Abatement of an Azo Dye on Structured C-Nafion/Fe-Ion Surfaces by Photo-Fenton Reactions Leading to Carboxylate Intermediates with a Remarkable Biodegradability Increase of the Treated Solution

• Published in: The journal of physical chemistry. B 2003-07, Vol.107 (29), p.7026-7035
• Main Authors: Parra, S., Guasaquillo, I., Enea, O., Mielczarski, E., Mielczarki, J., Albers, P., Kiwi-Minsker, L., Kiwi, J.
• Format: Article
• Language: English
• ISSN: 1520-6106; 1520-5207
• DOI: 10.1021/jp030045x

A novel C-Nafion/Fe-ion structured fabric capable of mediating Orange II decomposition in Fenton-immobilized photoassisted reactions is presented. The catalyst preparation requires the right balance between the amount of the Nafion necessary to protect the C-surface and the minimum encapsulation of the Fe-cluster catalytic sites inside the Nafion to allow the photocatalysis to proceed. The C-Nafion/Fe fabric can be used up to pH 10 under light to photocatalyze the disappearance of Orange II in the presence of H2O2. The photocatalysis mediated by the C-Nafion/Fe-ion fabric increased with the applied light intensity and reaction temperature in the reaction needing an activation energy of 9.8 kcal/mol. This indicates that ion− and radical−molecule reactions take place during Orange II disappearance. The build up and decomposition of intermediate iron complexes under light involves the recycling of Fe2+ and was detected by infrared spectroscopy (FTIR). This observation, along with other experimental results, allows us to suggest a surface mechanism for the dye degradation on the C-Nafion/Fe-ion fabrics. The C-Nafion/Fe-ion fabric in the presence of H2O2 under solar simulated light transforms the totally nonbiodegradable Orange II into a biocompatible material with a very high BOD5/COD value. X-ray photoelectron spectroscopy (XPS) and sputtering by Ar+-ions of the upper surface layer of the C-Nafion/Fe-ion fabric allow us to describe the intervention of the photocatalyst down to the molecular level. Most of the Fe clusters examined by transmission electron microscopy (TEM) showed particle sizes close to 4 nm due to their encapsulation into the Gierke cages of the Nafion thin film observed by scanning electron microscopy (SEM) and optical microscopy (OM).