Photocatalytic destruction of geosmin using novel pelleted titanium dioxide

Geosmin is produced by cyanobacteria and actinomycetes in surface waters. It causes undesirable earthy off-flavours in freshwater fish and is a major concern for the drinking water industry. This paper presents the first published study on the use of the novel pelleted Ti0₂ photocatalyst, Hombikat K01/C, for the removal of geosmin from water. Ti0₂ in pelleted form eliminates the requirement for the separation of the catalyst from the water following treatment which is normally the case with the widely used powdered catalysts. A laboratory reactor was designed to limit system loss since the compound adsorbs to a wide range of surfaces. Initial concentration, aeration rate and irradiation were evaluated. It was found that degradation of geosmin followed the Langmuir-Hinshelwood model. Elevated aeration had no effect on the photocatalytic removal of geosmin, but increasing irradiation was found to increase degradation rates. The catalyst proved effective within 10 min under optimum conditions. 

The application of Raman and anti-stokes Raman spectroscopy for in situ monitoring of structural changes in laser irradiated titanium dioxide materials

The use of Raman and anti-stokes Raman spectroscopy to investigate the effect of exposure to high power laser radiation on the crystalline phases of TiO₂ has been investigated. Measurement of the changes, over several time integrals, in the Raman and anti-stokes Raman of TiO₂ spectra with exposure to laser radiation is reported. Raman and anti-stokes Raman provide detail on both the structure and the kinetic process of changes in crystalline phases in the titania material. The effect of laser exposure resulted in the generation of increasing amounts of the rutile crystalline phase from the anatase crystalline phase during exposure. The Raman spectra displayed bands at 144 cm^-1 (A1g), 197 cm^-1 (Eg), 398 cm^-1 (B1g), 515 cm^-1 (A1g), and 640 cm^-1 (Eg) assigned to anatase which were replaced by bands at 143 cm^-1 (B1g), 235 cm^-1 (2 phonon process), 448 cm^-1 (Eg) and 612 cm^-1 (A1g) which were assigned to rutile. This indicated that laser irradiation of TiO₂ changes the crystalline phase from anatase to rutile. Raman and anti-stokes Raman are highly sensitive to the crystalline forms of TiO₂ and allow characterisation of the effect of laser irradiation upon TiO₂. This technique would also be applicable as an in situ method for monitoring changes during the laser irradiation process

On-line monitoring of laser modification of titanium dioxide using optical surface second harmonic

TiO₂ photocatalysis is a promising technology for the destruction of organic pollutants in both waste and potable waters with the mineralisation of a wide range of compounds having been reported. TiO ₂ has many advantages over other semiconductors, it is highly photoreactive, cheap, non-toxic, chemically and biologically inert, and photostable. The photocatalytic activity of TiO₂ has been shown to depend upon many criteria including the ratio of anatase/rutile crystal phase, particle size and oxidation state. This paper reports the use of optical surface second harmonic generation (SSHG) to monitor modifications in TiO ₂ powder induced following laser treatment. SSHG is a non-contact, non-destructive technique, which is highly sensitive to both surface chemical and physical changes. Results show that three different SSH intensities were observable as the TiO₂ samples were irradiated with the laser light. These regions were related to changes in chemical characteristics and particle size of the TiO₂ powder

The destruction of 2-methylisoborneol and geosmin using titanium dioxide photocatalysis

Geosmin (GSM) and 2-methylisoborneol (MIB) are semi-volatile compounds produced by cyanobacteria in surface waters. These compounds present problems to the drinking water industry and in aquaculture because they can taint water and fish producing an earthy-musty flavour. This paper presents an initial study on the use of TiO₂ photocatalysis for the destruction of these compounds in water. The process proved effective with the complete destruction of MIB and GSM being achieved within 60 min. These results suggest that TiO₂ photocatalysis will be a successful method for removal of taint compounds from potable water supplies and fish farms. 

Processes influencing surface interaction and photocatalytic destruction of microcystins on titanium dioxide photocatalysts

Microcystins are a family of hepatotoxic peptides produced by freshwater cyanobacteria. Their occurrence in drinking water is of concern since chronic exposure to these toxins causes tumor promotion. It is therefore essential to establish a reliable treatment strategy that will ensure their removal from potable water. We have previously described the rapid destruction of microcystin-LR using TiO₂ photocatalysis, however, since there are at least 70 microcystin variants it is essential that the destruction of a number of microcystins be evaluated. In this study the dark adsorption and destruction of four microcystins was followed over a range of pH. All four microcystins were destroyed although the efficiency of their removal varied. The two more hydrophobic microcystins (-LW and -LF) were found to have high dark adsorption (98 and 91% at pH 4) in contrast to microcystin-RR, which was found to have almost no (only 2-3%) dark adsorption across all pH. 

Hydrogen peroxide enhanced photocatalytic oxidation of microcystin-lR using titanium dioxide

Cyanobacterial toxins present in drinking water sources pose a considerable threat to human health. Conventional water treatment systems have proven unreliable for the removal of these toxins and hence new techniques have been investigated. Previous work has shown that TiO₂ photocatalysis effectively destroys microcystin-LR in aqueous solutions, however non-toxic by-products were detected. It has been shown that photocatalytic reactions are enhanced by utilisation of alternative electron acceptors. We report here enhanced photocatalytic degradation of microcystin-LR following the addition of hydrogen peroxide to the system. It was also found that hydrogen peroxide with UV illumination alone was capable of decomposing microcystin-LR although at a much slower rate than found for TiO₂. No HPLC detectable by-products were found when the TiO₂/UV/H₂O₂ system was used indicating that this method is more effective than TiO₂/UV alone. Results however indicated that only 18% mineralisation occurred with the TiO₂/UV/H₂O₂ system and hence undetectable by-products must still be present. At higher concentrations hydrogen peroxide was found to compete with microcystin-LR for surface sites on the catalyst but at lower peroxide concentrations this competitive adsorption was not observed. Toxicity studies showed that both in the presence and absence of H₂O₂ the microcystin solutions were detoxified. These findings suggest that hydrogen peroxide greatly enhances the photocatalytic oxidation of microcystin-LR.

The application of surface second harmonic sensor to probe laser induced modification of titanium dioxide

The effects of high power pulsed laser light on a TiO2 photocatalyst have been investigated using a surface second harmonic generation (SSHG) sensor. When TiO2 is irradiated with a laser at 355mm a visible change in colour from white to dark blue crystals was observed. X-ray diffraction studies indicate that the crystal structure of the TiO2 developed a more rutile form following laser exposure.

The Destruction of Cyanobacterial Toxins by Titanium Dioxide

Cyanobacterial (blue-green algal) toxins are extremely toxic naturally occurring substances which display hepato- and neurotoxic behaviour (1, 2). In this paper we report the application of titanium dioxide photocatalysis for the destruction of two of these compounds, microcystin-LR and anatoxin-a. The destruction of microcystin appears to follow Langmuir-Hinshelwood kinetics although a discrepancy was observed between adsorption constants determined for the photocatalytic process with those obtained from dark isotherms. A square root dependence between illumination intensity and rate of microcystin destruction was noted. When the destruction was performed in the presence of the naturally occurring pigment it appeared that the pigment also contributes to the destruction of the toxin. Toxicity studies on the photocatalysed toxin solutions indicates that the toxicity is substantially reduced within 30 min photolysis.

Suspension plasma sprayed coatings using dilute hydrothermally produced titania feedstocks for photocatalytic applications

Titanium dioxide coatings have potential applications including photocatalysts for solar assisted hydrogen production, solar water disinfection and self-cleaning windows. Herein, we report the use of suspension plasma spraying (SPS) for the deposition of conformal titanium dioxide coatings. The process utilises a nanoparticle slurry of TiO2 (ca. 6 and 12 nm respectively) in water, which is fed into a high temperature plasma jet (ca. 7000-20 000 K). This facilitated the deposition of adherent coatings of nanostructured titanium dioxide with predominantly anatase crystal structure. In this study, suspensions of nano-titanium dioxide, made via continuous hydrothermal flow synthesis (CHFS), were used directly as a feedstock for the SPS process. Coatings were produced by varying the feedstock crystallite size, spray distance and plasma conditions. The coatings produced exhibited ca. 90-100% anatase phase content with the remainder being rutile (demonstrated by XRD). Phase distribution was homogenous throughout the coatings as determined by micro-Raman spectroscopy. The coatings had a granular surface, with a high specific surface area and consisted of densely packed agglomerates interspersed with some melted material. All of the coatings were shown to be photoactive by means of a sacrificial hydrogen evolution test under UV radiation and compared favourably with reported values for CVD coatings and compressed discs of P25.

A solvent-based intelligence ink for oxygen

A solvent-based, irreversible oxygen indicator ink is described, comprising semiconductor photocatalyst nanoparticles, a solvent-soluble redox dye, mild reducing agent and polymer. Based on such an ink, a film - made of titanium dioxide, a blue, solvent-soluble, coloured ion-paired methylene blue dye, glycerol and the polymer zein - loses its colour rapidly (

Photochemical reduction of oxygen adsorbed to nanocrystalline TiO2 films: A transient absorption and oxygen scavenging study of different TiO2 preparations

Transient absorption spectroscopy (TAS) has been used to study the interfacial electron-transfer reaction between photogenerated electrons in nanocrystalline titanium dioxide (TiO2) films and molecular oxygen. TiO2 films from three different starting materials (TiO2 anatase colloidal paste and commercial anatase/rutile powders Degussa TiO2 P25 and VP TiO2 P90) have been investigated in the presence of ethanol as a hole scavenger. Separate investigations on the photocatalytic oxygen consumption by the films have also been performed with an oxygen membrane polarographic detector. Results show that a correlation exists between the electron dynamics of oxygen consumption observed by TAS and the rate of oxygen consumption through the photocatalytic process. The highest activity and the fastest oxygen reduction dynamics were observed with films fabricated from anatase TiO2 colloidal paste. The use of TAS as a tool for the prediction of the photocatalytic activities of the materials is discussed. TAS studies indicate that the rate of reduction of molecular oxygen is limited by interfacial electron-transfer kinetics rather than by the electron trapping/detrapping dynamics within the TiO2 particles.

The photo-oxidation of water by sodium persulfate, and other electron acceptors, sensitised by TiO2

A number of different electron acceptors are tested for efficacy in the oxidation of water to oxygen, photocatalysed by titanium dioxide. The highly UV-absorbing metal ion electron acceptors, Ce4+ and Fe3+, appear ineffective at high concentration (10(-2) M), due to UV-screening, but more effective at lower concentrations (10(-3) M). The metal-depositing electron acceptor, Ag+, is initially effective, but loses activity upon prolonged irradiation due to metal deposition which promotes electron-hole recombination as well as UV-screening the titania particles. Most striking of the electron acceptors tested is persulfate, particularly in alkaline solution (0.1 M NaOH). The kinetics of the photo-oxidation of water by persulfate, photocatalysed by titania are studied as a function of pH, [S2O82-] and incident light intensity (I). The initial rate of water oxidation increases with pH, is directly proportional to the concentration of persulfate present and depends upon I-0.6. The TiO2/alkaline persulfate photosystem is robust and shows very little evidence of photochemical wear upon repeated irradiation. The results of this work are discussed with regard to previous work in this area and current mechanistic thinking. The formal quantum efficiency of the TiO2/alkaline persulfate photosystem was estimated as ca. 2%. (C) 2004 Elsevier B.V. All rights reserved.