The photocatalytic degradation of azo dyes containing different functionalities has been reviewed using TiO2 as photocatalyst in aqueous solution under solar and UV irradiation. The mechanism of the photodegradation depends on the radiation used. Charge injection mechanism takes place under visible radiation whereas charge separation occurred under UV light radiation. The process is monitored by following either the decolorization rate and the formation of its end-products. Kinetic analyses indicate that the photodegradation rates of azo dyes can usually be approximated as pseudo-first-order kinetics for both degradation mechanisms, according to the Langmuir–Hinshelwood model. The degradation of dyes depend on several parameters such as pH, catalyst concentration, substrate concentration and the presence of electron acceptors such as hydrogen peroxide and ammonium persulphate besides molecular oxygen. The presence of other substances such as inorganic ions, humic acids and solvents commonly found in textile effluents is also discussed. The photocatalyzed degradation of pesticides does not occur instantaneously to form carbon dioxide, but through the formation of long-lived intermediate species. Thus, the study focuses also on the determination of the nature of the principal organic intermediates and the evolution of the mineralization as well as on the degradation pathways followed during the process. Major identified intermediates are hydroxylated derivatives, aromatic amines, naphthoquinone, phenolic compounds and several organic acids. By-products evaluation and toxicity measurements are the key-actions in order to assess the overall process.

TiO2-assisted photocatalytic degradation of azo dyes in aqueous solution: kinetic and mechanistic investigations A review

The degradation of acid red 14 (AR14), commonly used as a textile dye, can be photocatalysed by ZnO. Using advanced oxidation processes (AOPs), zinc oxide appears to be a suitable alternative to TiO2 for water treatment. In this study, a detailed investigation of photocatalytic degradation of acid red 14 is presented. Photodegradation efficiency was small when the photolysis was carried out in the absence of ZnO and it was also negligible in the absence of UV light. The semi-log plot of dye concentration versus time was linear, suggesting first order reaction (K=0.0548 min−1). The effects of some parameters such as pH, amount of photocatalyst, hydrogen peroxide and ethanol concentration were also examined. The addition of proper amount of hydrogen peroxide improved the decolorization, while the excess hydrogen peroxide could quenched the formation of hydroxyl radicals ( OH). As our results indicated that ethanol inhibited the photodegradation of dye, we concluded from the inhibitive effect of ethanol that hydroxyl radicals played a significant role in the photodegradation of dye. This should not undermine direct oxidation caused by positive holes.

Photocatalytic degradation of azo dye acid red 14 in water on ZnO as an alternative catalyst to TiO2

Acid Red 14 (AR14), commonly used as a textile dye, could be photocatalytically degraded using TiO 2 suspensions irradiated by a UV-C lamp (30 W). The experiments showed that TiO 2 and UV light had a negligible effect when they were used on their own. The semi-log plot of dye concentration versus time was linear, suggesting first order reaction ( K =1.41×10 −2  min −1 ). The effects of some parameters such as pH, the amount of TiO 2 and initial dye concentration were also examined. The photodegradation of AR14 was enhanced by the addition of proper amount of hydrogen peroxide, but it was inhibited by ethanol. From the inhibitive effect of ethanol it was deducted that hydroxyl radicals played a significant role in the photodegradation of dye, but a direct oxidation by positive holes was probably not negligible. Accordingly, it could be stated that the complete removal of color, after selecting optimal operational parameters could be achieved in a relatively short time, about 3.5 h.

Photocatalytic degradation of azo dye acid red 14 in water: investigation of the effect of operational parameters

The problem of textile dye pollution has been addressed by various methods, mainly physical, chemical, biological, and acoustical. These methods mainly separate and/or remove the dye present in water. Recently, advanced oxidation processes (AOP) have been focused for removal of dye from waste water due to their advantages such as ecofriendly, economic and capable to degrade many dyes or organic pollutant present in water. Photocatalysis is one of the advance oxidation processes, mainly carried out under irradiation of light and suitable photocatalytic materials. The photocatalytic activity of the photocatalytic materials mainly depends on the band gap, surface area, and generation of electron–hole pair for degradation dyes present in water. It has been observed that the surface area plays a major role in photocatalytic degradation of dyes, by providing higher surface area, which leads to the higher adsorption of dye molecule on the surface of photocatalyst and enhances the photocatalytic activity. This present review discusses the synergic effect of adsorption of dyes on the photocatalytic efficiency of various nanostructured high surface area photocatalysts. In addition, it also provides the properties of the water polluting dyes, their mechanism and various photocatalytic materials; and their morphology used for the dye degradation under irradiation of light along with the future prospects of highly adsorptive photocatalytic material and their application in photocatalytic removal of dye from waste water.

P.H. Ho

Papers

Solar photocatalytic decolorization of methylene blue in water.