Visible-light-induced selective photocatalytic oxidation of benzylamine into imine over supported Ag/AgI photocatalysts

Titanate nanotubes (TNT) supported AgI nanoparticles were prepared by a two-step method: the deposition of Ag2O on titanate nanotubes from AgNO3 solution and the subsequent I-adsorption process from NaI solution. It is found that the supported AgI samples exhibited excellent photoactivity for the selective oxidation of benzylamine to the corresponding imine under visible light illumination and the photocatalyst can be used for many times without apparent activity loss. X-ray diffraction studies, transmission electron microscopy, diffuse reflectance UV-Vis spectroscopy and nitrogen adsorption measurements were used for the characterization of the as-prepared and recycled AgI samples. It is found that under visible light irradiation, AgI partially decomposed to produce Ag/AgI nanostructure and thus stabilized. The photoactivity of supported Ag/AgI for the selective oxidation of benzylamine was studied in terms of the light intensity, wavelength, temperature and substituent. It is proposed that the formation of plasmonic Ag nanoparticles should be responsible for the high activity and selectivity.

Preparation of titania-based catalysts for formaldehyde photocatalytic oxidation from TiCl4 by the sol-gel method

Titania sols were prepared by acid hydrolysis of a TiCl4 precursor instead of titanium alkoxides. The effect of acid concentration on the particle size and stability of sol was investigated. Stable titania sols with mean particle size of 14 nm could be obtained when the H+/Ti molar ratio was 0.5. The titania sols were modified with Pt, SiO2, ZrO2, WO3 and MoO3 to prepare a series of modified catalysts, which were used for the photocatalytic oxidation of formaldehyde at 37 degreesC. They showed different photocatalytic activities due to the influence of the additives. Comparing with pure TiO2, the addition of silica or zirconia increased the photocatalytic activity, while the addition of Pt and MoO3 decreased the activity, and the addition Of WO3 had little effect on the activity. It is of great significance that the conversion of formaldehyde was increased up to 94% over the SiO2-TiO2 catalyst. The increased activity was partly due to higher surface area and porosity or smaller crystallite size. A comparison of our catalyst compositions with the literature in this field suggested that the difference in activity due to the addition of a second metal oxide maybe caused by the surface chemistry of the catalysts, particularly the acidity. (C) 2001 Elsevier Science B.V. All rights reserved.

Gas-phase photocatalytic oxidation of dichlorobutenes

Gas-phase photocatalysis of 1,4-dichlorobut-2-enes and 3,4-dichlorobut-1-ene (DCB) has been studied using TiO2 and 3%WO3/TiO2 supported on SiO2. DCB was found to oxidize efficiently over these catalysts; however, only low rates of CO2 formation were observed. With these chlorinated hydrocarbons, the catalysts were found to deactivate over time, probably via the formation of aldol condensation products of chloroacetaldehyde, which is the predominant intermediate observed. The variation in rate and selectivity of the oxidation reactions with O-2 concentration is reported and a mechanism is proposed. Using isotope ratio mass spectrometry, the initial step for the DCB removal has been shown not to be a carbon bond cleavage but is likely to be hydroxyl radical addition to the carbon-carbon double bond.

Photocatalytic oxidation of deposited sulfur and gaseous sulfur dioxide by TiO2 films

Thick (4 mu m) films of anatase titania are used to photocatalyze the removal of deposited films of amorphous sulfur, similar to 2.8 mu m, thick and under moderate illumination conditions (I = 5.6 mW cm(-2)) on the open bench the process is complete within similar to 8 or 18 h using UVC or UVA light, respectively. Using UVA light, 96% of the product of the photocatalytic removal of the film of sulfur is sulfur dioxide, SO2. The photonic efficiency of this process is similar to 0.16%, which is much higher (> 15 times) than that of the removal of soot by the same films, under similar experimental conditions. In contrast to the open bench work, in a closed system the photocatalytic activity of a titania film toward the removal of sulfur decreased with repeated use, due to the accumulation of sulfuric acid on its surface generated by the subsequent photocatalytic oxidation of the initial product, SO2. The H2SO4-inactivated films are regenerated by soaking in water. The problems of using titania films to remove SO2 from a gaseous environment are discussed briefly.

Photocatalytic oxidation of soot by P25TiO(2) films

The photomineralisation of soot by P25 titania films is studied using FT-IR and the process shown to involve the oxidation of carbon to CO2 exclusively. The efficiency of this process is low, however, with a formal quantum efficiency of 1.1 X 10(-4) molecules of carbon oxidized per incident photon of UVA light. The cause of this low efficiency is attributed largely to the less than intimate contact between the fibrous soot layer and the surface of the photocatalyst. (c) 2006 Elsevier Ltd. All rights reserved.

Quantum yield measurements for the photocatalytic oxidation of Acid Orange 7 (AO7) and reduction of 2,6-dichloroindophenol (DCIP) on transparent TiO2 films of various thickness

This work comprises the photoactivity assessment of transparent sol–gel TiO2 coatings of various thickness using two test systems. The initial rates of both photocatalytic reactions, namely the oxidative bleaching of Acid Orange 7 (AO7) and the reductive bleaching of 2,6-dichlorindophenol (DCIP) increase linearly with increasing titania film thickness as well as with increasing absorbed light flux. The latter work revealed quantum yields (QY) of 0.19% and 92% for the AO7 and DCIP test system, respectively. The low QY for the AO7 oxidation is due to the combination of a slow irreversible reduction of oxygen and also for the oxidation of AO7, thus favouring the high efficiency for electron–hole recombination that is typical for aqueous organic pollutants. In contrast, the very high QY for the photocatalysed reduction of DCIP is due to the presence of a vast excess of glycerol which traps the photogenerated holes efficiently and so allow time for the slower reduction of dye to take place. Furthermore, the oxidation of glycerol results in the generation of highly reducing R-hydroxyalkyl radicals that are able to also reduce DCIP. As a consequence of this ‘current doubling’ effect, the observed QY (92%) is much higher than the apparent theoretical value of 50%.

Mechanistic studies of the photocatalytic oxidation of microcystin-LR: An investigation of byproducts of the decomposition process

Microcystins (cyclic heptapeptides) are produced by a number of freshwater cyanobacteria and cause concern in potable water supplies due to their acute and chronic toxicity. The present study reports the structural characterization of the degradation products of the photocatalytic oxidation of microcystin-LR, so aiding the mechanistic understanding of this process. TiO₂ photocatalysis is a promising technology for removal of these toxins from drinking water. However, before it can be adopted in any practical application it is necessary to have a sufficient knowledge of degradation byproducts and their potential toxicity. Liquid chromatography-mass spectrometry analysis demonstrated that the major destruction pathway of microcystin appears to be initiated via three mechanisms: UV irradiation, hydroxyl radical attack, and oxidation. UV irradiation caused geometrical isomerization of microcystin converting the (4E), (6E) of the Adda configuration to (4E), 6(Z) or 4(Z), 6(E). Hydroxyl radical attack on the conjugated diene structure of Adda moiety produced dihyroxylated products. Further oxidation cleaved the hydroxylated 4-5 and/or 6-7 bond of Adda to form aldehyde or ketone peptide residues, which then were oxidized into the corresponding carboxylic acids. Photocatalysis also hydrolyzed the peptide bond on the ring structure of microcystin to form linear structures although this appeared to be a minor pathway.

Mechanistic and toxicity studies of the photocatalytic oxidation of microcystin-LR

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, a variety of by-products were generated. In this paper, we report a mechanistic study of the photocatalytic destruction of microcystin-LR. In particular, the toxicity by-products of the process have been studied using both brine shrimp and protein phosphatase bioassays. 

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.

Detoxification of microcystins (cyanobacterial hepatotoxins) using TiO2 photocatalytic oxidation

TiO₂ photocatalysis has been used to destroy microcystin-LR in aqueous solution. The destruction of this toxin was monitored by HPLC, and the disappearance was accompanied by the appearance of seven UV detectable compounds. Spectral analysis revealed that some of these compounds retained spectra similar to the parent compound suggesting that the Adda moiety, thought to be responsible for the characteristic spectrum, remained intact whereas the spectra of some of the other products was more radically altered. Six of the seven observed reaction products did not appear to undergo further degradation during prolonged photocatalysis (100 min). The degree to which microcystin-LR was mineralized by photocatalytic oxidation was determined. Results indicated that less than 10% mineralization occurred. Mass spectral analysis of the photocatalyzed microcystin-LR allowed tentative characterization of the reaction process and products. Reduction in toxicity due to the photocatalytic oxidation was evaluated using an invertebrate bioassay, which demonstrated that the disappearance of microcystin-LR was paralleled by a reduction in toxicity. These findings suggest that photocatalytic destruction of microcystins may be a suitable method for the removal of these potentially hazardous compounds from drinking water.

Photocatalytic oxidation of propene in gas phase at low concentration by optimized TiO2 nanoparticles

In the present study, nanocrystalline titanium dioxide (TiO2) was prepared by sol–gel method at low temperature from titanium tetraisopropoxide (TTIP) and characterized by different techniques (gas adsorption, XRD, TEM and FTIR). Variables of the synthesis, such as the hydrolyzing agent (acetic acid or isopropanol) and calcination temperatures (300–800 °C), were analyzed to get uniform size TiO2 nanoparticles. The effect that these two variables have on the structure of the resultant TiO2 nanoparticles and on their photocatalytic activity is investigated. The photocatalytic activities of TiO2 nanoparticles were evaluated for propene oxidation at low concentration (100 ppmv) under two different kinds of UV light (UV-A ∼ 365 nm and UV-C ∼ 257.7 nm) and compared with Degussa TiO2 P-25, used as reference sample. The results show that both hydrolyzing agents allow to prepare TiO2 nanoparticles and that the hydrolyzing agent influences the crystalline structure and its change with the thermal treatments. Interestingly, the prepared TiO2 nanoparticles possess anatase phase with small crystalline size, high surface area and higher photocatalytic activity for propene oxidation than commercial TiO2 (Degussa P-25) under UV-light. Curiously, these prepared TiO2 nanoparticles are more active with the 365 nm source than with the 257.7 nm UV-light, which is a remarkable advantage from an application point of view. Additionally, the obtained results are particularly good when acetic acid is the hydrolyzing agent at both wavelengths used, possibly due to the high crystallinity, low anatase phase size and high surface oxygen groups’ content in the nanoparticles prepared with it, in comparison to those prepared using isopropanol.

Titanium dioxide photocatalytic degradation of aliphatic ethers and their primary oxidation products

Two studies were performed to obtain fundamental mechanistic information on the TiO2 catalyzed degradation of organic substrates irradiated at 350 nm in dilute aqueous solutions under oxygenated conditions: (a) The photodecomposition of methyl tert-butyl ether (MTBE) and its intermediate products from β-oxidation, 2-methoxy-2-methylpropanol and 2-methoxy-2-methylpropanol. (b) The photodecomposition of two haloethers, bis-(2-chloroethyl) ether, and bis-(2-chloroisopropyl) ether. Controls were carried out throughout the two studies in the absence of light, and without the semiconductor in order to evaluate the role of photolysis. ^ The syntheses of proposed intermediate products, 2-methoxy-2-methylpropanol, 2-methoxy-2-methylpropanal, 2-methoxy-2-methylpropanoic acid, 2-chloroethyl formate, and 1-chloro-2-propyl acetate, were performed. The formation of these products in the titanium dioxide photocatalytic oxidation of the substrates of interest was also confirmed. TiO2 photocatalysis is a very effective method for the mineralization of aliphatic ethers and their primary oxidation products. ^

Role of Platinum Deposited on TiO2 in Photocatalytic Methanol Oxidation and Dehydrogenation Reactions

Titania modified nanoparticles have been prepared by the photodeposition method employing platinum particles on the commercially available titanium dioxide (Hombikat UV 100). The properties of the prepared photocatalysts were investigated by means of the Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), atomic force microscopy (AFM), and UV-visible diffuse spectrophotometry (UV-Vis). XRD was employed to determine the crystallographic phase and particle size of both bare and platinised titanium dioxide. The results indicated that the particle size was decreased with the increasing of platinum loading. AFM analysis showed that one particle consists of about 9 to 11 crystals. UV-vis absorbance analysis showed that the absorption edge shifted to longer wavelength for 0.5% Pt loading compared with bare titanium dioxide. The photocatalytic activity of pure and Pt-loaded TiO2 was investigated employing the photocatalytic oxidation and dehydrogenation of methanol. The results of the photocatalytic activity indicate that the platinized titanium dioxide samples are always more active than the corresponding bare TiO2 for both methanol oxidation and dehydrogenation processes. The loading with various platinum amounts resulted in a significant improvement of the photocatalytic activity of TiO2. This beneficial effect was attributed to an increased separation of the photogenerated electron-hole charge carriers.

Advances in heterogeneous photocatalytic degradation of phenols and dyes in wastewater : a review

The heterogeneous photocatalytic water purification process has gained wide attention due to its effectiveness in degrading and mineralizing the recalcitrant organic compounds as well as the possibility of utilizing the solar UV and visible light spectrum. This paper aims to review and summarize the recently published works in the field of photocatalytic oxidation of toxic organic compounds such as phenols and dyes, predominant in waste water effluent. In this review, the effects of various operating parameters on the photocatalytic degradation of phenols and dyes are presented. Recent findings suggested that different parameters, such as type of photocatalyst and composition, light intensity, initial substrate concentration, amount of catalyst, pH of the reaction medium, ionic components in water, solvent types, oxidizing agents/electron acceptors, mode of catalyst application, and calcinations temperature can play an important role on the photocatlytic degradation of organic compounds in water environment. Extensive research has focused on the enhancement of photocatalysis by modification of TiO2 employing metal, non-metal and ion doping. Recent advances in TiO2 photocatalysis for the degradation of various phenols and dyes are also highlighted in this review.