An investigation into the effect of thickness of titanium dioxide and gold-silver nanoparticle titanium dioxide composite thin-films on photocatalytic activity and photo-induced oxygen production in a sacrificial system

Thin films of titanium dioxide and titanium dioxide with incorporated gold and silver nanoparticles were deposited onto glass microscope slides, steel and titanium foil coupons by two sol-gel dip-coating methods. The film's photocatalytic activity and ability to evolve oxygen in a sacrificial solution were assessed. It was found that photocatalytic activity increased with film thickness (from 50 to 500 nm thick samples) for the photocatalytic degradation of methylene blue in solution and resazurin redox dye in an intelligent ink dye deposited on the surface. Contrastingly, an optimum film thickness of similar to 200 nm for both composite and pure films of titanium dioxide was found for water oxidation, using persulfate (S2O82-) as a sacrificial electron acceptor. The nanoparticle composite films showed significantly higher activity in oxygen evolution studies compared with plain TiO2 films.

Thick titanium dioxide films for semiconductor photocatalysis

Thick paste TiO2 films are prepared and tested for photocatalytic and photoinduced superhydrophilic (PSH) activity. The films are effective photocatalysts for the destruction of stearic acid using near or far UV and all the sol-gel films tested exhibited a quantum yield for this process of typically 0.15 %. These quantum yields are significantly greater (4-8-fold) than those for titania films produced by an APCVD technique, including the commercial self-cleaning glass product Activ(TM). The films are mechanically robust and optically clear and, as photocatalysts for stearic acid removal, are photochemically stable and reproducible. The kinetics of stearic acid photomineralisation are zero order with an activation energy of ca. 2.5 Kj mol(-1). All titania films tested, including those produced by APCVD, exhibit PSH. The light-induced fall, and dark recovery, in the water droplet contact angle made with titania paste films are similar in profile shape to those described by others for thin titania films produced by a traditional sol-gel route. (C) 2003 Elsevier Science B.V. All rights reserved.

Photodecomposition of ozone sensitised by a film of titanium dioxide on glass

High levels of ozone (typically 850 ppm) are readily decomposed by semiconductor photocatalysis, using a thin film of the semiconductor titanium dioxide (Degussa P25 TiO2) cast on a glass tube, and UVA light, i.e. light of energy greater than that of the bandgap of the semiconductor (ultra-bandgap light); in the absence of this light the thermal decomposition of ozone is relatively slow. The semiconductor films show no evidence of chemical or photochemical wear with repeated use. At high levels of ozone, i.e. 100 ppm less than or equal to [O-3] less than or equal to 1400 ppm, the initial rate of ozone decomposition by semiconductor photocatalysis is independent of [O-3], whereas, at lower ozone concentrations, i.e. 5 ppm less than or equal to [O-3] less than or equal to 100 ppm, the initial rate of ozone photodestruction decreases in a smooth, but non-linear, manner with decreasing [O-3]. The kinetics of ozone photodecomposition fit a Langmuir-Hinshelwood type kinetic equation and the possible mechanistic implications of these results are briefly discussed. (C) 2002 Elsevier Science B.V. All rights reserved.

Atmospheric pressure chemical vapour deposition of titanium dioxide coatings on glass

Atmospheric pressure chemical vapour deposition of titanium dioxide coatings on glass substrates was achieved by the reaction of TiCl4 and a co-oxygen source (MeOH, EtOH, (PrOH)-Pr-i or H2O) at 500-650degreesC. The coatings show excellent uniformity, surface coverage and adherence. Growth rates were of the order of 0.3 mum min(-1) at 500degreesC. All films are crystalline and single phase with XRD showing the anatase TiO2 diffraction pattern; a = 3.78(1), c = 9.51(1) Angstrom. Optically, the films show minimal reflectivity from 300-1600 nm and 50-80% total transmission from 300-800 nm. Contact angles are in the range 20-40degrees for as-prepared films and 1-10degrees after 30 min irradiation at 254 nm. All of the films show significant photocatalyic activity as regards the destruction of an overlayer of stearic acid.

A KINETIC-STUDY OF THE BLEACHING OF RHODAMINE-6G PHOTOSENSITIZED BY TITANIUM-DIOXIDE

The results of a kinetic study of the bleaching of the photostable dye rhodamine 6G by dissolved oxygen, photosensitized by TiO2, are reported. The observed variations in the initial rate of dye photobleaching as a function of the O2 percentage, temperature, incident light intensity and concentrations of rhodamine 6G and sacrificial electron donor are described and the results are rationalized using a proposed photochemical reaction scheme. The photosensitized bleaching of rhodamine 6G dye by TiO2 has a formal quantum yield of 2.65 X 10(-3), but the rate of complete photomineralization is about twofold slower. The overall activation energy for the semiconductor-sensitized dye photobleaching process is 15.0 +/- 1.5 kJ mol-1.

PHOTOMINERALISATION OF 4-CHLOROPHENOL SENSITIZED BY TITANIUM-DIOXIDE - A STUDY OF THE EFFECT OF ANNEALING THE PHOTOCATALYST AT DIFFERENT TEMPERATURES

The results of a study of the variation in photocatalytic activity of TiO2, as measured by its ability to photomineralise 4-chlorophenol, as a function of temperature used to anneal the TiO2, are reported. Heat treatment of the TiO2 leads to a marked decrease in its photocatalytic activity at annealing temperatures above 600-degrees-C. This decrease is associated with a concomitant drop in the specific surface area of the TiO2, owing to particle sintering, rather than the anatase to rutile transformation, which occurs largely at temperatures above 700-degrees-C. There is a reasonable correlation between photocatalytic activity and the surface area of the aggregate particles in the dispersions of the different heat-treated TiO2 samples.

PHOTOMINERALIZATION OF 4-CHLOROPHENOL SENSITIZED BY TITANIUM-DIOXIDE - A STUDY OF THE INITIAL KINETICS OF CARBON-DIOXIDE PHOTOGENERATION

The kinetics of photomineralization of 4-chlorophenol (4-CP) sensitized by Degussa P25 TiO2 in O2-saturated solution is studied as a function of the following different experimental parameters: pH, [TiO2], percentage O2 [O2], [4-CP], T, I, lambda and [KNO3]. At pH 2 and T=30-degrees-C the initial relative rate of CO2 photogeneration R(CO2) conforms to a Langmuir-Hinshelwood-type kinetic scheme and the relationship between R(CO2) and the various experimental parameters may be summarized as follows: R(CO2) = gammaK(O2)[O2](I(a))(theta)K(4-CP]0/(1 + K(O2])(1 + K(4-CP)[4-CP]0) where gamma is a proportionality constant, K(O2) = 0.044 +/- 0.005[O2]-1, theta = 0.74 +/- 0.05 and K(4-CP) = (29 +/- 3) x 10(3) dm3 mol-1. The overall activation energy for this photosystem was determined as 16 +/- 2 kJ mol-1. This work forms part of an overall characterization study in which it is proposed that the 4-CP-TiO2-O2 photosystem is adopted as a standard test system for incorporation into all future semiconductor-sensitized photomineralization studies in order to facilitate comparisons between the results of the different studies.

PHOTOMINERALISATION OF 4-CHLOROPHENOL SENSITIZED BY TITANIUM-DIOXIDE - A STUDY OF THE INTERMEDIATES

The photomineralisation of 4-chlorophenol (4-CP) sensitised by Degussa P25 TiO2 in O2-saturated solution represents a possible standard test system in semiconductor-sensitised photomineralisation studies. As part of a detailed examination of this photosystem, the results of the temporal variations in the concentrations of 4-CP, CO2, Cl- and the major organic intermediates, namely, 4-chlorocatechol (4-CC), hydroquinone (HQ), benzoquinone and 4-chlororesorcinol, are reported. The observed variations in [4-CP], [4-CC], [HQ] and [CO2] fit those predicted by a kinetic model which utilises kinetic equations with a Langmuir-Hinshelwood form and assumes that there are three major possible routes in which the photogenerated hydroxyl radicals can react with 4-CP, ie. 4-CP --> 4-CC, 4-CP --> HQ and 4-CP --> (unstable intermediate) --> CO2 and that these routes have the following probabilities of occurring: 48%, 10% and 42%.

Phenol degradation by powdered metal ion modified titanium dioxide photocatalysts

Conventional water purification and disinfection generally involve potentially hazardous substances, some of which known to be carcinogenic in nature. Titanium dioxide photocatalytic processes provide an effective route to destroy hazardous organic contaminants. This present work explores the possibility of the removal of organic pollutants (phenol) by the application of TiO2 based photocatalysts. The production of series of metal ions doped or undoped TiO2 were carried out via a sol–gel method and a wet impregnation method. Undoped TiO2 and Cu doped TiO2 showed considerable phenol degradation. The efficiency of photocatalytic reaction largely depends on the photocatalysts and the methods of preparation the photocatalysts. The doping of Fe, Mn, and humic acid at 1.0 M% via sol–gel methods were detrimental for phenol degradation. The inhibitory effect of initial phenol concentration on initial phenol degradation rate reveals that photocatalytic decomposition of phenol follows pseudo zero order reaction kinetics. A concentration of > 1 g/L TiO2 and Cu doped TiO2 is required for the effective degradation of 50 mg/L of phenol at neutral pH. The rise in OH- at a higher pH values provides more hydroxyl radicals which are beneficial of phenol degradation. However, the competition among phenoxide ion, Cl- and OH- for the limited number of reactive sites on TiO2 will be a negative influence in the generation of hydroxyl radical. The dependence of phenol degradation rate on the light intensity was observed, which also implies that direct sunlight can be a substitute for the UV lamps and that photocatalytic treatment of organic pollutants using this technique shows some promise.

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.

Melt-compounded nanocomposites of titanium dioxide atomic-layer-deposition-coated polyamide and polystyrene powders

Polyamide and polystyrene particles were coated with titanium dioxide films by atomic layer deposition (ALD) and then melt-compounded to form polymer nanocomposites. The rheological properties of the ALD-created nanocomposite materials were characterized with a melt flow indexer, a melt flow spiral mould, and a rotational rheometer. The results suggest that the melt flow properties of polyamide nanocomposites were markedly better than those of pure polyamide and polystyrene nanocomposites. Such behavior was shown to originate in an uncontrollable decrease in the polyamide molecular weight, likely affected by a high thin-film impurity content, as shown in gel permeation chromatography (GPC) and scanning electron microscope (SEM) equipped with an energy-dispersive spectrometer. Transmission electron microscope image showed that a thin film grew on both studied polymer particles, and that subsequent melt-compounding was successful, producing well dispersed ribbon-like titanium dioxide with the titanium dioxide filler content ranging from 0.06 to 1.12wt%. Even though we used nanofillers with a high aspect ratio, they had only a minor effect on the tensile and flexural properties of the polystyrene nanocomposites. The mechanical behavior of polyamide nanocomposites was more complex because of the molecular weight degradation. Our approach here to form polymeric nanocomposites is one way to tailor ceramic nanofillers and form homogenous polymer nanocomposites with minimal work-related risks in handling powder form nanofillers. However, further research is needed to gauge the commercial potential of ALD-created nanocomposite materials. Copyright (C) 2011 John Wiley & Sons, Ltd.

An Investigation into the Optimum Thickness of Titanium Dioxide Thin Films Synthesized by Using Atmospheric Pressure Chemical Vapour Deposition for Use in Photocatalytic Water Oxidation

Twenty eight films of titanium dioxide of varying thickness were synthesised by using atmospheric pressure chemical vapour deposition (CVD) of titanium(IV) chloride and ethyl acetate onto glass and titanium substrates. Fixed reaction conditions at a substrate temperature of 660 degrees C were used for all depositions, with varying deposition times of 5-60 seconds used to control the thickness of the samples. A sacrificial electron acceptor system composed of alkaline sodium persulfate was used to determine the rate at which these films could photo-oxidise water in the presence of 365 nm light. The results of this work showed that the optimum thickness for CVD films on titanium substrates for the purposes of water oxidation was approximate to 200 nm, and that a platinum coating on the reverse of such samples leads to a five-fold increase in the observed rate of water oxidation.

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.