Lipid Peroxidation Processes Photoinduced by Titanium Dioxide in Emulsion Systems,Representative of Sunscreen Formulations

This article studies the peroxidation of linoleic acid and of porcine skin lipids on ultraviolet B (UVB) irradiation, in the presence of various TiO₂ specimens used as inorganic sunscreen pigments in different emulsion systems. It was found that different TiO₂ specimens induce quite variable lipid peroxidation in the same emulsion system, which suggests that the different coatings widely differ in their effectiveness to lower the photocatalytic activity of TiO₂. However, it was also found that the extent of lipid peroxidation caused by the same TiO₂ pigment in different emulsions was even more variable than the effects of different pigments in the same system. This finding might imply that the choice of the formulation components different from TiO₂ could be of paramount importance as far as the potential skin damage induced by the photocatalytic activity of TiO₂ is concerned.     

Photodegradation of Caffeic Acid in W/O/W Emulsions in the Absence and in the Presence of TiO2

Caffeic acid, a natural phenol with antioxidant and sunscreen activity, can undergo photooxidation upon UV irradiation. The photodegradation of caffeic acid at different concentrations was assessed in water, at pH 4.0 and 6.0, without and with TiO₂. The study was then carried out on W/O/W emulsions entrapping the phenolic acid either in the inner or in the outer aqueous phase in the absence and in the presence of TiO₂, added in the external phase (pH 6.0 or 7.0). The degradation of caffeic acid followed a pseudo-zero order kinetic with an inverse dependence from its initial concentration; at increasing pH of the medium caffeic acid degraded faster. The addition of TiO₂ increased the initial photodegradation rate. Compared with water, W/O/W emulsions protected the phenol towards both the photodegradation and the photocatalytic activity of TiO₂. Multiple systems allowed to incorporate caffeic acid and TiO₂ in the same formulation avoiding any catalytic interactions.     

Study on the Photodegradation of Salicylic Acid in Different Vehicles in the Absence and in the Presence of TiO2

In this work, the direct photolysis of salicylic acid, generally used as keratolytic agent in many dermatological products and as preservative in cosmetics, was investigated. The photodegradation of the acid under UVB irradiation was evaluated in different vehicles, such as water solutions at different pH, propylene glycol/water, and ethanol/water mixtures, sodium dodecyl sulphate solutions, and O/W emulsions prepared with Montanov 68 and Amphysol K as emulsifiers. The increase of pH enhanced the photodegradation of salicylic acid while the different vehicles protected the acid from the action of UVB radiations. However, the best protection was observed dissolving the acid in the lipid core of O/W emulsions, which probably removes the active from the polar environment that can promote the photolysis. The photocatalytic activity of TiO₂ on the degradation of salicylic acid also was evaluated. TiO₂ frequently is used as sunscreen in many cosmetic preparations. Salicylic acid and the pigment can be contained in the same solar formulation; hence, it can be interesting to study their interaction under UVB. TiO₂ enhanced the photodegradation of salicylic acid in all the media previously reported and its photocatalytic activity was influenced by the pH and by the components of the vehicles.     

Parameters controlling the photocatalytic performance of ZnO/Hombikat TiO2 composites

Commercial TiO₂ (Hombikat, UV-100) was impregnated with different loadings of zinc nitrate solution and subsequently calcined at different temperatures in order to obtain a stable homogeneous solid composite of ZnO/TiO₂. The prepared samples were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HR-TEM), UV-vis and Raman spectroscopy, inductively coupled plasma mass spectroscopy (ICP), X-ray photoelectron spectroscopy (XPS) as well as N₂ adsorption and desorption measurements. Results show that ZnO was incorporated within the TiO₂ crystals and did not form a separate bulky phase or metallic zinc. Moreover, the calcination temperature dramatically modifies the texture properties of the prepared samples compared with original Hombikat TiO₂. The photocatalytic performance of the prepared samples was evaluated by monitoring the degradation of methyl orange dye under black light illumination. Three main parameters were studied; ZnO loading, surface area and initial pH of the methyl orange solution. The variation in ZnO loading appears to have less influence on the catalytic activity than either the surface area or the pH.     

Preparation of TiO2 nano-particle photocatalysts by a multi-gelation method: the effect of pH change

TiO₂ photocatalysts were prepared by a multi-gelation method and the effect of the changes in the pH during the pH swing times, i.e., by a controlled pH swing, on the morphology of the TiO₂ particles was investigated. The photocatalytic properties of the TiO₂ catalysts prepared by controlled pH swing were compared with TiO₂ particles prepared without adjusting the pH during the swing times. The photocatalytic degradation reaction of these TiO₂ catalysts was investigated by comparing their effectiveness in 2-propanol oxidation. The experimental results showed that the TiO₂ photocatalysts prepared without adjusting the pH performed better in controlling the important parameters of the catalysts such as particle size, surface area, anatase/rutile phase ratio and pore size, as well as pore volume than the TiO₂ photocatalysts prepared by a controlled pH swing method. Deceased.     

Synthesis of Nano‐Sized TiO2 Colloidal Sol and Its Optical Properties

Nano‐sized TiO₂ sol was prepared through a wet synthesis process. The synthesis procedure involved hydrolysis of TiCl₄, acid treatment, and a SiO₂ surface‐modifying process. Before surface modification, the TiO₂ suspension was treated with acid to remove Na ions, soluble TiO_2, and other impurities. The acid treatment of a TiO₂ suspension at a higher temperature was proved to be useful for effective SiO₂ modification. The colloidal sol provided high transparency in visible light as well as excellent UV‐shielding properties. Surface modification of TiO₂ particles with SiO₂ greatly improved both the dispersing stability in neutral pH and the photostability of TiO₂ colloidal sol.     

Patterning Effect of a Sol-Gel TiO2 Overlayer on the Photocatalytic Activity of a TiO2/SnO2 Bilayer-Type Photocatalyst

TiO₂ films with a thickness of 75 ± 5 nm (anatase) were formed on SnO₂-film (580 ± 80 nm) coated soda-lime glass substrates (SnO₂/SL-glass) by a sol-gel method. Although the photocatalytic activity for CH₃CHO oxidation (_ex > 300 nm) significantly exceeded that of a standard TiO₂/quartz sample, it decayed with illumination time (t) at t > 0.75 h. Stripes of anatase TiO₂ films of 40 nm in thickness and 1 mm in width were prepared on the SnO₂/SL-glass substrate in a 1-mm pitch by photolysis of an organically modified sol-gel film. The TiO₂ patterning further increased the photocatalytic activity by a factor of 4.1 as compared to the non-patterned sample, and it was also maintained at 0 < t < 2 h. The flat band potentials of the TiO₂ and SnO₂ films are determined to be –0.34 and +0.07 V (vs. SHE), respectively, at pH = 7 by the Mott-Schottky plots. On the basis of the results, the outstanding patterning effects could be rationalized in terms of the vectorial charge separation at the interface between TiO₂ and SnO₂.     

Synthesis of nanosized TiO2/SiO2 particles using microwave processes and their photocatalytic activity on the decomposition of orange II

The nanosized titania and TiO₂/SiO₂ particles were prepared by the microwave-hydrothermal method. The effect of physical properties TTIP/TEOS ratio and calcination temperature has been investigated. The major phase of the pure TiO₂ particle is of the anatase structure, and a rutile peak was observed above 800°C. In TiO₂/SiO₂ particles, however, no significant rutile phase was observed, although the calcination temperature was 900°C. No peaks for the silica crystal phase were observed at either silica/titania ratio. The crystallite size of TiO₂/SiO₂ particles decreases as compared to pure TiO₂ at high calcination temperatures. The TiO₂/SiO₂ particles show higher activity on the photocatalytic decomposition of orange II as compared to pure TiO₂ particles.     

Surface properties and photocatalytic activity of nanocrystalline titania films

In this work the efficiency and physicochemical details of a thin film produced by help of a microwave assisted sol gel technique is compared to different commercial powders (Degussa P25 and Hombikat UV100) deposited on glass substrates. Furthermore, a supercritical produced TiO₂ powder (SC 134) was included in the comparison.The prepared TiO₂ films were characterized using XRD, XPS, AFM, DSC and DLS. The photocatalytic activity was determined using stearic acid as a model compound. Investigation of the prepared films showed that the Degussa P25 film and the sol–gel film were the most photocatalytic active films. The activity of the films was found to be related to the crystallinity of the TiO₂ film and the amount of surface area and surface hydroxyl groups. Based on the XPS investigation of the films before and after UV irradiation it was suggested that the photocatalytic destruction of organic matter on TiO₂ films proceeds partly through formation of hydroxyl radicals which are formed from surface hydroxyl groups created by interactions between adsorbed water and vacancies on the TiO₂ surface. Furthermore a correlation between the amount of OH groups on the surface of the different TiO₂ films and the photocatalytic activity was found.     

Effect of electrolysis conditions on photocatalytic activities of the anodized TiO2 films

Photocatalytic activities of anodized TiO₂ films for decomposition of gaseous acetaldehyde were investigated. The anodized TiO₂ films were fabricated by galvanostatic anodization in a mixed electrolyte composed of H₂SO₄, H₃PO₄, and H₂O₂. Pre-nitridation treatment effectively enhanced the photocatalytic activity of the anodized TiO₂ films. The electrolysis parameters such as anodization time, current density, electrolyte temperature, and electrolyte composition significantly affected the photocatalytic activity of the anodized TiO₂ films. The improvement of photocatalytic activity of the anodized films is attributed to increase in surface areas of the anodized specimens.     

Photostability of Ferulic Acid and Its Antioxidant Activity Against Linoleic Acid Peroxidation

Ferulic acid (4‐hydroxy‐3‐methoxycinnamic acid), a phenyl‐propenoid derivative of cinnamic acid, can undergo photolysis upon UV irradiation. The photodegradation kinetics of ferulic acid were thus investigated in different systems. The micellar solutions did not protect the acid from photodegradation. On the contrary, they catalyzed its degradation at a variable extent depending on the surfactant structure. The photodegradation of ferulic acid in microemulsions was slower than in micelles and near to that in water. TiO₂, habitually employed as a physical sunscreen, showed photocatalytic action toward ferulic acid degradation especially at higher initial concentration of ferulic acid. The action of ferulic acid on the peroxidation of linoleic acid in micelles and microemulsions also was evaluated. When the ferulic acid is absent the peroxidation is continuous while when it is present an induction time of 40 minutes or higher was observed. Accordingly, it is likely that linoleic acid acts as photosensitizer for ferulic acid, and that in turn ferulic acid acts as an antioxidant for linoleic acid, reducing the rate of peroxidation.     

Influences of the H2PtCl6 Solution's pH on the Photocatalytic Activities of Platinum-Loaded TiO2 Nanotubes

By using H₂PtCl₆ and titanate nanotubes as precursor, platinum-loaded TiO₂ nanotubes (Pt/TiO₂NTs) are prepared at different pH by deposition-precipitation method. The prepared materials are characterized with powder x-ray diffraction (XRD) and x-ray photoelectron spectra (XPS). Their photocatalytic performance is evaluated by the degradation rates of methyl orange solution under UV-vis light irradiation. Obtained results indicate that the pH of H₂PtCl₆ solution has obvious influence on the catalytic performance of Pt/TiO₂NTs.     

Rapid Synthesis of Nanocrystalline TiO2/SnO2 Binary Oxides and Their Photoinduced Decomposition of Methyl Orange

A rapid and simple method, the so-called stearic acid method (SAM) was developed to prepare nanostructured TiO₂/SnO₂ binary oxides by combustion of stearic acid precursors. The preparative process was studied by Fourier transform infrared spectroscopy (FT-IR). During the preparative process, metal precursors were dispersed in stearic acid at molecular level. Microstructure of the samples was investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM), BET specific surface area measurement and the results were compared with those obtained by conventional sol-gel method. The photocatalytic decomposition of methyl orange was used as a model system to determine the relative influences of the preparation method and the concentration of SnO₂ on the photocatalytic activities. It was found that preparative methods affected the crystalline structure of TiO₂/SnO₂ powders and the anatase phase of TiO₂ was stabilized by the addition of SnO₂ in SAM. The samples prepared by SAM showed better dispersity, larger specific surface area and the TiO₂/SnO₂ (r=0.15, SAM) catalyst showed higher photocatalytic activity than Degussa P25.     

TiO2-石墨烯光催化剂：制备及引入石墨烯的方法对光催化性能的影响

利用溶胶-凝胶法原位制备了二氧化钛/石墨烯(TiO2-GE)复合光催化剂,研究了纯TiO2以及不同方法制备的TiO2-GE复合光催化剂对亚甲基蓝及罗丹明B光催化降解性能。结果表明:石墨烯的引入提高了TiO2的光催活性,这主要是得益于石墨烯优异的电子传输性能及较好吸附特性。不同方法制备TiO2-GE复合催化剂的光催化活性也存在较大差别。原位制备的TiO2-GE复合光催化剂表现出最佳的光催化活性。     

CNTs表面改性与TiO2-CNTs异质结光催化性能

碳纳米管(CNTs)混酸(H₂SO₄/HNO₃, 体积比为3:1)超声辅助纯化及氧化植入活性基团－COOH, 进一步借助其转化为酰氯基团, 分别于CNTs 表面共价嫁接亲水性赖氨酸及亲脂性正十八胺基团, 赋予赖氨酸表面改性CNTs 显著水溶(6.85 mg·mL-1)和十八胺表面改性CNTs 显著醇溶(10.15 mg·mL^-1)性能. 运用低温水热法以亲水性CNTs 复合TiO₂, 溶胶-凝胶法以亲脂性CNTs 复合TiO₂, 观察到复合催化剂光催化性能随CNTs 溶剂分散性能增加而明显提升. 运用傅里叶变换红外(FTIR)、激光拉曼、X射线衍射(XRD)、Brunauer-Emmett-Teller 低温氮气吸附、透射电镜(TEM)及X光电子能谱(XPS)等手段表征, 系统探讨CNTs 的表面改性机制及CNTs 溶解分散性能与复合催化剂的光活性的关联. 认为表面改性CNTs 借助Ti－O－C键合促进其与纳米TiO₂的异质结合, 从而充分利用CNTs的大比表面积及电荷传输性能促进催化剂的污染物光催化降解.     

Preparation and photocatalytic activity of Sb2S3/Bi2S3 doped TiO2 from complex precursor via gel-hydrothermal treatment

Sb₂S₃/Bi₂S₃ doped TiO₂ were prepared with the coordination compounds [M(S₂CNEt)₃] (M=Sb, Bi; S₂CNEt=pyrrolidinedithiocarbamate) as precursors via gel-hydrothermal techniques. The doped TiO₂ were characterized by XRD, SEM, XPS and UV-vis diffuse reflectance means. The photocatalyst based on doped TiO₂ for photodecolorization of 4-nitrophenol (4-NP) was examined. The optimal Bi₂S₃/Sb₂S₃ content, pH and different doped techniques have been investigated. Photocatalytic tests reveal that M₂S₃ doped TiO₂ via the gel-hydrothermal route performs better photocatalytic activity for photodegradation reaction of 4-nitrophenol (4-NP).     

Zeta potential of shape-controlled TiO2 nanoparticles with surfactants

Zeta potential of shape- and size-controlled TiO₂ nanoparticles obtained with the introduction of surfactants during synthesis was measured at different pH values. A unique finding is that TiO₂ nanoparticles shaped by sodium dodecyl sulfate (SDS) have double isoelectric points (IEPs), while other shape-controlled TiO₂ nanoparticles have only one IEP. The double IEPs might be due to the complex chemistry of TiO₂ nanoparticles with the presence of impurities (Na, S, C, etc.). At neutral pH, shape- and size-controlled TiO₂ nanoparticles have more negative zeta potential values and lower IEPs than TiO₂ nanoparticles obtained without the addition of surfactants during synthesis and the commercial anatase TiO₂ nanoparticles Degussa P-25. The lower IEPs could be attributed to the presence of carbonates on particle surfaces. The IEP value of TiO₂ nanoparticles increases with an increase in calcination temperature. The results suggest that the zeta potential of TiO₂ nanoparticles can be manipulated with the addition of surfactants during the synthesis process.     

低温静电自组装法制备贵金属修饰TiO_2纳米结构薄膜及其增强的光催化性能(英文)

以碱-水热法在金属Ti片上原位生长了TiO2纳米结构(纳米花和纳米线)薄膜,并采用低温静电自组装方法将超细贵金属(金、铂、钯)纳米颗粒均匀沉积于多孔TiO2薄膜上.负载于Ti片上的贵金属/TiO2纳米结构薄膜具有一体化结构、多孔架构和高光催化活性.超高分辨率场发射扫描电子显微镜(FESEM)直接观察表明贵金属纳米颗粒在TiO2表面分布均匀,且颗粒之间相互分离,金、铂、钯纳米颗粒的平均粒径分别约为4.0、2.0和10.0nm.俄歇电子能谱(AES)纵深成分分析表明贵金属不仅沉积于薄膜表面,且大量分布于TiO2纳米结构薄膜内部,其深度超过580 nm.X射线光电子能谱(XPS)分析表明,经300°C下在空气中热处理后,纳米金仍保持金属态,纳米铂部分被氧化成PtOabs,而钯粒子则完全被氧化成氧化钯(PdO).以低温静电自组装法沉积贵金属,贵金属负载量可通过调节组装时间与溶胶pH值来控制.光催化降解甲基橙的结果表明,沉积的纳米金和铂能显著增加TiO2纳米结构薄膜的光催化活性,说明金和铂粒子可促进光生载流子的分离;但负载的PdO对TiO2薄膜的光催化性能增强几乎无作用.     

Aggregation Behavior of Titanium Dioxide Nanoparticles in Aqueous Environments

We report on the stability of titanium dioxide nanoparticles suspended in various aqueous solutions with and without the presence of a model organic contaminant—salicylic acid. The stability of the suspended nanoparticles was revealed by measuring the isoelectric point by means of zetapotential scans and measuring the growth kinetics of the hydrodynamic particle size by means of dynamic light scattering (DLS) under different pH conditions. Aggregated nanoparticle sizes were also examined using atomic force microscopy. It was found that salicylic acid had a dramatic impact on the aggregation behavior of TiO₂ nanoparticles, suggesting that salicylic acid adsorbs to TiO₂ nanoparticles surfaces.     

Photocatalytic Crystalline and Amorphous TiO2 Nanotubes Prepared by Electrospinning and Atomic Layer Deposition

In this work core/shell composite polymer/TiO₂ nanofibers and from those TiO₂ nanotubes were prepared. First, poly(vinyl alcohol) (PVA) and poly(vinylpyrrolidone) (PVP) fibers were synthetized by electrospinning. They were covered with a 100 nm thick amorphous TiO₂ layer by atomic layer deposition at 50 °C. Later the polymer core was removed by two different methods: dissolution and annealing. In the case of dissolution in water, the as-prepared TiO₂ nanotubes remained amorphous, while when annealing was used to remove the polymers, the TiO₂ crystallized in anatase form. Due to this, the properties of amorphous and crystalline TiO₂ nanotubes with exactly the same structure and morphology could be compared. The samples were investigated by SEM-EDX, ATR-IR, UV-Vis, XRD and TG/DTA-MS. Finally, the photocatalytic properties of the TiO₂ nanotubes were studied by decomposing methyl-orange dye under UV light. According to the results, crystalline anatase TiO₂ nanotubes reached the photocatalytic performance of P25, while amorphous TiO₂ nanotubes had observable photocatalytic activity.