Ultraviolet Light-Induced Hydrophilicity Effect on TiO 2 (110)(1×1). Dominant Role of the Photooxidation of Adsorbed Hydrocarbons Causing Wetting by Water Droplets
Surface Science Center, Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15260, USA. The Journal of Physical Chemistry B
(Impact Factor: 3.3).
09/2005; 109(32):15454-62. DOI: 10.1021/jp058101c
The UV photoproduction of a hydrophilic TiO(2)(110)(1x1) surface has been investigated in a pressurized ultrahigh vacuum apparatus under controlled conditions of hydrocarbon concentration in oxygen gas at 1 atm pressure. Water droplet contact angles have been measured continuously as the droplet is exposed to UV irradiation, yielding the first observations of a sudden wetting process during irradiation. Using hexane as a model hydrocarbon, it is found that when low partial pressures of hexane are present, the sudden onset of surface wetting occurs during UV irradiation after an induction period under photooxidation conditions. The induction period to reach the critical condition for sudden wetting increases when the partial pressure (and equilibrium surface coverage) of hexane is increased. These results indicate that the removal of adsorbed hydrocarbons by photooxidation is the critical factor leading to the UV-induced hydrophilicity phenomenon on TiO(2). The phenomenon does not occur in the absence of O(2) gas. A concept concerned with kinetic screening of the TiO(2)-H(2)O interface from O(2) by water droplets is presented to explain the observation of sudden wetting in our experiments, compared to gradual wetting which is observed following UV irradiation in all other experiments reported in the literature. Complementary infrared spectroscopy measurements of the effect of UV irradiation in an O(2) atmosphere on adsorbed Ti-OH groups and on adsorbed H(2)O on the surface of a high-area TiO(2) powder show that no spectroscopic changes occur. This indicates that UV-induced changes in the -OH coverage or the nature of -OH bonding to TiO(2), as suggested by others, cannot be used to explain the photoinduced hydrophilicity effect.
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- "Titanium dioxide (TiO 2 ) as photocatalyst has been widely used for industrial and medical applications due to its useful physical and biological properties in the last two decades, such as disposal of wastewater, decontamination of air pollutants , and sterilization of bacteria    . It has been well known that photoinduced electrons and holes could be generated on the TiO 2 surface under exposure to ultraviolet (UV) light  . These excited electrons and holes have strong reduction and oxidation activities and could further react with hydroxyl ions or water resulting in the formation of various reactive oxygen species (ROS) which have been proved to significantly damage cancer cells   . "
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ABSTRACT: The Fe-N co-doped TiO2 nanocomposites were synthesized by a sol-gel method and characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray diffraction (XRD), ultraviolet-visible absorption spectroscopy (UV-vis) and X-ray photoelectron spectroscopy (XPS). Then the photocatalytic inactivation of Fe-N-doped TiO2 on leukemia tumors was investigated by using Cell Counting Kit-8 (CCK-8) assay. Additionally, the ultrastructural morphology and apoptotic percentage of treated cells were also studied. The experimental results showed that the growth of leukemic HL60 cells was significantly inhibited in groups treated with TiO2 nanoparticles and the photocatalytic activity of Fe-N-TiO2 was significantly higher than that of Fe-TiO2 and N-TiO2, indicating that the photocatalytic efficiency could be effectively enhanced by the modification of Fe-N. Furthermore, when 2 wt% Fe-N-TiO2 nanocomposites at a final concentration of 200 μg/mL were used, the inactivation efficiency of 78.5% was achieved after 30-minute light therapy.
Available from: Yoshihiko Sugita
- "The nature of a TiO2 layer hypothetically includes the architecture (ie, in nanonodular form), thickness (eg, it should be 300-nm thick or more), and surface area (eg, the larger, the better). Exposing TiO2 to UV light results in the excitement of an electron from the valence band to the conduction band.20,21 This physicochemical change – the excited electron along with the positive hole created in the superficial layer of TiO2 – is part of the explanation for why UV-mediated photocatalysis occurs. "
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ABSTRACT: Bioactivity and osteoconductivity of titanium degrade over time after surface processing. This time-dependent degradation is substantial and defined as the biological aging of titanium. UV treatment has shown to reactivate the aged surfaces, a process known as photofunctionalization. This study determined whether there is a difference in the behavior of biological aging for titanium with micro-nano-hybrid topography and titanium with microtopography alone, following functionalization. Titanium disks were acid etched to create micropits on the surface. Micro-nano-hybrid surfaces were created by depositioning 300-nm diameter TiO(2) nodules onto the micropits using a previously established self-assembly protocol. These disks were stored for 8 weeks in the dark to allow sufficient aging, then treated with UV light for 48 hours. Rat bone marrow-derived osteoblasts were cultured on fresh disks (immediately after UV treatment), 3-day-old disks (disks stored for 3 days after UV treatment), and 7-day- old disks. The rates of cell attachment, spread, proliferation, and levels of alkaline phosphatase activity, and calcium deposition were reduced by 30%-50% on micropit surfaces, depending on the age of the titanium. In contrast, 7-day-old hybrid surfaces maintained equivalent levels of bioactivity compared with the fresh surfaces. Both micropit and micro-nano-hybrid surfaces were superhydrophilic immediately after UV treatment. However, after 7 days, the micro-nano- hybrid surfaces became hydrorepellent, while the micropit surfaces remained hydrophilic. The sustained bioactivity levels of the micro-nano-hybrid surfaces were nullified by treating these surfaces with Cl(-)anions. A thin TiO(2) coating on the micropit surface without the formation of nanonodules did not result in the prevention or alleviation of the time-dependent decrease in biological activity. In conclusion, the micro-nano-hybrid titanium surfaces may slow the rate of time-dependent degradation of titanium bioactivity after UV photofunctionalization compared with titanium surfaces with microtopography alone. This antibiological aging effect was largely regulated by its sustained electropositivity uniquely conferred in TiO(2) nanonodules, and was independent of the degree of hydrophilicity. These results demonstrate the potential usefulness of these hybrid surfaces to effectively utilize the benefits of UV photofunctionalization and provide a model to explore the mechanisms underlying antibiological aging properties.
Available from: Radim Beranek
- "In following years further photochemical applications of TiO 2 have been realized, most of them motivated particularly by the advantageous combination of its low cost, nontoxicity, and excellent stability against photocorrosion. One important example is the rapidly growing field of heterogeneous photocatalysis         , in which TiO 2 has been successfully employed in photooxidation reactions utilizing aerobic oxygen for the complete removal of pollutants from water and air [17–22, 24–39], in preparation of superhydrophilic and antifogging surfaces    , in photocatalytic organic syntheses [44– 49], or in antitumor medicinal applications     . "
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ABSTRACT: TiO2-based nanomaterials play currently a major role in the development of novel photochemical systems and devices. One of the key parameters determining the photoactivity of TiO2-based materials is the position of the band edges. Although its knowledge is an important prerequisite for understanding and optimizing the performance of photochemical systems, it has been often rather neglected in recent research, particularly in the field of heterogeneous photocatalysis. This paper provides a concise account of main methods for the determination of the position of the band edges, particularly those suitable for measurements on nanostructured materials. In the first part, a survey of key photophysical and photochemical concepts necessary for understanding the energetics at the semiconductor/solution interface is provided. This is followed by a detailed discussion of several electrochemical, photoelectrochemical, and spectroelectrochemical methods that can be applied for the determination of band edge positions in compact and nanocrystalline thin films, as well as in nanocrystalline powders.
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