Photocatalytic activity and biodegradation of polyhydroxybutyrate films containing titanium dioxide

This study aims to evaluate the photocatalytic activity and biodegradation of polyhydroxybutyrate (PHB) films containing titanium dioxide (TiO₂). Nanosized TiO₂ photocatalysts were immobilized onto PHB film to overcome the difficulty of the recovery process. PHB is a suitable base material as it is naturally biodegradable and is produced from renewable resources. The photocatalytic degradation of organic compounds, photocatalytic sterilization activity and biodegradation rate in garden soil of PHB-TiO₂ composite films were investigated. After an hour under solar illumination, 96% of methylene blue solution was decolorized. The antibacterial activity against Escherichia coli (E. coli) using PHB-TiO₂ composite film exhibited enhanced photocatalytic sterilization activity over time. As for the ability to biodegrade, PHB-TiO₂ composite films placed on soil surface with no direct solar illumination showed slower degradation rate compared to those receiving direct solar illumination. Interestingly, the latter composite films showed faster degradation rates compared to pure PHB films indicating that the degradation is mainly due to photocatalytic activity. PHB-TiO₂ composite films buried in soil generally showed slower degradation rates compared to pure PHB films and were dependent on the soil microbial activity.     

Degradation of estrogen conjugates using titanium dioxide as a photocatalyst.

Estrogen conjugates (estradiol-3-glucuronide, -17-glucuronide, estrone-glucuronide and -sulfate) were subjected to photodegradation using titanium dioxide immobilized on glass beads as a catalyst. Their time courses were measured by HPLC and compared with those of the unconjugated estrogens. Estradiol, its 17-glucuronide and estrone, which have an unconjugated phenolic hydroxy group at the C-3 position, were almost completely degraded by UV irradiation within 4 h. On the other hand, significant amounts of estradiol- and estrone-3-glucuronide (ca. 20%, 25%) and estrone sulfate (ca. 90%), which were conjugated at the 3-hydroxy group, remained after a 6.5 h irradiation. These results supported the hypothesis that the photodegradation of estrogens was initiated at the phenolic hydroxy group.     

Photocatalytic degradation of 1,5-naphthalenedisulfonate on colloidal titanium dioxide

Photocatalytic degradation of 1,5-naphthalenedisulfonate (NDS) was investigated by monitoring the absorption and emission spectral changes, chemical oxygen demand, total organic carbon (TOC) content as well as pH and sulfate concentration. Intermediates formed during the irradiation were also detected by liquid chromatographic-mass spectrometric analysis. The results obtained by the applied analytical techniques clearly indicate that the initial step of degradation is oxygenation (hydroxylation) of the starting surfactant resulting in the formation of an 8-hydroxy derivative, although desulfonation and some mineralization, that is, decrease of TOC indicating carbon dioxide generation, also take place at this stage. Further oxygenation and desulfonation lead to the destruction of the diaromatic naphthalene system, then to ring fission, producing diols, aldehydes, and carboxylic acids on the side-chains. A tentative scheme involving possible pathways of degradation is proposed, taking the intermediates detected by mass spectrometry into consideration. On the basis of the results of quantum chemical calculations, the most possible points of attack by HO radical were identified, supplementing the MS results, and elucidating the initial oxidation step in the degradation of NDS and the benzenesulfonate (BS) intermediate. Thus, in the case of NDS para position is favored for hydroxylation, while for BS, formation of the ortho-hydroxy derivative is preferred.     

N掺杂TiO2对聚乙烯复合薄膜的光催化降解研究

以快速溶胶-凝胶法制备了具有不同N掺杂量的TiO2光催化剂,在室温光照240 h条件下,用于固相光催化降解碳酸钙填充聚乙烯复合材料薄膜;采用X射线光电子能谱仪(XPS)、X射线衍射仪(XRD)、紫外-可见光漫反射仪(UV-Vis)、傅立叶变换红外光谱仪(FTIR)、扫描电子显微镜(SEM)等手段分析了催化剂和薄膜的形貌...     

A plasmonic photocatalyst consisting of silver nanoparticles embedded in titanium dioxide

Titanium dioxide (TiO2) displays photocatalytic behavior under near-ultraviolet (UV) illumination. In another scientific field, it is well understood that the excitation of localized plasmon polaritons on the surface of silver (Ag) nanoparticles (NPs) causes a tremendous increase of the near-field amplitude at well-defined wavelengths in the near UV. The exact resonance wavelength depends on the shape and the dielectric environment of the NPs. We expected that the photocatalytic behavior of TiO2 would be greatly boosted if it gets assisted by the enhanced near-field amplitudes of localized surface plasmon (LSP). Here we show that this is true indeed. We named this new phenomenon "plasmonic photocatalysis". The key to enable plasmonic photocatalysis is to deposit TiO2 on a NP comprising an Ag core covered with a silica (SiO2) shell to prevent oxidation of Ag by direct contact with TiO2. The most appropriate diameter for Ag NPs and thickness for the SiO2 shell giving rise to LSP in the near UV were estimated from Mie scattering theory. Upon implementing a device that took these design considerations into account, the measured photocatalytic activity under near UV illumination of such a plasmonic photocatalyst, monitored by decomposition of methylene blue, was enhanced by a factor of 7. The enhancement of the photocatalytic activity increases with a decreased thickness of the SiO2 shell. The plasmonic photocatalysis will be of use as a high performance photocatalyst in nearly all current applications but will be of particular importance for applications in locations of minimal light exposure.     

Photocatalytic degradation of dimethyl terephthalate in aqueous suspensions of titanium dioxide

The photocatalytic degradation of dimethyl terephthalate (DMT, 1) has been investigated in aqueous suspensions of titanium dioxide (TiO2) by monitoring the depletion of Total Organic Carbon (TOC) content as a function of irradiation time under a variety of conditions. The degradation kinetics were studied using different parameters such as pH, substrate and photocatalyst concentration, a different kind of titanium dioxide and the presence of electron acceptors such as H2O2, KBrO3 and (NH4)2S2O8 in addition to molecular oxygen. The photocatalytic activity was better for Degussa P25 as compared to the other photocatalysts. From the obtained kinetic data a detailed account of the influence of various parameters on the degradation rate for the mineralization of the compound is given. The degradation products were analyzed using the GC/MS technique and probable pathways for the formation of different products have been proposed.     

Photocatalytic lithography based on thin films of amorphous hydrated titanium dioxide

The mechanism of photoactivation of amorphous hydrated titanium dioxide thin films containing palladium ions toward the reaction of electroless deposition of nickel was studied. It was shown that the photocatalytic reduction of palladium ions during UV irradiation results in the formation of intermediate Pd(I) states that subsequently disproportionate, yielding a Pd nanophase. The palladium nanoparticle-catalyzed electroless deposition of nickel on exposed areas of the titanium dioxide photolayer makes it possible to fabricate metal patterns having a 5-μm resolution, with the fast and irreversible capture of photoelectrons at the latent image formation step preventing the image from blurring, including the process on conducting substrates.     

纳米二氧化钛粉体及薄膜制备的研究进展

本文对近几年有关纳米二氧化钛粉体及薄膜的制备研究进行综述。重点介绍及评述了以无机钛盐和有机钛盐为前驱体制备纳米二氧化钛粉体及利用自组装方法制备二氧钛薄膜的最新研究成果。对今后研究工作的趋势进行了探讨。     

Photocatalytic carbon dioxide reduction by photocatalyst innovation

The photocatalytic conversion of carbon dioxide into sustainable fuel methanol using carbon quantum dots is highlighted in this paper. The multifaceted roles of carbon quantum dots in photocatalytic reactions and future directions of CQD materials are outlined.     

Photocatalytic degradation of anionic surfactant using zinc oxide nanoparticles

In this paper the photocatalytic degradation of anionic surfactant LABS was studied by a batch process using ZnO nanoparticles with diameter size of 20 nm catalyst on irradiation with UV light and their behavior comparatively examined with respect to ZnO commercial powder. The effect of parameters such as initial surfactant concentration, initial solution pH has been studied. Also degradation at LABS in the presence of an electron acceptor like potassium peroxydisulfate and effect of anion presence on surfactant degradation has been systematically investigated. The obtained result demonstrated a high photocatalytic activity of nanosize semiconducting particles.     

Photocatalytic activity of titanium dioxide nanoparticles produced by methods of high-energy physical dispersion

Photocatalytic activity of titanium dioxide nanoparticle samples under study is almost uncorrelated with their phase composition and, in particular, with the content of the anatase phase. The photocatalytic activity depends on the annealing temperature of the nanoparticles. The photocatalytic activity is positively affected by an ultrasonic radiation of the nanoparticles. The highest photocatalytic activity, comparable with that of the AEROXIDE P25 reference nanopowders, is observed for nanoparticles produced by a method of electrical explosion of wires.     

Photocatalytic degradation of wastewater pollutants: titanium dioxide mediated degradation of methyl orange and beta-naphthol orange

The photocatalytic degradation of azo dyes such as methyl orange and beta-naphthol orange in aqueous suspensions of TiO2 has been investigated under a variety of conditions. The kinetics of degradation was studied under different conditions such as reaction pH, substrate and catalyst concentration, and types of titanium dioxide used and in the presence of electron acceptors and electron donors. The degradation rates of the dyes have been found to be strongly influenced by all the above parameters. Carbon dioxide yield measurements indicate that only partial mineralization occurs in the initial phase of oxidation.     

Characterization of titanium dioxide nanoparticles using molecular dynamics simulations

Molecular dynamics simulations of titanium dioxide nanoparticles in the three commonly occurring phases (anatase, brookite, and rutile) are reported. The structural properties inferred by simulated X-ray diffraction patterns of the nanoparticles were investigated. The titanium-oxygen bond length as a function of size, phase, and temperature was determined and was found to be dependent on the coordination environment of the titanium and independent of phase and size. The equilibrium Ti-O bond length is 1.86 A for a four-coordinated titanium ion, 1.92 A for a five-coordinated titanium ion, and 1.94 A for an octahedral titanium ion. Smaller nanoparticles are characterized by a higher fraction of titanium ions that are four and five coordinated, due to the larger surface area-to-volume ratios. The surface energies for anatase, rutile, and brookite particles were reported. The surface energy of the nanoparticle increases and approaches a constant value as the particle gets bigger. The surface energies of small rutile particles are higher than that for anatase particles of a similar size, consistent with anatase being the more stable phase of nanocrystalline titanium dioxide.     

Nickel(II) oxide surface-modified titanium(IV) dioxide as a visible-light-active photocatalyst

The electronic modification of TiO(2) with highly dispersed NiO particles smaller than ca. 2 nm by the chemisorption-calcination-cycle technique has given rise to a high level of visible-light-activity exceeding that of iron oxide-surface modified TiO(2) simultaneously with the UV-light-activity being significantly increased.     

纳米多孔二氧化钛电极辅助光电化学降解乙酰氨基酚及伐昔洛韦

作为一类具有较高生物活性的物质,药物及个人护理品对环境的污染引起人们越来越多的关注.对乙酰氨基酚和伐昔洛韦是两种使用广泛的药物,由于其潜在的对人类健康和生态安全的威胁而逐渐成为研究热点.而电化学辅助光氧化技术因其具备能够高效处理难降解化学品的优点而得到广泛使用.本文合成了纳米多孔二氧化钛电极,研究了电化学还原处理对纳米多孔二氧化钛电极辅助光电化学降解对乙酰氨基酚和伐昔洛韦的影响.使用扫描电镜和色散谱技术对合成的纳米多孔二氧化钛电极的形态和元素组成进行了表征.循环伏安法、莫特-肖特基曲线、紫外-可见分光光度计和总有机碳分析仪被用来研究对乙酰氨基酚和伐昔洛韦的光电化学降解过程.结果显示,对乙酰氨基酚和伐昔洛韦的光化学降解和电化学降解过程非常缓慢,在研究的时间范围内其浓度未见明显变化,因此可以忽略不计.但是对乙酰氨基酚和伐昔洛韦的光电化学降解速度比较快,与未经处理的纳米多孔二氧化钛电极相比,经过电化学还原处理的电极可以使对乙酰氨基酚和伐昔洛韦的光电化学降解分别提高86.96%和53.12%.这可能是由于在电化学还原处理过程中生成了Ti3+, Ti2+和氧空位以及导电性的提高.还研究了温度对对乙酰氨基酚和伐昔洛韦光电化学降解的影响,随着温度升高,对乙酰氨基酚和伐昔洛韦的光电化学降解速率增大.     

Photocatalytic degradation of dimethyl phthalate ester using novel hydrophobic TiO2 pillared montmorillonite photocatalyst

TiO₂ pillared montmorillonites were prepared by introducing Ti⁴⁺ into a layer of montmorillonite modified with or without cetyltrimethylammonium bromide. The components and texture of the prepared composites were characterized by thermogravimetric analysis, X-ray powder diffraction and scanning electron misroscopy. The adsorption and photocatalytic degradation performance of a model environmental endocrine disruptor, dimethyl phthalate ester, were investigated using this newly prepared hydrophobic TiO₂ pillared montmorillonite photocatalyst. The adsorption of dimethyl phthalate ester from water varied from 9% to 28% on the prepared hydrophobic photocatalyst. Although the experimental results showed that the photocatalytic activity of the hydrophobic photocatalyst was slightly lower than that of hydrophilic one, electron spin resonance verified that hydroxyl radicals were also generated in hydrophobic TiO₂ pillared montmorillonite photocatalyst under UV irradiation. To elucidate the decomposition mechanism of dimethyl phthalate ester, 12 main photocatalytic intermediates were identified during the photocatalytic degradation process, and a plausible degradation mechanism was also proposed.     

Simultaneous separation of eight beta-adrenergic drugs using titanium dioxide nanoparticles as additive in capillary electrophoresis

The analysis is described for separating seven beta-adrenergic blocking agents (atenolol, celiprolol, clorprenaline, fenoterol, metoprolol, propranolol, terbutaline) and clenbuterol (sympathomimetic beta-2 receptor stimulating agonist, decongestant and bronchodilator, illicit anabolic used in athletics) by CE with UV detection. In order to simultaneously separate all analytes, Tris-H3PO4 solution was applied containing titanium dioxide nanoparticles (TiO2 NPs) as BGEs. The effects of important factors, such as concentration of TiO2 NPs, optimum pH, run buffer concentration, and separation voltage, were investigated so as to achieve best CE separation. The eight analytes could be well separated applying a separation voltage of 15 kV in 75 mM Tris-H3PO4 buffer at a pH of 2.40, containing 6.0 x 10(-6) g/mL TiO2 NPs. Under these optimal conditions, the RSDs for peak areas and for migration times were less than 2.7 and 2.3%, respectively. The detection limits were 0.1 microg/mL for celiprolol, 0.1 microg/mL for propranolol, 0.2 microg/mL for fenoterol, 1.0 microg/mL for atenolol, 1.0 microg/mL for clenbuterol, 1.0 microg/mL for clorprenaline, 1.0 microg/mL for metoprolol, and 1.0 microg/mL for terbutaline. The proposed method was successfully applied for the rapid CE determination of the frequently applied antihypertensive beta-blocking compounds atenolol, metoprolol, terbutaline, and propranolol in pharmaceutical tablets.     

Thermodynamic aspects of fibroblastic spreading on diamond-like carbon films containing titanium dioxide nanoparticles

The combination of low friction, wear resistance, high hardness, biocompatibility, and chemical inertness makes diamond-like carbon (DLC) films suitable in numerous applications in biomedical engineering. The cytotoxicity of DLC films containing TiO₂ nanoparticles was practical and theoretically evaluated. The films were grown on 316L stainless steel substrates from a dispersion of TiO₂ nanopowder in hexane. Raman spectroscopy shows that the presence of TiO₂ increased the graphite-like bonds in the films. The incorporation of TiO₂ nanoparticles into DLC films increases surface roughness, decreases water contact angle (increased hydrophilic character), and increases the total free surface energy due to the higher polar component. As the concentration of TiO₂ increased, the films increased the cell viability (MTT assay), becoming more thermodynamically favorable to cell spreading (??F _Adh values became more negative). This was evidenced through the increasing number of projections (philopodia and lamellipodia), indicating a higher adhesion between the L929 cells and the films. The practical and theoretical findings of this study show that the incorporation of TiO₂ into DLC films is effective in enhancing cell viability. These results show the potential use of DLC and TiO₂-DLC films in biomedical applications.