Mohamed Sarakha

Iron (III) aquacomplexes as effective photocatalysts for the degradation of pesticides in homogeneous aqueous solutions.

The degradation of the herbicide asulam (4-amino-benzosulfonyl-methylcarbamate) was studied by excitation of iron (III) aquacomplexes in aqueous solutions at 365 nm as well as by exposition to solar light. Sulfanilamide was also studied as a model molecule. The initial step of asulam disappearance was shown to be due to the formation of hydroxyl radicals generated from the excitation of Fe(OH)2+, the most photoactive iron (III) monomeric species. However, when the iron (III) species was totally photoreduced to iron (II), the degradation of asulam in the presence of oxygen continued to completion. A photoreactivity of iron (II) species and/or iron (II) complexes under our experimental conditions was proposed. The experimental results indicate that the presence of iron (III), iron (II) and molecular oxygen is the condition for achieving the complete mineralization of the solution. The proposed photocatalytic cycle could provide an interesting tool for oxidations in the environment.

Fe(III)-solar light induced degradation of diethyl phthalate (DEP) in aqueous solutions.

The degradation of diethyl phthalate (DEP) photoinduced by Fe(III) in aqueous solutions has been investigated under solar irradiation in the compound parabolic collector reactor at Plataforma Solar de Almeria. Hydroxyl radicals *OH, responsible of the degradation, are formed via an intramolecular photoredox process in the excited state of Fe(III) aquacomplexes. The primary step of the reaction is mainly due to the attack of *OH radicals on the aromatic ring. For prolonged irradiations DEP and its photoproducts are completely mineralized due to the regeneration of the absorbing species and the continuous formation of *OH radicals that confers a catalytic aspect to the process. Consequently, the degradation photoinduced by Fe(III) could be an efficient method of DEP removal from water.

Assessing the photochemical transformation pathways of acetaminophen relevant to surface waters: transformation kinetics, intermediates, and modelling.

This work shows that the main photochemical pathways of acetaminophen (APAP) transformation in surface waters would be direct photolysis (with quantum yield of (4.57 ± 0.17)⋅10(-2)), reaction with CO3(-·) (most significant at pH > 7, with second-order rate constant of (3.8 ± 1.1)⋅10(8) M(-1) s(-1)) and possibly, for dissolved organic carbon higher than 5 mg C L(-1), reaction with the triplet states of chromophoric dissolved organic matter ((3)CDOM*). The modelled photochemical half-life time of APAP in environmental waters would range from days to few weeks in summertime, which suggests that the importance of phototransformation might be comparable to biodegradation. APAP transformation by the main photochemical pathways yields hydroxylated derivatives, ring-opening compounds as well as dimers and trimers (at elevated concentration levels). In the case of (3)CDOM* (for which the triplet state of anthraquinone-2-sulphonate was used as proxy), ring rearrangement is also hypothesised. Photochemistry would produce different transformation products (TPs) of APAP than microbial biodegradation or human metabolism, thus the relevant TPs might be used as markers of APAP photochemical reaction pathways in environmental waters.

Photooxidation of 4-chlorophenol sensitised by iron meso-tetrakis(2,6-dichloro-3-sulfophenyl)porphyrin in aqueous solution

The photosensitised degradation of 4-chlorophenol (4-CP) by iron meso-tetrakis(2,6-dichloro-3-sulfophenyl)porphyrin (FeTDCPPS) has been studied in aerated aqueous solution, and is shown to lead to formation of p-benzoquinone (BQ) and p-hydroquinone (HQ) as main photoproducts. In deaerated solution no p-benzoquinone was formed. The photolysis products were identified by high performance liquid chromatography (HPLC) and UV-visible spectroscopy. The photodegradation in aerated solution was also carried out in the presence of sodium azide (NaN(3)) as a singlet oxygen [(1)O(2)((1)[capital Delta](g))] quencher, and showed a significant decrease in the rate of photolysis, suggesting under these conditions, that Type II sensitisation is one of the dominant mechanisms of 4-CP degradation. Support for this comes from laser flash photolysis and time-resolved singlet oxygen phosphorescence measurements. However, these also show direct reaction between the excited porphyrin and 4-CP, indicating that there are two mechanisms involved in the chlorophenol photodegradation.

Comparison of several titanium dioxides for the photocatalytic degradation of benzenesulfonic acids

Abstract The photocatalytic efficiency of several TiO 2 (namely Degussa P25 and Millennium PC50, PC100, PC105, PC500) used as suspensions are compared for the photocatalytic degradation of 3-nitrobenzenesulfonic acid (3-NBSA) and 2,5-anilinedisulfonic acid (2,5-ADSA). With 3-NBSA, P25 is clearly the most efficient and there is no apparent relationship between photocatalytic activity and specific surface area. This result is consistent with that obtained with phenol, but a contrast was noticed with 2,5-ADSA where PC500 is more efficient than P25 in spite of a higher adsorption of the latter. In the case of TiO 2 Millennium relative photonic efficiencies ζ r are smaller with 3-NBSA than with 2,5-ADSA, that is consistent with the electron-withdrawing effect of nitro group. For the same reason the direct phototransformation in sunlight is much more rapid with of 2,5-ADSA than for 3-NBSA and 4-nitrotoluene-2-sulfonic acid.

A comparative study of water soluble 5,10,15,20-tetrakis(2,6-dichloro-3-sulfophenyl)porphyrin and its metal complexes as efficient sensitizers for photodegradation of phenols

5,10,15,20-Tetrakis(2,6-dichloro-3-chlorosulfophenyl)porphyrin and its tin and zinc complexes were synthesized with high yields and fully characterized. The corresponding water-soluble 5,10,15,20-tetrakis(2,6-dichloro-3-sulfophenyl)porphyrins were obtained by hydrolysis with water. An extensive photophysical study of the new water soluble porphyrinic compounds was carried out including absorption and fluorescence spectra, fluorescence quantum yields, triplet absorption spectra, triplet lifetimes, triplet and singlet oxygen quantum yields. These sensitizers were successfully used in the photodegradation of 4-chlorophenol and 2,6-dimethylphenol. A comparison is made of their efficiencies, and some mechanistic considerations are highlighted.

Zinc(II) phthalocyanines immobilized in mesoporous silica Al-MCM-41 and their applications in photocatalytic degradation of pesticides

In the present study the authors investigated a set of three new zinc(II) phthalocyanines (zinc(II) tetranitrophthalocyanine (ZnTNPc), zinc(II) tetra(phenyloxy)phthalocyanine (ZnTPhOPc) and the tetraiodide salt of zinc(II)tetra(N,N,N-trimethylaminoethyloxy) phthalocyaninate (ZnTTMAEOPcI)) immobilized into Al-MCM-41 prepared via ship-in-a-bottle methodology. The samples were fully characterized by diffuse reflectance-UV-vis spectroscopy (DRS-UV-vis), luminescence, thermogravimetric analysis (TG/DSC), N(2) adsorption techniques and elemental analysis. A comparative study was made on the photocatalytic performance upon irradiation within the wavelength range 320-460nm of these three systems in the degradation of pesticides fenamiphos and pentachlorophenol. ZnTNPc@Al-MCM-41 and ZnTTMAEOPcI@Al-MCM-41 were found to be the most active systems, with the best performance observed with the immobilized cationic phthalocyanine, ZnTTMAEOPcI@Al-MCM-41. This system showed high activity even after three photocatalytic cycles. LC-MS product characterization and mechanistic studies indicate that singlet oxygen ((1)O(2)), produced by excitation of these immobilized photosensitizers, is a key intermediate in the photocatalytic degradation of both pesticides.

The photo-oxidation of 2,6-dimethylphenol and monophenylphenols by uranyl ion in aqueous solution

Abstract The photo-oxidation of 2,6-dimethylphenol and o -, m - and p -phenylphenols by uranyl ion was investigated in aqueous solution. Steady state and dynamic luminescence quenching studies at pH 0.8 show the rapid dynamic deactivation of excited uranyl ions by the phenols. At the natural pH of uranyl salt solutions (pH 2.3), differences are observed between the steady state and dynamic quenching behaviour, and it is suggested that these differences are due to uranyl hydrolysis. Flash photolysis studies with uranyl ion in the presence of 2,6-dimethylphenol and m - and p -phenylphenols show that the initial photoreaction leads to phenoxyl radical formation. The photolysis products were identified by high performance liquid chromatography (HPLC) and UV absorption spectroscopy. With 2,6-dimethylphenol in aerated solution, both quinone and dimer formation are observed. Kinetic studies show that these processes occur concurrently. In contrast, photolysis of degassed solutions leads to dimer formation only. The quantum yields for these processes are reported. The photo-oxidation of aerated solutions of o -phenylphenol in the presence of uranyl ions leads to the production of two dimers and the quinone, whereas with degassed solutions only the dimers are observed. The photo-oxidation of these substrates by uranyl ion is contrasted with the behaviour of [Co(NH 3 ) 5 N 3 ] 2+ as photooxidant of the same substrates. With m -phenylphenol, quinone and dimers are observed in aerated solution, whereas only the dimer is observed in deoxygenated solution. With p -phenylphenol, only dimer formation is observed. Possible mechanistic origins of the differences in the selectivity of oxidation by the different metal complexes are discussed.

Deactivation processes of the lowest excited state of [UO2(H2O)5]2+ in aqueous solution

A detailed analysis of the photophysical behaviour of uranyl ion in aqueous solutions at room temperature is given using literature data, together with results of new experimental and theoretical studies to see whether the decay mechanism of the lowest excited state involves physical deactivation by energy transfer or a chemical process through hydrogen atom abstraction. Comparison of the radiative lifetimes determined from quantum yield and lifetime data with that obtained from the Einstein relationship strongly suggests that the emitting state is identical to that observed in the lowest energy absorption band. From study of the experimental rate and that calculated theoretically, from deuterium isotope effects and the activation energy for decay support is given to a deactivation mechanism of hydrogen abstraction involving water clusters to give uranium(v) and hydroxyl radicals. Support for hydroxyl radical formation comes from electron spin resonance spectra observed in the presence of the spin traps 5,5-dimethyl-1-pyrroline N-oxide and tert-butyl-N-phenylnitrone and from literature results on photoinduced uranyl oxygen exchange and photoconductivity. It has previously been suggested that the uranyl emission above pH 1.5 may involve an exciplex between excited uranyl ion and uranium(v). Evidence against this mechanism is given on the basis of quenching of uranyl luminescence by uranium(v), together with other kinetic reasoning. No overall photochemical reaction is observed on excitation of aqueous uranyl solutions, and it is suggested that this is mainly due to reoxidation of UO2+ by hydroxyl radicals in a radical pair. An alternative process involving oxidation by molecular oxygen is analysed experimentally and theoretically, and is suggested to be too slow to be a major reoxidation pathway.

Photochemical processes involving the UV absorber benzophenone-4 (2-hydroxy-4-methoxybenzophenone-5-sulphonic acid) in aqueous solution: reaction pathways and implications for surface waters.

The sunlight filter benzophenone-4 (BP-4) is present in surface waters as two prevailing forms, the singly deprotonated (HA-) and the doubly deprotonated one (A(2-)), with pKa2 = 7.30 ± 0.14 (μ ± σ, by dissociation of the phenolic group). In freshwater environments, BP-4 would mainly undergo degradation by reaction with ·OH and direct photolysis. The form HA(-) has a second-order reaction rate constant with ·OH (k(·OH)) of (1.87 ± 0.31)·10(10) M(-1) s(-1) and direct photolysis quantum yield Φ equal to (3.2 ± 0.6)·10(-5). The form A(2-) has (8.46 ± 0.24)·10(9) M(-1) s(-1) as the reaction rate constant with ·OH and (7.0 ± 1.3)·10(-5) as the photolysis quantum yield. The direct photolysis of HA(-) likely proceeds via homolytic breaking of the O-H bond of the phenolic group to give the corresponding phenoxy radical, as suggested by laser flash photolysis experiments. Photochemical modelling shows that because of more efficient direct photolysis (due to both higher sunlight absorption and higher photolysis quantum yield), the A(2-) form can be degraded up to 3 times faster than HA(-) in surface waters. An exception is represented by low-DOC (dissolved organic carbon) conditions, where the ·OH reaction dominates degradation and the transformation kinetics of HA(-) is faster compared to A(2-). The half-life time of BP-4 in mid-latitude summertime would be in the range of days to weeks, depending on the environmental conditions. BP-4 also reacts with Br2(·-), and a rate constant k(Br2(·-),BP-4) = (8.05 ± 1.33)·10(8) M(-1) s(-1) was measured at pH 7.5. Model results show that reaction with Br2(·-) could be a potentially important transformation pathway of BP-4 in bromide-rich (e.g. seawater) and DOM-rich environments.