Preparation and antibacterial behavior of Fe-doped nanostructured TiO2 thin films

Fe³⁺-doped nanostructured TiO₂ thin films with antibacterial activity were prepared on soda–lime–silica glass slides by using sol–gel technology. Water containing Escherichia coli K-12 with TiO₂ thin films in was exposed to low intensity fluorescent light and antibacterial efficiency was evaluated with spread plate techniques. The films are porous and have anatase phase. Iron ions increased luminous energy utilization as the absorption edge of the Fe³⁺-doped film has a red shift compared to that of the pure TiO₂ film in the UV–VIS absorption spectrum. The bacterial removal efficiency reached 95% at the optimum concentration of iron ion (about 0.5% (mol)) after 120 min irradiation. The antibacterial behavior of the doped TiO₂ films was explicitly observed using scanning electron microscopy and cell wall damage was found.     

Microstructural, photocatalysis and electrochemical investigations on CeTi2O6 thin films

The properties of sol–gel derived CeTi₂O₆ thin films deposited using a solution of cerium chloride heptahydrate and titanium propoxide in ethanol are discussed. The effect of annealing temperature on structural, optical, photoluminescence, photocatalysis and electrochemical characteristics has been examined. Lowest annealing temperature for the formation of crystalline CeTi₂O₆ phase in these samples is identified as 580 °C. The optical transmittance of the films is observed to be independent of the annealing temperature. The optical energy bandgap of the 600 °C annealed film for indirect transition is influenced by the presence of anatase phase of TiO₂ in its structure. Fourier transform infrared spectroscopy investigations have evidenced increased bond strength of the Ti–O–Ti network in the films as a function of annealing temperature. The photoluminescence intensity of the films has shown dependence on the annealing temperature with the films fired at 450 °C exhibiting the maximum photoluminescence activity. The decomposition of methyl orange and eosin (yellow) under UV–visible light irradiation in the presence of crystalline CeTi₂O₆ films shows the presence of photoactivity in these films. The photocatalytic response of CeTi₂O₆ films is found to be superior to the TiO₂ films. In comparison to crystalline films, the amorphous films have shown superior electrochemical characteristics. The 500 °C annealed amorphous films have exhibited the most appropriate properties for incorporation in electrochromic devices comprising tungsten oxide as the primary electrochromic electrode.     

Preparation and activity evaluation of p-n junction photocatalyst NiO/TiO2

p–n Junction photocatalyst NiO/TiO₂ was prepared by sol–gel method using Ni(NO₃)₂·6H₂O and tetrabutyl titanate [Ti(OC₄H₉)₄] as the raw materials. The p–n junction photocatalyst NiO/TiO₂ was characterized by UV–vis diffuse reflection spectrum, X-ray powder diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The photocatalytic activity of the photocatalyst was evaluated by photocatalytic reduction of Cr₂O₇²⁻ and photocatalytic oxidation of rhodamine B. The results show that, for photocatalytic reduction of Cr₂O₇²⁻, the optimum percentage of doped-NiO is 0.5% (mole ratio of Ni/Ti). The photocatalytic activity of the p–n junction NiO/TiO₂ is much higher than that of TiO₂ on the photocatalytic reduction of Cr₂O₇²⁻. However, the photocatalytic activity of the p–n junction photocatalyst NiO/TiO₂ is much lower than that of TiO₂ on the photocatalytic oxidation of rhodamine B. Namely, the p–n junction photocatalyst NiO/TiO₂ has higher photocatalytic reduction activity, but lower photocatalytic oxidation activity. Effects of heat treatment on the photocatalytic activity of p–n junction photocatalyst NiO/TiO₂ were investigated. The mechanisms of influence on the photocatalytic activity were also discussed by the p–n junction principle.     

Photocatalyzed degradation of flumequine by doped TiO2 and simulated solar light

Titanium dioxide was obtained in its pure form (TiO₂) and in the presence of urea (u-TiO₂) and thiourea (t-TiO₂) using the sol–gel technique. The obtained powders were characterized by BET surface area analysis, Infrared Spectroscopy, Diffuse Reflectance Spectroscopy and the Rietveld refinement of XRD measurements. All the prepared catalysts show high anatase content (>99%). The a and b-cell parameters of anatase increase in the order TiO₂ < u-TiO₂ < t-TiO₂, while the c-parameter presents the opposite trend. Because of the interplay in cell dimensions, the cell grows thicker and shorter when prepared in the presence of urea and thiourea, respectively. The cell volume decreases in the order t-TiO₂ > u-TiO₂ > TiO₂. The photocatalytic activities of the samples were determined on flumequine under solar-simulated irradiation. The most active catalysts were u-TiO₂ and t-TiO₂, reaching values over 90% of flumequine degradation after 15 min irradiation, compared with values of 55% for the pure TiO₂ catalyst. Changing simultaneously the catalyst amount (t-TiO₂) and pH, multivariate analysis using the response surface methodology was used to determine the roughly optimal conditions for flumequine degradation. The optimized conditions found were pH below 7 and a catalyst amount of 1.6 g L⁻¹.     

Preparation and visible photocatalytic dye degradation of Mn-TiO2/sepiolite photocatalysts

The performance of Mn-TiO₂/sepiolite photocatalysts prepared by the sol-gel method and calcinated at different temperatures was studied in the photocatalytic degradation of direct fast emerald green dye under visible light irradiation, and a series of analytical techniques such as XRD, SEM, FTIR, TG-DSC, XPS, UV-vis-DRS and Raman spectroscopy were used to characterize the morphology, structure and optical properties of the photocatalysts. It is found that the anatase TiO₂ was formed in all photocatalysts. Mn⁴⁺ might incorporate into the lattice structure of TiO₂ and partially replace Ti⁴⁺, thus causing the defects in the crystal structure and the broadening of the spectral response range of TiO₂. At the same time, TiO₂ particles were dispersed on the surface of the sepiolite, which immobilized TiO₂ particles with sepiolite via the bond of Ti−O−Si. Mn-TiO₂/sepiolite calcined at 400 °C exhibits the highest photocatalytic activity and the degradation rate of direct fast emerald green is up to 98.13%. Meanwhile, it also shows good stability and universality.     

Effect of SnO2 on the photocatalytical properties of TiO2 films

TiO₂/SnO₂ thin films with different tin atomic percentages were successfully prepared on glass substrates by the spray pyrolysis method from an alcoholic solution of TiO[C₅H₇O₂]₂ with different concentrations of SnCl₄. The TiO₂/SnO₂ thin films prepared at 450 °C presented the anatase phase in polycrystalline configuration from %Sn = 0 in the starting solution up to %Sn = 20, at higher tin content the films present an amorphous configuration. The resulting thin films have a homogeneous surface structure with some porosity. The photocatalytical properties of the films were evaluated with the degradation of methylene blue. The products of the degradation reaction were identified by ¹H nuclear magnetic resonance and the film properties were studied by atomic force microscopy, scanning electron microscopy, UV–Vis spectroscopy, and X-ray diffraction.     

Densification of sol–gel TiO2 very thin films studied by SPR measurements

Very thin TiO₂ films have been prepared by sol–gel and deposited on a silver layer for Surface Plasmon Resonance (SPR) measurements. Densification of the samples has been studied by determining from SPR measurements the optical index (ranging from 1.68 to 1.92) and thickness (ranging from 6 to 2 nm) at each step of the annealing procedure. The structure of the layer (amorphous and/or crystalline) has been checked at the final stage of the thermal treatment by High Resolution Transmission Electron Microscopy (HRTEM).     

Comparison of the electrochemical behavior of CeO2–SnO2 and CeO2–TiO2 electrodes produced by the Pechini method

CeO₂–SnO₂ and CeO₂–TiO₂ thin films were prepared by the Pechini method and their characteristics were compared, using a fractional factorial design to quantify the effect of five preparation variables. It was observed that CeO₂–SnO₂ electrodes show a greater electrochemical response than the CeO₂–TiO₂ films. The best intercalation charge densities were 18.11 and 9.91 mC/cm² for CeO₂–SnO₂ and CeO₂–TiO₂, respectively. Both films were optically inactive with transparencies, in most cases, higher than 90%.     

铕掺杂的TiO2空心微球的制备及光催化性能

通过溶胶-凝胶法制备未掺杂和铕掺杂的TiO₂空心微球, 采用XRD、SEM、TEM、HRTEM、BET和XPS等技术对样品进行表征, 以亚甲基蓝的光催化降解为目标反应, 评价其光催化活性。结果表明, 钛酸四丁酯(TBOT)的加入量对微球的形貌影响较大, 当滴加1.5 mL的TBOT时, 可得结构清晰、分散性良好的TiO₂空心微球。XRD分析表明, 400℃煅烧的纳米TiO₂空心微球为锐钛矿, 掺铕可抑制TiO₂的晶相转变。光催化实验表明, 铕掺杂能显著提高TiO₂空心微球的活性。当铕掺量为0.7%时, 所得样品粒径和孔径最小, 比表面积最大, 光催化活性最高。     

锐钛矿型TiO2纳米棒薄膜的溶胶-凝胶法制备研究

以钛酸丁酯Ti（OC₄H₉）₄、冰醋酸、去离子水和聚乙二醇（PEG）1000为原料,采用溶胶-凝胶法和旋转涂膜工艺,在玻璃衬底上制备出锐钛矿型TiO₂纳米棒。利用X射线衍射仪（XRD）、SEM和紫外可见光谱（UV/Vis）对TiO₂纳米棒薄膜进行了表征。结果表明,实验制备的TiO₂纳米棒为锐钛矿晶型,在TiO₂反应体系中,胶体粒子在加热过程中偶联在一起,1h后形成了TiO₂纳米棒,其直径为30～50nm,长度为100～200nm。同时,在42mL钛的胶体溶液中添加0.30g PEG（1000）后,纳米TiO₂薄膜的可见光透射峰值降低,TiO₂薄膜表面孔径为20～50nm。     

钴掺杂TiO2纳米管阵列薄膜的制备及其光催化还原性能

用磁控溅射法在ITO玻璃基底上制备Ti-Co合金薄膜,对其阳极氧化处理制备出钴掺杂TiO₂纳米管阵列薄膜,研究了钴掺杂对纳米管阵列薄膜的形貌、结构、吸收光谱以及光催化还原性能的影响。结果表明：钴掺杂TiO₂纳米管阵列薄膜为锐钛矿相,管状阵列的管径均一、排列规整。钴掺杂使薄膜形成(001)择优取向。随着钴掺杂量的提高,薄膜吸收可见光的能力提高。钴含量(原子分数)为0.19%的薄膜光催化性能最优,可见光照150 min后对Cr(VI)的还原率可达98.4%。     

Controllable formation of Er–Yb codoped Al2O3 films by the non-aqueous sol–gel method

1 mol%Er³⁺–10 mol%Yb³⁺ codoped Al₂O₃ thin films have been prepared on thermally oxidized SiO₂/Si(110) substrates by a dip-coating process in the non-aqueous sol–gel method from the hydrolysis of aluminum isopropoxide [Al(OC₃H₇)₃] under isopropanol environment. Addition of N,N-dimethylformamide (DMF) as a drying control chemical additive (DCCA) into the sol suppresses formation of the cracks in the Er³⁺–Yb³⁺ codoped Al₂O₃ thin films when the rare-earth ion is doped with a high doping concentration. Homogeneous, smooth and crack-free Er³⁺–Yb³⁺ codoped Al₂O₃ thin films form at the conditions by a molar ratio of 1:1 for DMF:Al(OC₃H₇)₃. A strong photoluminescence spectrum with a broadband extending from 1.400 to 1.700 µm centered at 1.533 µm is obtained for the Er³⁺–Yb³⁺ codoped Al₂O₃ thin films, which is unrelated to the addition of DMF. Controllable formation of the Er³⁺–Yb³⁺ codoped Al₂O₃ thin films may be explained by the fact that the DMF assisted the deprotonation process of Al–OH at the surfaces of gel particles, resulting in enhancement of the degree of polymerization of sols and improvement of the mechanical properties of gel thin films.     

Transmission electron microscopy studies of nanophase TiO2

The chemical and microstructural properties of nanosized TiO₂, obtained by sol—gel procedure, were investigated. The samples were characterized by analytical electron microscopy combining electron diffraction, high resolution electron microscopy and atomic force microscopy. These methods were supported by X-ray diffraction and thermal analysis. The chemical and structural properties, as well as the size of grains, depended on the temperature of TiO₂ preparation. In the temperature range between 293 and 820 K the TiO₂ grains consisted of anatase, as the dominant phase, and brookite. High resolution electron microscopy showed that the sample heated at 573 K had grain sizes from 2 to 10 nm, the average being (5 ± 1) nm, and the pore sizes from 4.5 to 12 nm. The sample heated at820 K revealed larger grain sizes, from 7 to 12 nm, the average being (9 ± 1) nm, and the pore sizes from 6 to 10 nm. These values were confirmed by X-ray diffraction broadening.     

Thickness and erbium doping effects on the electrical properties of lead zirconate titanate thin films

Thin films of erbium doped lead zirconate titanate (PZT) of different thickness were deposited by sol–gel technique on Pt/TiO₂/SiO₂/Si substrates. Capacitance–voltage measurements show that the dielectric constant continuously increases with the thickness. This is interpreted in terms of effects due to a low permittivity interfacial layer in series with the ferroelectric bulk. The linear fit of the reciprocal of capacitance vs. thickness leads to a true dielectric constant of the ferroelectric of 774 and interfacial capacitance of 14.6 nF. The leakage current properties also depend on thickness and temperature. The calculated interfacial potential barrier height amounts to 0.81 and 0.74 eV, respectively for erbium doped and pure PZT thin films.     

On the optical, structural, and morphological properties of ZrO2 and TiO2 dip-coated thin films supported on glass substrates

This article reports the optical and morphological properties of dip-coated TiO₂ and ZrO₂ thin films on soda-lime glass substrates by metal-organic decomposition (MOD) of titanium^IV and zirconium^IV acetylacetonates respectively. Thermogravimetric and differential thermal analysis (DTA–TG) were performed on the precursor powders, indicating pure TiO₂ anatase and tetragonal ZrO₂ phase formation. Phase crystallization processes took place in the range of 300–500 °C for anatase and of 410–500 °C for ZrO₂. Fourier Transform Infrared Spectroscopy (FT-IR) was used to confirm precursor bidentate ligand formation with keno-enolic equilibrium character. Deposited films were heated at different temperatures, and their structural, optical and morphological properties were studied by grazing-incidence X-ray Diffraction (GIXRD) and X-Ray Photoelectron Spectroscopy (XPS), Ultraviolet Visible Spectroscopy (UV-Vis), and Atomic Force Microscopy (AFM) respectively. Film thinning and crystalline phase formation were enhanced with increasing temperature upon chelate decomposition. The optimum annealing temperature for both pure anatase TiO₂ and tetragonal ZrO₂ thin films was found to be 500 °C since solid volume fraction increased with temperature and film refractive index values approached those of pure anatase and tetragonal zirconia. Conditions for clean stoichiometric film formation with an average roughness value of 2 nm are discussed in terms of material binding energies indicated by XPS analyses, refractive index and solid volume fraction obtained indirectly by UV-Vis spectra, and crystalline peak identification provided by GIXRD.     

Hydrophilicity on carbon-doped TiO2 thin films under visible light

Carbon-doped TiO₂ thin films in the anatase phase with dopant concentrations of 1.1, 0.9, and 0.7 mol% were fabricated by a radio-frequency magnetron sputtering method. Dopant carbons were located at the oxygen sites. Carbon substitution caused the absorbance edge and/or the shoulder of TiO₂ to shift to a higher wavelength region. Carbon-doped TiO₂ thin films underwent a hydrophilic conversion when irradiating with visible light (400–530 nm). The hydrophilic property under visible light was inferior to that under ultraviolet light, which is explained by considering that the visible light sensitivity originates from the localized C 2p formed in the band-gap.     

Er3+掺杂TiO2空心球的制备及其光催化性能研究

以钛酸四丁酯、氧化铒、硝酸等为原料, 采用碳球模板法制备了TiO₂: Er³⁺空心球材料, 利用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线衍射(XRD)等测试方法, 对样品的结构和形貌进行了表征。并利用紫外-可见(UV-Vis)分光光度计考察了TiO₂: Er³⁺空心球材料在催化染料罗丹明B、亚甲基蓝、茜素红、甲基橙的脱色降解过程中的应用性能。系统研究了Er³⁺掺杂浓度、不同离子型染料和染料水溶液的pH等因素对催化降解效率的影响。实验结果表明: 经600℃煅烧3 h制备的TiO₂: Er³⁺为锐钛矿晶型, 空心球结构, 尺寸均匀, 粒径约为120 nm, 比表面积约为60.5 m²/g; Er³⁺掺杂量为0.5mol%的样品对甲基橙染料的催化降解效率最高; 对四种不同离子型染料, 茜素红的催化降解效果显著, 在紫外光照射下, 催化效率较未掺杂Er³⁺的TiO₂提高了约30%。     

Dynamic Formation of Diffraction Grating in a Photorefractive Liquid Crystal Cell With Mesoporous $hbox{TiO}_{2}$ Layers

We report the photorefractive effect of a layer-structured liquid crystal cell using N3-chemisorbed mesoporous TiO₂ layers as photoconductive layers. Well-organized mesoporous thin films were prepared using surfactant templates. N3 was chemisorbed on the mesoporous TiO₂ layer to effectively generate excited electrons, which could be injected in the TiO₂ layer and participate in the generation of a space-charge field in the LC cell. The prepared liqud crystal cell shows unique characteristics of an inorganic photoconductive layer, a temporal diffraction grating formation.     

介孔电气石/TiO2复合材料的制备及其模拟太阳光光催化性能

采用一步溶胶-凝胶共缩合结合溶剂热合成技术制备出一系列介孔电气石/TiO₂复合材料,表征了复合材料的相结构、形貌、孔隙率、光吸收性质以及组成结构.结果表明:制备的电气石/TiO₂复合材料具有纯锐钛矿晶相、均匀的介孔结构、较大的比表面积(205~242 m²·g^-1)、均匀的孔径分布(3.4~3.8 nm)以及较低的带隙能(3.0 eV).在模拟太阳光照射下,电气石/TiO₂复合材料可以被成功地应用于水中有机污染物罗丹明B和诺氟沙星的降解.降解动力学研究表明:电气石的掺杂提高了TiO₂的光催化量子效率,降低了TiO₂的带隙能.对罗丹明B的降解,电气石掺杂量为1wt%~5wt%的电气石/TiO₂复合材料表现出比纯TiO₂更高的降解速率,对诺氟沙星的降解,电气石/TiO₂复合材料的降解速率高于纯TiO₂的.     

Nanoscale ZnS/TiO2 composites: Preparation, characterization, and visible-light photocatalytic activity

Photoactive ZnS/TiO₂ nanocomposites were prepared via microemulsion-mediated solvothermal method. The structure, composition, physicochemical property, and morphology of the composites were characterized by powder X-ray diffraction (XRD), Raman scattering studies, UV diffuse reflectance spectroscopy (UV/DRS), photoluminescence (PL) spectroscopy, and transmission electron microscopy (TEM). It showed that the composites were cube-shaped with particle sizes of 10 to 15 nm, and the phase structure for ZnS and TiO₂ in the composites was cubic and anatase, respectively. The content of the ZnS in the composites was 2.1%, 10.7%, and 19.9%, respectively. Compared with the solitary anatase TiO₂, the ZnS/TiO₂ exhibited enhanced visible-light photocatalytic activity for the aqueous parathion-methyl degradation. Factors including the interactions between the phases of ZnS and TiO₂, strong adsorption of the substrate at the surface of the ZnS/TiO₂ nanocomposites, and preassociation of the substrate and composites are responsible for this enhancement photocatalytic activity.