Pascal Wong-Wah-Chung

Photochemical behavior of PVA as an oxygen-barrier polymer for solar cell encapsulation

Polyvinyl alcohol (PVA) is a water-soluble polymer that is anticipated to be a good candidate for incorporation into multilayer coatings of organic solar cells due to its high transparency and ability to form a barrier to oxygen. Because a long lifetime is a prerequisite for successful applications, it was necessary to study the photochemical behavior of PVA under solar light. PVA films were exposed to UV-visible light irradiation (λ > 300 nm) in accelerated aging conditions representative of natural ageing. Modifications in the chemical structure of aged samples irradiated at ambient air were recorded. Due to the low oxygen permeability of PVA films, it was shown that the photooxidative degradation of PVA films is restricted to the surface (<5 μm) and results in a large amount of chain scissions, with a progressive erosion of the surface of the irradiated material. The oxidation products formed along the macromolecular chains, and low molecular weight species trapped in the matrix or emitted in the gas phase were also identified. An oxidation mechanism was then proposed to account for these modifications. However, irradiation in the absence of oxygen demonstrated the high photostability of PVA films, which permits the use of PVA as a sublayer in inorganic/organic multilayer encapsulation systems.

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.

Dissolved gaseous mercury formation under UV irradiation of unamended tropical waters from French Guyana

Filtered and non-filtered natural waters from French Guyana were irradiated with lamps emitting within the wavelength range 300-450 nm for 4 days with and without oxygen. Dissolved gaseous mercury (DGM) evolution was observed and quantified in the course of the irradiation. Measurements of total mercury in waters prior to and after the irradiations were also performed. The mass balance in the various mercury species (Hg(total), Hg(reactive) and DGM) proves the capability of the light to extract the mercury linked to the organic matter. DGM evolvement was greater in N2- than in air-saturated solutions, and the formation of volatile oxidized species can account for the inhibiting effect of oxygen. Filtration did not affect the mercury photoreduction, but reduced the formation of DGM in the dark. Great care has to be taken with regard to the following artifact: it was found that DGM originated not only from the natural waters, but also from the experimental device itself when exposed to the light. These non-expected DGM entries were quantitatively evaluated. This stresses the difficulty in measuring mercury at environmental concentrations.

Photochemical Degradation of the Plant Growth Regulator 2-(1-Naphthyl) acetamide in Aqueous Solution Upon UV Irradiation

The photochemical degradation of 2‐(1‐naphthyl) acetamide (NAD) in aqueous solution using simulated sunlight excitation as well as UV light within the 254–300 nm range was investigated to obtain an insight into the transformation mechanism that could occur under environmental conditions. Several photoproducts were identified using HPLC/MS/MS techniques. The degradation quantum yield was found to be independent of the excitation wavelength, but showed a dependence of oxygen concentration. This increased by a factor of approximately 3 from aerated to oxygen‐free solutions. There is a clear involvement of both triplet and singlet excited states in NAD photoreactivity. The participation of singlet oxygen as a significant route in NAD degradation was ruled out by comparison with the behavior using Rose Bengal as a photosensitizer. A mechanistic pathway implying hydroxylation process through NAD radical cation species as well as an oxidation reaction by molecular oxygen is proposed. The photochemical behavior of NAD appears to mainly involve the aromatic moieties without any participation of the amide side chain. Toxicity tests clearly show that the generated primary photoproducts are responsible for a significant increase in the toxicity. However, upon prolonged irradiation this toxicity tends to decrease.

Efficient degradation of methabenzthiazuron photoinduced by decatungstate anion in water: Kinetics and mechanistic studies

This study concerns the elimination of methabenzthiazuron (MBTU) photocatalysed by sodium decatungstate salts W10O32(4-)·(DTA) in aqueous solution under irradiation at 365 nm. Ninety percentage of MBTU (10(-4) M) is mineralised in the presence of the photocatalyst (2×10(-4) M) after 7 d under exposure and the formation of nitrate, sulphate and ammonium confirmed this phenomenon. In aerated conditions, the photodegradation rate of MBTU clearly increased in the presence of DTA by a factor of 40 when compared to direct photolysis with ΦMBTU=2.5×10(-2) and t1/2 (MBTU)=1.4 h. Oxygen appeared essential since 2 times inhibition of MBTU disappearance and the photocatalytic cycle interrupt were observed in the absence of oxygen. The degradation mechanism has been elucidated through the photoproducts identification by LC-ESI-MS analysis. Two processes were implied in the degradation: electron transfer and H atom abstraction reactions both involving W10O32(4-∗) excited state species. In the primary steps of the degradation, the aromatic ring hydroxylation was observed by electron transfer leading to OH-MBTU isomers and H atom abstraction reaction gave benzthiazuron and a supposed demethylated product. Secondary oxidations permitted the hydroxylation of both products.

Competitive oxidative cleavage and epoxidation of 4,4′-diaminostilbene-2,2′-disulfonic acid by Fe(III) aqua complexes

4,4′-Diaminostilbene-2,2′-disulfonic acid (DSD) has been investigated as a model compound of fluorescent whitening agents. The reaction of DSD with Fe(III) aqua complexes has been studied in the dark at room temperature: a fast degradation of DSD was observed under our experimental conditions. HPLC analysis was used to follow the kinetics of the redox reaction. The process involves epoxidation, leading to DSD epoxide (1), and the oxidative cleavage of the double bond, leading to 5-amino-2-formyl-benzenesulfonic acid (2) together with the reduction of Fe(III) into Fe(II). The dependence of the redox process on [Fe(H2O)5(OH)]2+ concentration indicates that the dominant reaction pathway is a reaction between DSD and the Fe(III) monomeric species, [Fe(H2O)5(OH)]2+. The complete degradation of DSD is observed with an excess of oxidant; the ratio [Fe(H2O)5(OH)]2+∶[DSD] has to be higher than 2. A mechanism giving rise to the two degradation products is proposed.

Iron(III) photoinduced degradation: Catalytic method for 4,4'-diaminostilbene-2,2'-disulfonic acid removal from water

The Fe(III)-photoinduced degradation of 4,4′-diaminostilbene-2,2′-disulfonic acid (DSD), used as a model compound of fluorescent whitening agents, was investigated in aqueous solution. The mixing of DSD and iron(III) solutions immediately led to DSD degradation into two oxidation products 5-amino-2- formyl-benzene sulfonic acid (1) and DSD epoxide (2) together with the formation of Fe(II). The behaviour of the latter solution was investigated under monochromatic excitation at 365 nm. The irradiation of the solution resulted in a photoredox process that yielded Fe(II) and HO• radicals; [Fe(H2O)5(OH)]2