Eric Puzenat

PHOTOCATALYTIC DEGRADATION OF VARIOUS TYPES OF DYES (ALIZARIN S, CROCEIN ORANGE G, METHYL RED, CONGO RED, METHYLENE BLUE) IN WATER BY UV-IRRADIATED TITANIA

Abstract The photocatalytic degradation of five various dyes has been investigated in TiO 2 /UV aqueous suspensions. It was attempted to determine the feasibility of such a degradation by varying the chemical structures, either anthraquinonic (Alizarin S (AS)), or azoic (Crocein Orange G (OG), Methyl Red (MR), Congo Red (CR)) or heteropolyaromatic (Methylene Blue (MB)). In addition to a prompt removal of the colors, TiO 2 /UV-based photocatalysis was simultaneously able to fully oxidize the dyes, with a complete mineralization of carbon into CO 2 . Sulfur heteroatoms were converted into innocuous SO 4 2− ions. The mineralization of nitrogen was more complex. Nitrogen atoms in the −3 oxidation state, such as in amino-groups, remain at this reduction degree and produced NH 4 + cations, subsequently and very slowly converted into NO 3 − ions. For azo-dye (OG, MR, CR) degradation, the complete mass balance in nitrogen indicated that the central NN azo-group was converted in gaseous dinitrogen, which is the ideal issue for the elimination of nitrogen-containing pollutants, not only for environmental photocatalysis but also for any physicochemical method. The aromatic rings were submitted to successive attacks by photogenerated OH radicals leading to hydroxylated metabolites before the ring opening and the final evolution of CO 2 induced by repeated subsequent “photo-Kolbe” reactions with carboxylic intermediates. These results suggest that TiO 2 /UV photocatalysis may be envisaged as a method for treatment of diluted colored waste waters not only for decolorization, but also for detoxification, in particular in textile industries in semi-arid countries.

Why inorganic salts decrease the TiO2 photocatalytic efficiency

Methylene Blue (MB) has been chosen as a model molecule to evaluate the impact of inorganic salts, present in textile waste waters, on the adsorption properties and on the photocatalytic efficiency of TiO2. No OH∘ radical scavenging by anions such as NO3−, Cl−, SO42−, PO43−, and CO32− was observed at neutral and basic pH, while this phenomenon can be suggested at acidic pH for some anions except carbonate anions which are totally neutralized and/or eliminated as CO2 in these conditions. The decrease in the rate MB photocatalytic degradation in the presence of inorganic salts was shown to be due to the formation of an inorganic salt layer at the surface of TiO2, which inhibits the approach of MB molecules. The correlation between the amount of MB adsorbed and the rate of its photocatalytic degradation, whatever the nature of the salt, its concentration and the pH of the solution, indicates (i) that photocatalysis occurs at the surface and not in the solution and (ii) that OH− ions added at basic pH do not participate to the increase in the photocatalytic efficiency by inducing an increase in OH∘ formation. They increase the surface density in adsorption sites TiO−. The effect of various salts is similar on various titania samples of industrial origin (Millennium TiO2 PC 500, PC 50, and Degussa P 25). It is however more important on Millennium PC 10 probably because of its smaller surface area.

From the fundamentals of photocatalysis to its applications in environment protection and in solar purification of water in arid countries

A specially designed titania photocatalyst was prepared by coating Ahlstrom non-woven paper, used as a flexible photocatalytic support, with Millennium PC500 anatase. At the same time, a new solar photoreactor (STEP) was designed based on the multi-step cascade falling-film principle to ensure a good exposure to sunlight and a good oxygenation of the effluent to be treated. Several types of reactants were treated: 4-chlorophenol as a model organic pollutant; formetanate, a widely used pesticide in horticulture; a mixture of pesticides used in vineyards; and Indigo Carmine and Congo Red, which are complex multifunctional dye molecules. Each reaction was performed simultaneously in a solar CPC slurry photoreactor and in the STEP photoreactor under identical solar exposure to better evaluate and validate the results obtained. The STEP solar reactor was found to be as efficient as the CPC reactor for 4-chlorophenol, formetanate and pesticides mixture total degradation.

Solar purification and potabilization of water containing dyes

Organic pollutant removal is the main field of water photocatalytic decontamination. Molecules such as pesticides (herbicides, insecticides, fungicides, etc.) or dyes are totally destroyed and mineralized into CO2 and innocuous inorganic anions (Cl−, SO42−, NO3−). Presently, two azo-dyes (i.e., containing the-N=N-azo group), Cibacron Brilliant Red 3B-A and Remazol Black B (Reactive Black 5), were successfully destroyed and totally mineralized. The stoichiometric coefficients of the total degradation, as well as the mass balances have been established with different analytical tools: TOC for carbon, DCO for oxygen, ionic-HPLC for heteroatoms (N, S, P) and pH-metry for hydrogen. Moreover, nitrogen balance has been established during the photocatalytic degradation of the dyes by considering not only nitrate and ammonium ions in the solution, but also the formation of N2 in the gas phase. The quantification of N2 molecules suggests that the photocatalytic degradation of azo-compounds is 100% selective in generating gaseous dinitrogen. The reaction mechanism was first determined in a laboratory photoreactor, before degradation in larger pilot solar photoreactors, using UV-A radiant flux from the sun in a new sub-discipline called heliophotocatalysis.

Fate of nitrogen atoms in the photocatalytic degradation of industrial (congo red) and alimentary (amaranth) azo dyes. Evidence for mineralization into gaseous dinitrogen

The photocatalytic degradation of two azo-dyes–an industrial one (Congo Red (CR)), and an alimentary one (Amaranth (AM))–has been investigated in TiO2/UV aqueous suspensions. In addition to a prompt removal of the colors, TiO2/UV-based photocatalysis was simultaneously able to fully oxidize the dyes, with a complete mineralization of organic carbon into CO2. In particular, the aromatic rings were submitted to successive attacks by photogenerated OH∘ radicals leading to hydroxylated metabolites before the ring opening and the final evolution of CO2 induced by repeated subsequent “photo-Kolbe” reactions with carboxylic intermediates. Simultaneously, sulfur heteroatoms were converted into innocuous SO42− ions. The mineralization of nitrogen was more complex to analyze. Nitrogen atoms in the -3 oxidation state, such as in the amino-groups of CR, initially remained at this reduction degree and produced NH4

Photocatalytic efficiencies of self-cleaning glasses. Influence of physical factors

Two commercial types of self-cleaning glass (SCG) have been tested to confirm the real photocatalytic nature of their properties. This was done by using four photocatalytic tests: (i) in the gas phase with the total oxidation of acetylene; (ii) in water with the total degradation of malic acid, (iii) in water with the total degradation of methylene blue, and (iv) in the solid phase with the total oxidative degradation of a layer of stearic acid deposited on the self-cleaning glass surface, in contact with the superficial titania coating. The influence of various factors (temperature, humidity, wavelength, radiant flux, presence of inorganic particles stuck at the glass surface) was explained in line with the fundamentals of photocatalysis. The results helped to understand the behaviour of self-cleaning glass.

Photocatalytic synthesis of thio-organic compounds: case study of propan-1-thiol

Abstract Photocatalytic synthesis of propan-1-thiol has been performed at room temperature under dynamic conditions by addition of H 2 S on propene in contact with illuminated TiO 2 or CdS catalysts. Both photocatalysts were found to be active and selective in this reaction. Propan-1-thiol was selectively obtained according to a reaction mechanism implying photogenerated SH radicals. This work illustrates the potentialities of photocatalysis in the field of thiochemistry.

EFICIENCIA SOLAR DE UN NUEVO FOTO-CATALIZADOR TiO2 DEPOSITADO SOBRE UN PAPEL FOTO-INERTE PARA LA DEGRADACIÓN TOTAL DE VARIOS PLAGUICIDAS Y COLORANTES

A specially designed titania photocatalyst was prepared by coating Ahlstrom non-woven paper, used as a flexible photocatalytic support, with Millennium PC500 anatase. At the same time, a new solar photoreactor (STEP) was designed based on the multi-step cascade falling-film principle to ensure good exposure to sunlight and good oxygenation of the effluent to be treated. Several types of reactants were treated: 4-chlorophenol as a model organic pollutant; formetanate, a widely used pesticide in horticulture; a mixture of pesticides used in vineyards; and Indigo Carmine and Congo Red, which are complex multifunctional dye molecules. Each reaction was performed simultaneously in a solar CPC slurry photoreactor and in the STEP photoreactor under identical solar exposure to better evaluate and validate the results obtained. The STEP solar reactor was found to be as efficient as the CPC one for 4-chlorophenol and formetanate total degradation.

Effect of Oxygen and Water in the CO Photocatalytic Oxidation with TiO2

TiO2 P25 catalyst was used to study the photocatalytic oxidation of CO to CO2 at 288K. Two parameters, O2 and H2O were used to study its effect on the photocatalytic process. The dependency of the reaction rate on the CO concentration and water vapor was explained in terms of Langmuir-Hinshelwood mechanism. The presence of a high concentration of water vapor inhibits the CO photocatalytic oxidation at low oxygen concentration. We have noted an adsorption competition between CO and H2O on the TiO2 active sites.