Ezio Pelizzetti

Exploiting the interparticle electron transfer process in the photocatalysed oxidation of phenol, 2-chlorophenol and pentachlorophenol : chemical evidence for electron and hole transfer between coupled semiconductors

The photocatalysed oxidation of phenol, 2-chlorophenol and pentachlorophenol was re-examined under conditions in which TiO2 anatase was sensitized by CdS in air-equilibrated aqueous media; this was to assess whether or not the interparticle electron transfer pathway, first discovered a decade ago (N. Serpone, E. Borgarello and M. Gratzel, J. Chem. Soc., Chem. Commun., (1984) 342) and subsequently applied to enhance reductive processes on titania, could also be applied to photo-oxidative processes. The results indicate that combinations such as CdS/TiO2 lead to an enhanced rate of disappearance of the initial substrate by a factor greater than two, consistent with the notion that (irradiated) CdS electrons are vectorially displaced onto the non-illuminated TiO2 particulates. Cadmium sulphide is a poorer photo-oxidation catalyst than titania. Other semiconductor materials have also been examined under a variety of conditions of pH and irradiation wavelength. The data also show that when both semiconductors in a coupled system are illuminated simultaneously and their valence and conduction bands are suitably disposed, both electron and hole transfer occur (as in the CdS/TiO2, ZnO/TiO2, TiO2/Fe2O3 and ZnO/Fe2O3 couples), which will influence the efficiency of photo-oxidation. N2O-saturated aqueous dispersions of TiO2 have no effect on the photo-oxidation of phenol, although it was expected that nitrous oxide would scavenge the photogenerated electrons in a manner similar to chemisorbed molecular oxygen, and enhance the efficiency. It is suggested that the role of oxygen in photo- oxidations may be more than just a simple electron scavenger.

TiO2-assisted photodegradation of dye pollutants II. Adsorption and degradation kinetics of eosin in TiO2 dispersions under visible light irradiation

Abstract The TiO2-assisted photodegradation of anionic eosin has been examined in TiO2 aqueous dispersions under illumination by visible light. Eosin is easily decomposed photochemically by visible light in the presence of TiO2 particles. The degradation kinetics followed a Langmuir-Hinshelwood type equation. The rate was greater in acid media than in neutral and alkaline media, which correlates with the adsorption behavior of eosin on the TiO2 surface. Adsorption of eosin is a prerequisite for the TiO2-assisted photodegradation. The evolution of CO2 occurred concomitantly with the photodegradation of eosin. A plausible mechanism of degradation is discussed.

Analytical applications of organized molecular assemblies

Abstract Organized molecular assemblies have great potential utility in many types of analytical method. This review is concerned with recent of micelles, reversed micelles and micro-emulsions in shifting acid-base equilibria, and in electrochemical measurements, ultraviolet-visible spectrophotometry, micellar-echanced phosphorimetry and fluorimetry, liquid-liquid extraction, flame and plasmas atomic spectrometry, and high-performance and thin-layer liquid chromatography.

Photocatalytic degradation of phenol in aqueous titanium dioxide dispersions

The results of a study of photocatalytic degradation of phenol using aqueous oxygenated TiO2 (anatase) suspensions in a batch Pyrex photoreactor are reported. The influence on the photodegradation rate of various parameters as pH, phenol and TiO2 content, oxygen partial pressure, anions present in the dispersions was investigated. A complete oxidation of phenol was observed. Intermediate compounds, catechol and quinone, were detected. It was observed that the photodegradation also proceeded with sunlight radiation. A mechanistic and kinetic model, which accounts for the results obtained, is given. Likely reasons for inactivity of the rutile modification for this reaction are also given.

Chemical degradation of chlorophenols with Fenton's reagent (Fe2+ + H2O2)

Aqueous solutions of Fentons reagent (Fe2+ + H2O2) have been used to effect the total decomposition of the chlorophenols: 2-chlorophenol, 3-chlorophenol, 4-chlorophenol, 3,4-dichlorophenol and 2,4,5-trichlorophenol. The mineralization of these chlorinated aromatic substrates to CO2 and free Cl− has been studied as a function of [Fe2+] and [HClO4]. Increasing the concentration of Fe2+ enhances the decomposition process, while an increase in the concentration of HClO4, inhibits the reaction. The presence of Fe3+ alone (without any Fe2+) with H2O2 has no effect on the degradation of the chlorophenols. In all cases, the stoichiometric quantity of free Cl− was obtained at the completion of the decomposition reaction; but the rates of disappaearance of the chlorophenol and of the formation of the Cl− are not similar. This suggests that some chlorinated aliphatic species may be formed as possible intemediates.

Standardization protocol of process efficiencies and activation parameters in heterogeneous photocatalysis: relative photonic efficiencies ζr

The quantum yield Φ is crucial in homogeneous photochemistry; in heterogeneous photocatalysis this term remains elusive since the number of absorbed photons remains experimentally difficult to asses. A comprehensive method to standardize and compare process efficiencies in heterogeneous photocatalysis was proposed earlier by describing the relative photonic efficiency ζr (J. Photochem. Photobiol., A: Chem., 73 (1993) 11). The method of determining ζr is herein tested for the photocatalyzed degradation of phenol as the standard process and Degussa P25 TiO2 as the standard photocatalyst. The effects of light intensity, reactor geometry, pH, temperature, concentration of reactant and concentration of TiO2 on ζr were examined for the photodegradation of three substituted phenols: 2-methylphenol, 2,4-dimethylphenol and 4-chlorophenol. Relative photonic efficiencies of other phenolic substrates are reported for a given set of conditions. Efficiencies on varying the nature and the source of TiO2 for the photodegradation of phenol were also explored. These ζr are useful to assess process quantum yields once the actual quantum yield for a standard process (Φstand, for a given photocatalyst and a standard organic substrate) has been rigorously determined; thus Φ = ζrΦstand.

Photochemical reactions in the tropospheric aqueous phase and on particulate matter

This paper is a tutorial review in the field of atmospheric chemistry. It describes some recent developments in tropospheric photochemistry in the aqueous phase and on particulate matter. The main focus is regarding the transformation processes that photochemical reactions induce on organic compounds. The relevant reactions can take place both on the surface of dispersed particles and within liquid droplets (e.g. cloud, fog, mist, dew). Direct and sensitised photolysis and the photogeneration of radical species are the main processes involved. Direct photolysis can be very important in the transformation of particle-adsorbed compounds. The significance of direct photolysis depends on the substrate under consideration and on the colour of the particle: dark carbonaceous material shields light, therefore protecting the adsorbed molecules from photodegradation, while a much lower protection is afforded for the light-shaded mineral fraction of particulate. Particulate matter is also rich in photosensitisers (e.g. quinones and aromatic carbonyls), partially derived from PAH photodegradation. These compounds can induce degradation of other molecules upon radiation absorption. Interestingly, substrates such as methoxyphenols, major constituents of wood-smoke aerosol, can also enhance the degradation of some sensitisers. Photosensitised processes in the tropospheric aqueous phase have been much less studied: it will be interesting to assess the photochemical properties of Humic-Like Substances (HULIS) that are major components of liquid droplets. The main photochemical sources of reactive radical species in aqueous solution and on particulate matter are hydrogen peroxide, nitrate, nitrite, and Fe(iii) compounds and oxides. The photogeneration of hydroxyl radicals can be important in polluted areas, while their transfer from the gas phase and dark generation are usually prevailing on an average continental scale. The reactions involving hydroxyl radicals can induce very fast transformation of compounds reacting with (*)OH at a diffusion-controlled rate (10(10) M(-1) s(-1)), with time scales of an hour or less. The hydroxyl-induced reactivity in solution can be faster than in the gas phase, influencing the degradation kinetics of water-soluble compounds. Moreover, photochemical processes in fog and cloudwater can be important sources of secondary pollutants such as nitro-, nitroso-, and chloro-derivatives.

Photodegradation of dichlorophenols and trichlorophenols in TiO2 aqueous suspensions: kinetic effects of the positions of the Cl atoms and identification of the intermediates

The photocatalytic degradation of six dichlorophenols (DCPs) and three trichlorophenols (TCPs) in TiO2 aqueous suspensions was studied. The apparent first-order rate constants kapp of disappearance of these CPs and monochlorophenols (MCPs) were found to correlate with their Hammett constants λ and their 1-octanol-water partition coefficients Kow: kaw (h−1)= −10σ+5.2 log Kow−7.5 under the conditions used (correlation coefficient, 0.987, if 2,4,6-TCP was omitted). The aromatic intermediates identified by their UV spectra (high performance liquid chromatography (HPLC) separation) and mass spectra (gas chromatography (GC) separation) corresponded to the hydroxylation of the aromatic nucleus with the following order of reactivity para> ortho>meta. Para-benzoquinones with 0–2 Cl atoms and 0 or 1 OH group and intermediates with two aromatic or quinone rings were also detected. The temporal variations of some intermediates were determined. All of these compounds, in which the C6 ring subsisted, were very unstable, so that their maximum concentration was very low compared with the initial CP concentration. The release of chloride and the evolution of CO2 also followed apparent first- order kinetics within the first part of the degradation. The effects of the number and position of Cl atoms on these fkinetics are discussed.

Photocatalytic transformation of organic compounds in the presence of inorganic ions

The influence of halide ions on the photocatalytic process on titanium dioxide has been investigated carefully. Chloride and bromide ions, acting as hole scavengers, generate active radical species (e.g., ·Cl and ·Br) that participate in reactions with the organic compounds and the transient intermediates. Chloride and bromide ions have shown to deeply inhibit the degradation rate of chloroform and tetrachloromethane and to modify both the qualitative and quantitative distribution of their intermediates formed during the degradation process. In the presence of bromide, CBrCl3 is detected as intermediate during CCl4 degradation, while in the presence of chloride, formation of CCl4 is observed in the CHCl3 degradation. Fluoride ions, differently from the other halides, cannot be oxidized by the valence hole and may be used as a diagnostic tool in mechanistic studies. The influence of fluoride on phenol has been investigated, and, by choosing appropriate experimental conditions, it was possible to evaluate the role of the different active species in the photocatalytic process.

Large solar plant photocatalytic water decontamination: Degradation of pentachlorophenol

Abstract The photocatalytic degradation of pentachlorophenol in the large solar plant built at the Plataforma Solar de Almeria is presented. Degradation of cubic meters per hour of pentachlorophenol at a concentration of mg L−1 is demonstrated and is easily achieved in short residence times. Details of the plant based on parabolic solar concentrators, together with the examination of the main factors affecting total efficiency are discussed in comparison with small scale laboratory experiments. Experiments carried out with addition of peroxydisulphate show a noticeable increment in the degradation efficiency and are suggested for the treatment of concentrated or refractory pollutants.