Photochemical and photocatalytic degradation of trans-resveratrol.

Photochemical and photocatalytic degradation of the emerging pollutant trans-resveratrol has been studied under different irradiation wavelengths and using different TiO2 catalysts. trans-Resveratrol was more easily degraded when irradiated using the whole spectral range (UV-Vis) rather than with UV and near-UV to visible irradiation. The main intermediate of trans-resveratrol phototransformation was identified as its isomer cis-resveratrol. Different TiO2 catalysts were used to carry out the photocatalytic degradation of trans-resveratrol. Catalysts properties such as crystallite dimensions, surface area and presence of hydroxy surface groups are shown to be crucial to the photocatalytic efficiency of the materials tested. From the point of view of trans-resveratrol abatement, the photocatalytic process was more efficient than the pure photochemical one resulting in higher degradation rates and higher organic content removal. Six photoproducts of trans-resveratrol phototransformation were identified mainly resulting from the attack of the hydroxyl radical to the organic molecule.

Influence of excitation wavelength (UV or visible light) on the photocatalytic activity of titania containing gold nanoparticles for the generation of hydrogen or oxygen from water.

Gold nanoparticles supported on P25 titania (Au/TiO(2)) exhibit photocatalytic activity for UV and visible light (532 nm laser or polychromatic light λ > 400 nm) water splitting. The efficiency and operating mechanism are different depending on whether excitation occurs on the titania semiconductor (gold acting as electron buffer and site for gas generation) or on the surface plasmon band of gold (photoinjection of electrons from gold onto the titania conduction band and less oxidizing electron hole potential of about -1.14 V). For the novel visible light photoactivity of Au/TiO(2), it has been determined that gold loading, particle size and calcination temperature play a role in the photocatalytic activity, the most active material (Φ(H2) = 7.5% and Φ(O2) = 5.0% at 560 nm) being the catalyst containing 0.2 wt % gold with 1.87 nm average particle size and calcined at 200 °C.

Photocatalytic oxidation of phenolic compounds by using a carbon nanotube-titanium dioxide composite catalyst.

A nanostructured multiwalled carbon nanotube (CNT) and titanium dioxide composite catalyst is prepared by a modified acid-catalyzed sol-gel method. Pure anatase TiO(2) and the CNT-TiO(2) composite are tested in the photocatalytic degradation of four para-substituted phenols: 4-chlorophenol, 4-aminophenol, 4-hydroxybenzoic acid and 4-nitrophenol. The effect of several operational parameters on the photoefficiency of the composite catalyst is studied by using 4-chlorophenol as model compound, namely catalyst loading, pH of the medium, hydrogen peroxide concentration, substrate concentration. A relationship between the Hammett constant of each para-substituted phenolic compound and its degradability by the photocatalysts is found. The effect of the carbon phase in the catalyst is ascribed to its photosensitizer action. A clear beneficial effect is observed for the degradation of 4-aminophenol and 4-chlorophenol. For the molecules with stronger electron-withdrawing (deactivating) groups, such as 4-hydroxybenzoic acid and 4-nitrophenol, no synergy effect is observed.

Enhanced efficiency of the visible-light photocatalytic hydrogen generation by the ruthenium tris(2,2'-bipyridyl)-methyl viologen system in the presence of cucurbit[n]urils.

Cucurbiturils are cyclic oligomers of glycoluril units whose molecular shape defines an internal hollow space accessible through carbonyl portals. It is known that methyl viologen forms strong host-guest complexes with CB[7] and CB[8]. In the latter case even a dimer can be hosted inside CB[8]. Classical solution systems for visible light H(2) generation use methyl viologen as an electron relay. In this work we have found that the efficiency for H(2) generation of the photocatalytic system comprising EDTA-ruthenium tris(2,2'-bipyridyl)-methyl viologen-Pt increases when cucurbiturils are present in the solution. The enhancement follows the order CB[6] < CB[7] < CB[8]. By means of laser flash photolysis we have established that this efficiency increase arises from the combination of an increase in the relative quantum yield of charge separation (higher efficiency in the formation of MV*(+)) and a decrease of MV*(+) lifetime.

Anatase vs. rutile efficiency on the photocatalytic degradation of clofibric acid under near UV to visible irradiation.

Titanium dioxide (TiO(2)) powder, a semiconductor material typically used as a photocatalyst, is prepared following an acid-catalyzed sol-gel method starting from titanium isopropoxide. The xerogel calcination temperature is used to control surface and morphological properties of the material. Materials are extensively characterized by spectroscopic, micrographic and calorimetric techniques. The different TiO(2) catalysts are used in the visible-light-driven photocatalytic degradation of clofibric acid, a lipid regulator drug. The photoefficiency of TiO(2) catalysts, quantified in terms of kinetic rate constant, total organic carbon removal and initial quantum yield, increases with calcination temperature up to 673 K. A further increase in the calcination temperature leads to a decline in the photoefficiency of the catalysts, which is associated with the phase transformation from anatase to rutile concomitant with an increase in crystallite dimensions. The photochemical and photocatalytic oxidation of clofibric acid follows a pseudo-first order kinetic rate law. 4-Chlorophenol, isobutyric acid, hydroquinone, benzoquinone and 4-chlorocatechol are detected as main intermediates.