the photocatalytic activity of TiOE.The relationship among the composition of the catalyst, the amount of photocatalyst, the illumination time, and the decolorizing rate of methyl orange （MO） were discussed. The results show that the decolorizing rate of MO can reach 82.3% using WO3/TiO2 as the photocatalyst, with the composition of WO3/TiO2 -3：97, the mass of catalyst = 0.400 g, the initial concentration of MO = 20 mg/L, pH = 6.5, and the illumina- tion time = 7 h.     

等离子喷涂Al2O3/TiO2复合粉末的Sol-Gel法制备

传统热喷涂粉末由小颗粒粉体混合团聚制得,流动性差、致密度低,制得的涂层均匀性差、性能不稳定。以有机金属盐为原料,采用溶胶-凝胶法及喷雾干燥法制备出氧化钛质量分数为13%的氧化铝-氧化钛(AT-13)复合前驱体粉末。采用TG-DSC、XRD、FESEM、霍尔流量计研究了粉体反应机理、物相组成、微观结构及流动性能,同时利用维氏硬度计、FESEM-EDS对制得的涂层性能进行了分析比较。结果表明,凝胶经喷雾干燥工艺后可获得球形Ti(OH)4/Al OOH复合粉体,直径约为40μm;与传统团聚粉体相比,前驱体粉末流动性更为优异,为43 s/50 g;由该粉末制得的涂层表面光滑、元素分布均匀、力学性能稳定、耐磨损性能优良,平均显微硬度达873.8 HV0.3,磨损量较团聚粉末涂层减少三分之一。     

Fe3+掺杂TiO2薄膜的制备与表征

利用射频磁控溅射技术在载玻片衬底上沉积了TiO2及Fe3+掺杂的TiO2薄膜,并利用X射线衍射、拉曼光谱和紫外-分光光度计对所制备的薄膜进行了结构与性能表征。结果表明,所制备的TiO2薄膜为锐钛矿相结构,Fe3+掺杂后TiO2薄膜的晶化程度降低,光催化活性减弱。     

Glass fibers templated preparation of TiO2 microtubes assembled from nano/micro hierarchical TiO2 crystals

The unique rutile TiO₂ microtubes with the larger specific surface area and the distinct external/internal surface morphology have been fabricated in large-scale by a sol-gel-hydrothermal method via the readily available glass fibers as templates. The crystal phase, morphology and surface area of as-obtained samples were measured by XRD, SEM, TEM and BET. The results indicate that these microtubes with the inner diameter of ca. 8 μm and the wall thickness of 2-3 μm have a novel double-layer structure, which is built from closely associated TiO₂ rod arrays and TiO₂ gel film. Detailed electric microscopy investigations on such TiO₂ rod arrays exhibit that they are mainly constructed by flower-like rod clusters, and each TiO₂ rod derives from the assembly of the parallel-growth TiO₂ nanowires with the diameter of ca. 10 nm. Such unique hierarchical nano/micro TiO₂ structure enhances the specific surface area of these microtubes effectively, which makes them have more potential applications in the fields of catalysis, sensors, and drug delivery.     

Characterization of mechanical properties of suspension plasma sprayed TiO2 coatings using scratch test

The study aimed at characterizing mechanical properties of TiO₂ coatings obtained by the use of aqueous suspensions of fine rutile and anatase particles onto metal substrates. Thickness of the coatings was found with the use of optical microscope observations of metallographical cross-sections. The coatings morphology was found with scanning electron microscope (SEM) and their phase composition was determined by X-ray diffraction method. The mechanical properties were characterized using scratch test. The test enabled to characterize the adhesion of coatings by determination of critical force necessary to peel off the coatings from the substrate and, on the other hand, to estimate their cohesion by the measurement of the scratch hardness. The hardness was calculated using the width of the scratch and the value of force applied. The design of experiments (DOE) of spraying with the use of a 2³ full factorial plan was applied to rutile powder. The coatings were sprayed onto aluminium substrate. The DOE enabled to find the effects of three principal parameters, i.e. electric power input to plasma, spray distance and suspension feed rate onto coating adhesion expressed by critical force. A preliminary data for anatase powder sprayed with one set of operational parameters onto stainless steel substrate are also shown.