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.     

B掺杂TiO2光催化剂的制备和光催化性能

采用溶胶-凝胶法合成了B掺杂的TiO₂光催化剂,并用XRD、SEM、XPS、FT-IR、BET等手段进行了表征。结果表明,掺杂B可抑制TiO₂晶体的长大,对TiO₂表面形貌没有显著的影响,B-TiO₂催化剂的比表面积随着B离子掺杂量的提高而增大;B离子主要进入晶格间隙并与TiO₂晶体形成固溶体,以B-O-Ti结构存在。B掺杂量（质量分数）为3%时,制备出的TiO₂光催化剂对甲基橙的降解效果最好。N₂吸附-脱附结果表明,3%B-TiO₂的BET比面积为127.84 m²/g、平均孔径为10.53 nm。     

Structural, optical and electrical characterization of spray-deposited TiO2 thin films

Titanium oxide (TiO₂) thin films were deposited onto glass substrates by means of spray pyrolysis method using methanolic titanyl acetyl acetonate as precursor solution. The thin films were deposited at three different temperatures namely 350, 400 and 450 °C. As-deposited thin films were amorphous having 100–300 nm thickness. The thin films were subsequently annealed at 500 °C in air for 2 h. Structural, optical and electrical properties of TiO₂ thin films have been studied. Polycrystalline thin films with rutile crystal structure, as evidenced from X-ray diffraction pattern, were obtained with major reflexion along (1 1 0). Surface morphology and growth stages based on atomic force microscopy measurements are discussed. Electrical properties have been studied by means of electrical resistivity and thermoelectric power measurements. Optical study shows that TiO₂ possesses direct optical transition with band gap of 3.4 eV.     

Densification and grain growth during pressureless sintering of TiO2 nanoceramics

Anatase titania nanopowders with mean particle sizes of 7, 15, 26 and 38 nm synthesized by sol–gel method were used to sinter bulk TiO₂ nanoceramics. The relative densities and average grain sizes of the TiO₂ nanoceramics were studied as a function of the compaction pressure on green sheet, sintering temperature, and mean particle size of the starting TiO₂ nanopowders. The relative density of the TiO₂ nanoceramics increases rapidly and average grain size increases slowly with increasing sintering temperature below 800 °C. Sintering at higher temperatures above 800 °C enhances the densification of the TiO₂ nanoceramics and leads to a increase of the grain size. Bulk TiO₂ nanoceramics with an average grain size of less than 60 nm and relative density over 95% was obtained by a phase-transformation-assisted pressureless sintering at a relatively low temperature (800 °C).     

Synthesis,characterization, antibacterial and photocatalytic performance of Ag/AgI/TiO2 hollow sphere composites

Dispersed TiO₂ hollow spheres were successfully prepared which was obtained via Ostwald ripening under solvothermal conditions without any templates or surfactants. Then, the AgI/TiO₂ was synthesized by the deposition−precipitation process. Finally, Ag/AgI/TiO₂ was obtained by a photocatalytic reduction way. Their characteristics were analyzed by XRD, SEM, HRTEM, N₂ adsorption−desorption measurements and UV-vis absorption spectra. To demonstrate the potential applications of such composites, their antibacterial activity against Escherichia coli (E. coli) was studied by microcalorimetry for the first time, and their photocatalytic performance for degradation of different organic dyes under simulated UV and visible light was discussed. The results indicated that Ag/AgI/TiO₂ hollow spheres revealed elevated antibacterial and photocatalytic activity because of their unique morphology, hollow structure and high surface area. The mechanism of the excellent antibacterial and photocatalytic activity of Ag/AgI/TiO₂ hollow spheres are discussed which are attributed to the synergetic effect of Ag, AgI and TiO₂. It suggested that the new Ag/AgI/TiO₂ photocatalyst has broad application prospects in solar cell, sensor, antibacterial, catalysis and nanotechnology.     

TiO2/静电纺PAN基碳复合材料的制备及光催化性能

为了同时提高催化剂的光催化和回收能力,以聚丙烯腈(PAN)和钛酸四丁酯(TBT)作为碳纳米纤维(CNFs)和TiO₂前驱体,通过静电纺丝和热处理方法制备了TiO₂/CNFs复合材料,并通过SEM、XRD、Raman、UV-vis分光光度计等对TiO₂/CNFs复合材料的形貌、晶体结构、光吸收性能、导电性和光催化性能进行了研究。结果表明:随TBT添加量的逐渐增多,TiO₂/CNFs复合材料在热处理过程中卷曲形态逐渐消失,并且TBT在碳化过程中完全转化为锐钛矿TiO₂;TiO₂/CNFs复合材料光吸收边缘由纯TiO₂的紫外光区扩展至可见光区,提高了催化剂对太阳光的利用率;同时,在模拟太阳光照射180 min,TiO₂/CNFs复合材料对RhB的光催化降解率最大可达到95.71%,并且在连续重复使用5次后光催化降解效率仍可达到约90%。      

Effects of peptizing conditions on nanometer properties and photocatalytic activity of TiO2 hydrosols prepared by H2TiO3

TiO₂ hydrosols were prepared from metatitanic acid (H₂TiO₃) by chemical precipitation–peptization method under various peptizing conditions. The effects of peptizing conditions on nanosized properties and photocatalytic activity of TiO₂ hydrosols were investigated. The crystal structure, crystallinity, particle size distribution, and transparency (T%) of as-obtained hydrosols were characterized by means of X-ray diffraction, transmission electron microscopy, light-scattering size analyzer, and UV–vis transmittance spectra. The results showed that the properties of hydrosols depended on peptizing conditions including a molar ratio of H⁺/Ti, temperature, and solid content. The photoactivity of TiO₂ hydrosols was evaluated in terms of the degradation of rhodamine B (RhB) in aqueous solution, and formaldehyde (HCHO) and methyl mercaptan (CH₃SH) in gaseous phase. The results showed that increase in H⁺/Ti ranging 0.19–0.75 led to the decrease in particle size and the increase in transparency. With increasing of temperature, particle sizes increased while the transparency and photoactivity decreased steadily when the temperature was higher than 65 °C. The particle size, transparency and photoactivity of the hydrosols hardly depended on solid content when it was not less than 2%. It should be confirmed that the hydrosols with higher crystallinity, smaller particle size and higher transparency could have the higher photoactivity for the degradation of RhB, CH₃SH, and HCHO. In this study, the optimal peptizing conditions were determined to be H⁺/Ti = 0.75, temperature = 65 °C and solid content = 2–6%.     

Ag对TiO2@Ag/聚偏氟乙烯复合薄膜性能的影响

采用光化学沉积法和溶液刮膜法制备不同Ag含量的TiO₂@Ag/聚偏氟乙烯(PVDF)复合薄膜,并采用电子万能材料试验机、紫外可见近红外分光光度计和XRD等对TiO₂@Ag/PVDF复合薄膜的物理性能和光催化性能进行表征和分析。研究发现:与TiO₂/PVDF复合薄膜相比,TiO₂@Ag/PVDF复合薄膜的拉伸强度明显提高,但断裂伸长降低,且复合薄膜的响应光谱范围拓宽至可见光区;TiO₂@Ag/PVDF复合薄膜的光催化降解能力随Ag负载量的增加而呈先升高后降低的趋势;同时TiO₂@Ag/PVDF复合薄膜具有优异的重复利用性和可见光区自清洁作用。综上所述,实验所制备的TiO₂@Ag/PVDF复合薄膜能够满足实际应用需要,因此其在光催化降解领域具有潜在的应用前景。      

多孔竹炭/二氧化钛纳米复合材料制备及其光催化作用

本工作合成了一种具有高吸附性能和光催化性能的表面改性竹炭/二氧化钛(SMBC/TiO₂)纳米复合材料。通过湿法氧化处理廉价、天然绿色的竹炭(BC), 制备了具有良好吸附性、化学稳定性的表面改性竹炭(SMBC)。经过改性, BC表面生成大量含氧官能团, 因此SMBC粒子易分散于水中, 并且与TiO₂有较强的相互作用, 确保TiO₂均匀地负载在SMBC表面。SMBC/TiO₂比BC/TiO₂有更大的比表面积, 能提供更强的吸附性能。SMBC/TiO₂的饱和吸附容量大约是BC/TiO₂的1.6倍, 是TiO₂的12.1倍。吸附和催化的协同作用使SMBC/TiO₂复合材料降解MB具有更高的光催化活性, SMBC/TiO₂光催化降解MB的速率常数分别是BC/TiO₂ 和TiO₂的7倍和6倍。     

TiO2-g-C3N4-Bi2O3复合异质结构催化材料在水处理中的应用

异质结光催化材料在降解有毒有害污染物方面体现出优良的效果。以苯酚有机废水作为研究对象,球磨法所制备的TiO₂-g-C₃N₄和TiO₂-g-C₃N₄-Bi₂O₃两种光催化材料作为实验材料,探究不同光源条件下TiO₂-g-C₃N₄、TiO₂-g-C₃N₄-Bi₂O₃的光催化特性及其对苯酚废水处理效果。结果表明,在可见光和紫外光单独照射条件下,三元体系的TiO₂-g-C₃N₄-Bi₂O₃均比TiO₂-g-C₃N₄具有更高的光催化活性,并且可见光条件下,TiO₂-g-C₃N₄-Bi₂O₃比TiO₂-g-C₃N₄的优势更明显;在可见光和紫外光同时照射时,TiO₂-g-C₃N₄-Bi₂O₃、TiO₂-g-C₃N₄对苯酚废水的降解效率分别达到99.44%、96.67%。表征结果表明,Bi₂O₃的掺杂有效地增强了催化剂在全光谱范围内对光的吸收,并且三元体系的构建有效地促进了光生电子与空穴的分离。研究结果表明,通过简单可控的球磨-微波加热-煅烧工艺,可以实现TiO₂-g-C₃N₄-Bi₂O₃的制备,并且证实了TiO₂-g-C₃N₄-Bi₂O₃材料在有机废水处理方面的良好前景。      

Ag-Ag2O/TiO2-g-C3N4纳米复合材料的制备及可见光催化性能

近年来,半导体光催化技术作为一项快速发展的新型环保技术,在降解水体中污染物和可再生清洁能源的生产领域有很大的应用前景。本文以所制备出的20 wt%类石墨烯碳氮化合物(g-C₃N₄)/TiO₂为基质,利用水热法中纳米Ag颗粒部分氧化行为成功合成了Ag修饰异质结型Ag-Ag₂O/TiO₂-g-C₃N₄复合材料。利用X射线衍射(XRD)、扫描电子显微镜(SEM)、X射线光电子能谱(XPS)、紫外-可见漫反射光谱(UV-Vis DRS)、光致荧光光谱(PL)、瞬态光电流响应等分析测试手段对Ag-Ag₂O/TiO₂-g-C₃N₄复合材料的晶体结构、形貌、光学性质等进行表征和分析。以亚甲基蓝溶液为目标降解物,研究了Ag-Ag₂O/TiO₂-g-C₃N₄复合材料的可见光催化性能。结果表明:在纳米Ag颗粒修饰的Ag-Ag₂O/TiO₂-g-C₃N₄复合材料中,Ag部分氧化成Ag₂O;与g-C₃N₄的协同作用使Ag-Ag₂O/TiO₂-g-C₃N₄复合催化剂具有良好的可见光催化活性;可见光照射4 h后,Ag-Ag₂O/TiO₂-g-C₃N₄复合催化剂对亚甲基蓝的降解率接近50%。      

N与La共掺杂纳米TiO_2/电气石复合材料的制备及其光催化性能

采用超声辅助溶胶-凝胶法,以钛酸丁酯为原料,尿素为N源,硝酸镧为La源,制备了N与La共掺杂纳米TiO_2/电气石复合材料。采用XRD、UV-Vis、SEM-EDS和XPS对复合材料的结构和性能进行了表征。以2,4,6-三硝基甲苯作为目标污染物,考察了N与La共掺杂纳米TiO_2/电气石复合材料的光催化活性及再生利用性能。结果表明:N与La共掺杂并负载电气石后,两者协同作用使TiO_2晶粒更加细化,光吸收范围向可见光区拓展,N与La共掺杂纳米TiO_2/电气石复合材料具有良好的光催化活性和再生利用性能,且在模拟可见光照射条件下对2,4,6-三硝基甲苯具有良好的去除效果。     

Composite of Carboxyl-Modified Multi-walled Carbon Nanotubes and TiO2 Nanoparticles: Preparation and Photocatalytic Activity

The composite of carboxyl-modified multi-walled carbon nanotubes (MWNT-COOHs) and TiO₂ nanoparticles was prepared by improved solvothermal process. X-ray diffraction (XRD), transmission electron microscope (TEM) and UV-Vis spectra were used to characterize the products. The results show that MWNT-COOHs were “welded” by the TiO₂ nanoparticles attached to the open ends of MWNT-COOHs. Compared with pure TiO₂ nanoparticles, the composite displays higher photocatalytic activity with 99.9% of degradation ratio of copper sulfophthalocyanine after 3 h irradiation.     

Ag/TiO2纳米粒子的制备及其光催化降解苯酚的性能研究

采用溶胶-凝胶法制备了TiO₂和Ag/TiO₂纳米粒子,采用涂覆法制备了TiO₂和Ag/TiO₂纳米粒子光催化剂基板样品。使用XRD、SEM和拉曼光谱等手段,对TiO₂和Ag/TiO₂纳米粒子进行了晶格结构和表面形貌研究;通过UV-Vis,研究了TiO₂和Ag/TiO₂纳米粒子光催化剂基板样品在光催化反应器中对苯酚的光催化降解性能。结果表明,制备的TiO₂和Ag/TiO₂纳米粒子均为纯净的金红石相,二者表面形貌并没有明显区别,Ag单质粒子成功负载在TiO₂纳米材料上;Ag单质粒子的负载,明显增强了TiO₂纳米粒子对可见光的吸收,且Ag/TiO₂纳米粒子薄膜对苯酚的光催化降解性能明显优于TiO₂纳米粒子薄膜;在光催化降解1 h后,TiO₂纳米粒子薄膜仅催化降解了溶液中30%(质量分数)的苯酚,且光催化降解出现了饱和趋势,而Ag/TiO₂纳米粒子薄膜可催化降解溶液中50%(质量分数)的苯酚,且在光催化降解3 h后,仍未出现饱和趋势。     

Synthesis of nanocrystalline photocatalytic TiO2 thin films and particles using sol–gel method modified with nonionic surfactants

A simple sol–gel route has been developed for the preparation of nanocrystalline photocatalytic TiO₂ thin films and particles at 500 °C. The synthesis involved a novel chemistry method employing nonionic surfactant molecules as a pore directing agent along with acetic acid-based sol–gel route without direct addition of water molecules. This study investigated the effect of surfactant type and concentration on the homogeneity, morphology, light absorption, dye adsorption and degradation, and hydrophilicity of TiO₂ films as well as on the structural properties of the corresponding TiO₂ particles. The method resulted in the synthesis of mesoporous TiO₂ material with enhanced structural and catalytic properties including high surface area, large pore volume, pore size controllability, small crystallite size, enhanced crystallinity, and active anatase crystal phase. The prepared TiO₂ thin films were super-hydrophilic and possessed thermally stable spherical bicontinuous mesopore structure with highly interconnected network. Highly porous TiO₂ films prepared with polyethylene glycol sorbitan monooleate surfactant exhibited four times higher photocatalytic activity for the decoloration of methylene blue dye than the nonporous control TiO₂ films prepared without the surfactant. This sol–gel method modified with surfactant templates is useful in the preparation of nanostructured anatase TiO₂ thin films with high photocatalytic activity and desired pore structure.     

Fabrication of robust Bi3.25La0.75Ti3O12 thin film resistant to hydrogen damage

Ferroelectric bismuth lanthanum titanate (Bi_3.25La_0.75Ti₃O₁₂; BLT) thin films were deposited on Pt/TiO₂/SiO₂/Si substrate by chemical solution deposition method. The films were crystallized in the temperature range of 600–700 °C. The spontaneous polarization (P_s) and the switching polarization (2P_r) of BLT film annealed at 700 °C for 30 min were 22.6 μC/cm² and 29.1 μC/cm², respectively. Moreover, the BLT capacitor did not show any significant reduction of hysteresis for 90 min at 300 °C in the forming gas atmosphere.     

Photocatalytic degradation of Orange G on nitrogen-doped TiO2 catalysts under visible light and sunlight irradiation

In this paper, the degradation of an azo dye Orange G (OG) on nitrogen-doped TiO₂ photocatalysts has been investigated under visible light and sunlight irradiation. Under visible light irradiation, the doped TiO₂ nanocatalysts demonstrated higher activity than the commercial Dugussa P25 TiO₂, allowing more efficient utilization of solar light, while under sunlight, P25 showed higher photocatalytic activity. According to the X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and UV–vis spectra analyses, it was found that both the nanosized anatase structure and the appearance of new absorption band in the visible region caused by nitrogen doping were responsible for the significant enhancement of OG degradation under visible light. In addition, the photosensitized oxidation mechanism originated from OG itself was also considered contributing to the higher visible-light-induced degradation efficiency. The effect of the initial pH of the solution and the dosage of hydrogen peroxide under different light sources was also investigated. Under visible light and sunlight, the optimal solution pH was both 2.0, while the optimal dosage of H₂O₂ was 5.0 and 15.0 mmol/l, respectively.     

Cracking behavior of oxide scale formed on Ti3SiC2-based ceramic

The cyclic oxidation and acoustic emission (AE) tests were carried out for studying cracking behavior of oxide scales formed on Ti₃SiC₂-based ceramic at 1100 °C. A duplex oxide scale with an outer layer of pure TiO₂ and an inner layer of a mixture of TiO₂ and SiO₂ was formed. The oxide scale did not spall from substrate during the cyclic oxidation at 1100 °C for 360 times. However, a great number of micro-cracks penetrating whole inner oxide layer were detected. AE test showed that the oxide scale did not crack during the isothermal oxidation at 1100 °C for 1 h, however, the scale cracked during the cooling stage. Comparing the growth rate and thickness between the oxide layers formed during the isothermal oxidation and cyclic oxidation, respectively, indicated that cracks in the inner oxide layer served as paths mainly for outward diffusion of titanium and for inward diffusion of oxygen, resulting in increased growth rate of the outer oxide layer. Because of entire and compact TiO₂ consisted of outer oxide layer, and low thermal stress resulting from small mismatch of thermal expansion coefficients between the oxides and the substrate, Ti₃SiC₂ exhibited excellent cyclic oxidation resistance at 1100 °C for 360 cycles.     

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.     

纳米TiO2/碳化植物纤维复合材料的制备与光催化性能

以碳化植物纤维(CPF)为载体,将纳米TiO₂附着于纤维表面,通过浸渍煅烧法和溶剂热法合成纳米TiO₂/CPF复合光催化剂,并对其光催化性能进行了研究。通过SEM、HRTEM、XRD、EDS分析了纳米TiO₂/CPF复合光催化剂的微观结构和化学组成;以光催化降解亚甲基蓝为模型反应,考察复合材料中不同纤维种类和TiO₂负载量对光催化活性的影响。结果表明,在一定范围内随TiO₂负载量的增加,纳米TiO₂/CPF复合材料光催化性能先增强后减弱。纳米TiO₂/CPF复合材料的光催化性能明显提高是由于在TiO₂和碳纤维界面的良好电荷分离能力。降解染料的活性物种有超氧负离子和羟基自由基,但羟基自由基是主要物种。此外,浸渍煅烧法和溶剂热法生成的纳米TiO₂在纤维表面的存在形式不同,浸渍煅烧法生成纳米TiO₂薄膜,包裹纤维;而溶剂热法生成的TiO₂结晶成纳米颗粒,附着于纤维表面。